CN101276665A - Rare earth magnet and manufacturing method thereof - Google Patents

Abstract

A structure of a magnet wherein a magnet consisting of a magnetic body including iron and rare earths, a plurality of fluorine compound layers or oxyfluorine compound layers are formed interior of the magnetic body, and the fluorine compound layer or oxyfluorine compound layer has a major axis which is greater than the mean particle size of the crystal grains of the magnetic body.

Description

Rare earth element magnet and manufacture method thereof

Technical field

The present invention relates to rare earth element magnet and manufacture method thereof, particularly reduce the use amount of heavy rare earth dvielement and have the magnet and the manufacture method thereof of high energy product or high-fire resistance.

Background technology

In recent years, in order to improve the characteristic of magnet, carried out developmental research for the structure of the rare earth element magnet that contains fluorine compounds or oxygen fluorine compounds.For example, in following patent documentation 1-5, announcing has the mixture that uses pulverous fluorine compounds or pulverous fluorine compounds and solvent, forms the technology of the phase that contains fluorine at magnet surface.

Patent documentation 1 spy opens the 2003-282312 communique

Patent documentation 2 spies open the 2006-303436 communique

Patent documentation 3 spies open the 2006-303435 communique

Patent documentation 4 spies open the 2006-303434 communique

Patent documentation 5 spies open the 2006-303433 communique

In the conventional art, in order in the NdFeB magnetic, to form the phase contain fluorine with stratiform, with the comminuted powder of fluorine compounds etc. as raw material, and not at the record of the state of solution.For this reason, for spread necessary heat treatment temperature high and under the temperature lower than sintered magnet magnetic characteristic can take place in the magnetic of deterioration, will be difficult to realize the raising of magnetic characteristic or the low concentration of rare earth element.

Among the above-mentioned patent documentation 1-5,, therefore be difficult to form the phase that contains fluorine effectively along the magnetic iron powder surface because used fluorine compounds are Powdered or the mixture of powder and solvent in handling.In addition, in the above-mentioned gimmick in the past, used fluorine compounds and magnetic surface are to contact in the processing, contain fluorine be not easy mutually carry out face with magnetic and contact, therefore need be in processing raw material more than the essential degree and the heat treatment under the high temperature.In addition, about not explanation of the iron in the fluorine compounds, there is not the record that contains of the iron in the relevant fluorine compounds.

Summary of the invention

The present invention is based on this kind problem and the invention that proposes, the processing gimmick of more simple and effective fluorine compounds compared with the past is provided and utilizes the formation of the magnet that this method realizes.

In order to address the above problem, using the fluorine compounds that do not contain comminuted powder and have a light transmission among the present invention is solution.By using this kind solution, form the fluorine compounds of tabular or stratiform at crystal boundary or intragranular, making these fluorine compounds is that the particle diameter of stratiform thing is grown greatlyyer than the average grain diameter of parent phase, thereby can realize two aspects of guaranteeing of the increase of coercive force and remanence simultaneously.

As the feature of solution, can enumerate and have light transmission, the fluorine compounds of solution can contact with the surface in the micro-crack, can unsetting wait the ferromagnetic powder surface surfacewise shape cover equably, can utilize coatings such as rotation coating machine on body material surface.In addition, the part of the fluorine compounds that solution is contained has and the different crystal structure of body material fluorine compounds, the half breadth broad that the peak had of X-ray diffraction spectrogram.

As the gimmick of fluorine compounds being made stratiform, can utilize the surface treatment of having used above-mentioned solution.Surface treatment is to contain more than one fluorine compounds or the local fluorine oxide (following note is made oxyfluoride) that the contains aerobic gimmick of coating the magnetic surface of alkali metal, alkali earths element or rare earth element.

In the treatment process of this magnet, have: be first operation of solution at coating fluorine compounds on the magnetic, heating magnetically body and remove second operation desolvate after this first operation.At this moment, be solution as fluorine compounds, use the solution that in alcoholic solvent, has disperseed the gel fluorine compounds.With this solution coat behind the magnetic surface, utilize and solvent to be removed from 200 ℃ to 400 ℃ heat treatment, utilize to make oxygen, rare earth element and fluorine compounds constitute element from 500 ℃ to 800 ℃ heat treatment fluorine compounds and magnetic, to spread.

In magnetic, contain 10 to 5000ppm oxygen, contain light element such as H, C, P, Si, Al or Mo, Cr, Ti, Nb, transition metals such as Cu, Sn as other impurity element.Oxygen contained in the magnetic not only exists as the oxide of light elements such as rare-earth oxide or Si, Al, and goes back the existence mutually as the oxygen that contains the composition that has departed from the chemical theory composition in parent phase or in the crystal boundary.Contain meeting of this kind oxygen and reduce the magnetization of magnetic, also influential to the shape of magnetization curve.Promptly, cause the reduction, the minimizing of coercive force, the increase of irreversible demagnetization rate, the increase of heat demagnetization, the change that plays magnetic characteristic, corrosion resistance deteriorations, mechanical property reduction etc. of rectangularity of minimizing, the demagnetization curve of reduction, the anisotropy field of the value of remanence, the reliability reduction of magnet.Because oxygen impacts a lot of characteristics like this, considered that therefore enforcement does not make it to residue in the operation in the magnetic.

Form under the situation of terres rares fluorine compounds on the magnetic surface, make REF ₃Perhaps REF ₂Growth (RE is a rare earth element) in the heat treatment below 400 ℃ is in vacuum degree 1 * 10 ^-4Below the Torr, from 500 to 800 ℃ of heating maintenances down.Retention time is 30 minutes.Utilize this heat treatment, the iron atom of magnetic or rare earth element, oxygen spread to fluorine compounds, thereby can be at REF ₃, REF ₂Perhaps see among the RE (OF) or near their crystal boundary.

By using above-mentioned treatment fluid, just can under from 200 to 800 ℃ lower temperature, make fluorine compounds magnetropism body diffusion inside, can obtain advantage as follows thus.1) can reduce necessary fluorine compounds amount in the processing.2) can form thin fluorine compound layer and thick tabular fluorine compounds on crystal boundary is the stratiform thing.3) under the tiny situation of the crystal grain of parent phase, can form stratiform or the tabular fluorine compounds bigger than the size of microcrystal of parent phase.4) can form tabular fluorine compounds discontinuously.5) owing to do not use powder, therefore reliability improves for the parts that require cleannes.6) with powder or use its slip to compare, can reduce heavy rare earth class use amount, control diffusion length easily, diffusion length is longer.Because these features, the effects such as raising of putting forward high and low lossization, mechanical strength of the raising of the rectangularity of the increase of remanence, coercive force increase, demagnetization curve, the raising of heat demagnetization characteristic, the raising that plays magnetic, anisotropic raising, corrosion resistance will be more obvious.

Feature as the magnet after the fluorine compounds processing has above-mentioned 2)～4).In the magnet of the present invention, form a plurality of (discontinuous) fluorine compound layer (or oxygen fluorine compound layer) in the inside of the magnetic that constitutes magnet.In addition, its feature is that also these fluorine compounds (or oxygen fluorine compounds) have the bigger major axis of average grain diameter than the crystal grain of magnetic.

Specifically, under the situation below the above 50nm of 10nm, the major axis of fluorine compound layer (or oxygen fluorine compound layer) will reach the following bigger size of ratio parent phase of the above 500nm of 50nm in the average grain diameter of the crystal grain of magnetic.In addition, fluorine compound layer (or oxygen fluorine compound layer) forms tabular elongated shape, and the ratio of major axis/minor axis reaches about 2～20.

And said here magnetic is under the situation of magnetic, and fluorine compound layer (or oxygen fluorine compound layer) is separated out to the inside of each magnetic, with the compression molding of this kind magnetic, constitutes magnet.

In addition, be under the situation of sintered magnet at magnetic, it is bigger that the average grain diameter of crystal grain can become, however even in such cases, fluorine compound layer (or oxygen fluorine compound layer) also can precipitate into the inside of sintered magnet.

At magnetic is under the situation of NdFeB system, and Nd, Fe, B or interpolation element, impurity element spread in fluorine compounds under the heating-up temperature more than 200 ℃.A part fluorine in addition under the temperature below 200 ℃, just begin the diffusion.Fluorine concentration under the said temperature in the fluorine compound layer is different and different along with the place, with stratiform or the tabular REF that forms discontinuously ₂, REF ₃(RE is a rare earth element) or their oxygen fluorine compounds.

In addition, parent phase crystal boundary at the periphery of these tabular fluorine compounds, can confirm that according to electron energy loss spectroscopy (EELS) fluorine compounds have thickness below 1/10 or the segregation of the fluorine atom below the 2nm, not necessarily segregation on whole crystal boundaries is continuously planted form thus and can be regarded as the layer that contains tabular fluorine compounds or oxygen fluorine compounds or fluorine and rare earth element discontinuous.

The part of fluorine atom also can be replaced with the boron or the iron atom of parent phase.The actuating force of diffusion is temperature, stress (distortion), concentration difference, defective etc., utilize the result after electron microscope etc. can be confirmed to spread, yet owing to can spread at low temperatures by the solution that uses the fluorine compounds comminuted powder, therefore the thickness of fluorine compounds becomes discontinuous easily as mentioned above like that, can reduce the use amount of fluorine compounds, in case for being made as high temperature then magnetic characteristic will deterioration the situation of NdFeB magnetic iron powder particularly effective.Though elements such as Nd in the fluorine compounds or B are not the elements that changes the magnetic characteristic of fluorine compounds significantly, yet, therefore can will be made as certain value as the magnetic characteristic of magnet by limiting its concentration because iron atom can change the magnetic characteristic of fluorine compounds because of its concentration.If the aggregate value of the element beyond the B is made as 100%, then be made as below the 50 atom %, just can keep the structure of fluorine compounds by concentration with iron, and when surpassing 50%, then can show with noncrystalline or iron phase, mix the little phase of coercive force as parent.So, the concentration of iron in the fluorine compounds need be made as below 50%.Above-mentioned NdFeB is in the magnetic, contains to comprise and Nd in principal phase ₂Fe ₁₄The magnetic of the phase that the crystal structure of B is equal also can contain transition metal such as Al, Co, Cu, Ti in above-mentioned principal phase.In addition, also the part of B can be made as C.In addition, beyond principal phase, also can contain Fe ₃B or Nd ₂Fe ₂₃B ₃Deng compound or oxide.Because to demonstrate than NdFeB under the temperature below 800 ℃ is the higher magnetic resistance of magnetic to fluorine compound layer, therefore utilize the formation of fluorine compound layer can increase the magnetic resistance of NdFeB sintered magnet, consequently, can reduce the loss.

In fluorine compound layer, except fluorine compounds, so long as little to magnetic characteristic influence, near room temperature, do not show ferromagnetic element, it is also no problem then to contain as impurity.For the purpose that forms high magnetic resistance, also can be in fluorine compounds the particulate of mixed nitride thing or carbide etc.Because as mentioned above, utilize solution-treated and heat treatment also can improve the magnetic characteristic that NdFeB is a sintered magnet, therefore go for electronic component-use magnet used among the HDD, be particularly suitable for the permanent magnet of voice coil motor or spindle drive motor.In addition, owing to carry out solution-treated, thereby can corresponding various pattern processing procedures or etching process, can realize the Local treatment of 10nm width, the diffusion length that begins from the surface of magnet can be controlled, depth direction magnetic characteristic control can be realized from surface 10nm to 100mm.Based on these situations, go for loud speaker, earphone, CD pick up light device, camera the lifting motor, focus on actuator, stepping motor, printer with actuator, accelerator, radiating light with in Medical Instruments, the micromachines etc. such as undulator, polarisation magnet, automobile electrical apparatus, MRI.

The application of the invention, the magnet that can realize having formed high reluctivity, hangs down coercive force, high magnetic flux density.In addition, by this magnet is applied in the rotating machinery, can realize low iron loss, high induction voltage, what go for comprising various rotating machineries is in the magnetic loop of feature with low iron loss.

Description of drawings

Fig. 1 is illustrated in the bright-field picture of the TEM that observes in the magnetic of the present invention cross section.

Fig. 2 is illustrated in the EDX analysis of measuring in the fluorine compound layer (1) that observes among Fig. 1.

Fig. 3 is illustrated in the bright-field picture of the TEM that observes in the magnetic of the present invention cross section.

Fig. 4 has represented to use the structure of the voice coil motor of magnet of the present invention.

Fig. 5 represents that near the TEM (TEM) of the crystal boundary in magnet cross section is as ((a): magnet of the present invention, (b) magnet in the past).

Fig. 6 is an example of the CONCENTRATION DISTRIBUTION in sintered magnet cross section.

Fig. 7 is an example of the CONCENTRATION DISTRIBUTION in sintered magnet cross section.

Fig. 8 is an example of the CONCENTRATION DISTRIBUTION in sintered magnet cross section.

Fig. 9 is an example of the CONCENTRATION DISTRIBUTION in sintered magnet cross section.

Figure 10 is an example of the CONCENTRATION DISTRIBUTION in sintered magnet cross section.

Figure 11 is an example of the CONCENTRATION DISTRIBUTION in sintered magnet cross section.

Wherein, 11 yokes, 12 sintered magnets, 13 moving coils, 14 copper pipes.

Embodiment

To describe being used to implement best mode of the present invention below.

＜embodiment 1 〉

As NdFeB is that powder is made with Nd ₂Fe ₁₄B is main chilling powder, forms fluorine compounds on their surface.Form DyF on chilling powder surface ₃Situation under, as raw material with Dy (CH ₃COO) ₃Use H ₂HF is added in the O dissolving.Utilize the interpolation of HF can form the DyF of gelatin-like ₃XH ₂O or DyF ₃X (CH ₃COO) (X is a positive number).With its centrifugation, remove and desolvate, mix with above-mentioned NdFeB powder as solution with light transmission.With the solvent evaporation of mixture, utilize heating that hydrate water is evaporated.Coverlay to formation like this utilizes XRD to study.Consequently, be to be lower than under 200 ℃ the temperature in heating-up temperature, the half breadth at X-ray diffraction peak is more than 2 times of peak width after thereafter the heat treatment, comprises wide peak.The half breadth at the peak that this is wide is more than 1 degree.Utilize the heat treatment than 200 ℃ of higher temperature sides, the crystal structure of fluorine compounds film changes, and distinguishes by DyF ₃, DyF ₂, formation such as DyOF.By with NdFeB be magnetic particle diameter from 1 to 300 μ m powder with the heat treatment temperature that reduces as magnetic characteristic less than temperature heating in anti-oxidation of 800 ℃, just can obtain having formed the magnetic of remanence more than 0.8T of high magneto-resistive layer on the surface.If particle diameter is less than 1 μ m, then oxidation easily, the easy deterioration of magnetic characteristic.In addition, under situation greater than 300 μ m, high magnetic resistanceization or as other the forming the magnetic characteristic that causes by fluorine compounds and improve effect and will diminish of effect.In the middle of the magnetic characteristic of magnetic, coercive force is about 10 to 20% from increasing because of from 600 to 800 ℃ heat treatment, is difficult to demagnetization.The magnetic characteristic of the magnetic of gained is, remanence is 0.8-1.0T, and coercive force is 10-20kOe, though the magnetic resistance of magnetic according to the thickness of the fluorine compounds that cover and difference, yet if the thickness more than the 50nm reaches M (1,000,000) Ω.

＜embodiment 2 〉

As NdFeB is that powder is made with Nd ₂Fe ₁₄B is main chilling powder, forms fluorine compounds on their surface.Form DyF on chilling powder surface ₃Situation under, as raw material with Dy (CH ₃COO) ₃Use H ₂HF is added in the O dissolving.Utilize the interpolation of HF can form the DyF of gelatin-like ₃XH ₂O.With its centrifugation, remove and desolvate.The terres rares fluoride concentration of gel state is at 10g/dm ³More than, optical path length is that the transmitance of 1cm is more than 5% under the wavelength of the 700nm of this treatment fluid.The solution that this kind is had light transmission mixes with above-mentioned NdFeB powder.With the solvent evaporation of mixture, utilize heating that hydrate water is evaporated.Distinguish and utilize 500 ℃ heat treatment, the crystal structure of fluorine compounds is by NdF ₃Structure, NdF ₂Formations such as structure.

Utilize the magnetic cross section after TEM is observed heat treatment.Bright-field is looked like to be shown among Fig. 1.The crystal particle diameter of parent phase is below 50nm, and its crystal orientation is at random basically.Can see the tabular crystal bigger than parent grain, as representing with the arrow of Fig. 1 (1), (2), form is different with parent phase.The long axis length of plate body (1) is about 250nm, and the major axis of the plate body of (2) is about 150nm, compares bigger with the particle (50nm is following) of parent phase.In plate body, can also see contrast, can think owing to the orientation difference of plate body, separated by crystal grain or formed contrast due to the distortion.(1), the plate body of (2) as shown in Figure 1, separated by the crystal grain of parent phase, and discontinuous, be not to be grown on whole crystal boundaries of parent phase.

The length of the minor axis of plate body is about 20-50nm, becomes thickness equal with the crystal grain of parent phase or below it.The axial ratio of the major axis/minor axis of plate body is 2 to 20, both has been present in magnetic central authorities, also grows in the parent grain in the parent phase crystal boundary.Surround plate body ground and can see contrast, illustrate between plate body and parent phase to have lattice deformability.This plate body is to coat fluorine that the fluorine compounds in the outside of magnetic spread in the crystal boundary of parent phase because of heat treatment, rare earth element etc. to form with the reaction of part parent phase.

Like this, being characterised in that in the present embodiment, is the plate body that the inside of magnetic forms fluorine compound layer at NdFeB, and this plate body is to compare bigger size with the average grain diameter of the crystal grain of parent phase.

To the EDX explosion views that the place (diameter 10nm) of Fig. 1 (1) is measured be shown among Fig. 2.

Can see fluorine (F), neodymium (Nd), iron (Fe) and molybdenum (Mo) as the peak of EDX.Mo uses in the sample web of electron microscope, and is irrelevant with magnetic.Peak from sample is F, Nd, three kinds of elements of Fe.Wherein, the element that just always exists before the coating procedure in parent phase is Nd and Fe.The ratio of Fe: Nd: F is 14: 15: 71.To rare earth element: the ratio of fluorine has carried out various evaluations, and the result is 1: 1 to 1: 7 a scope.

In addition, see the situation at the peak of oxygen or carbon in addition in comprising the EDX explosion views of fluorine, the plate body of (1) or (2) can be thought to be made of F, Nd, Dy, Fe, C, O.And B can't utilize EDX to detect, though the reason of not knowing, a part spreads and exists with fluorine, also is not inconceivable.(1) or the plate body of (2) be certain of fluorine compounds or oxygen fluorine compounds, oxygen fluorocarbons, yet mainly be fluorine compounds or the local oxygen fluorine compounds that contain fluorine that the part contains aerobic.Compare above-mentioned plate body with Dy and contain more Nd, yet be used to form in the part of the evolving path of plate body, compare with plate body and contain more Dy.Can infer according to this kind result, the CONCENTRATION DISTRIBUTION of the rare earth element of the evolving path of plate body or plate body, oxygen and fluorine helps coercive force to increase.Promptly, Dy or the segregation of Nd, the Nd of plate body or the segregation of Dy and fluorine of utilization in the evolving path that has formed plate body, the minimizing that the lattice match raising of the increase of anisotropy energy, crystal boundary, fluorine help the magnetic moment of the raising of magnetic characteristic, near the crystal boundary NdFeB or crystal boundary to rise and fall to the reduction of parent phase.

＜embodiment 3 〉

The formation treatment fluid of terres rares fluoride or alkaline-earth metal fluoride coat film is after acetic acid terres rares or acetic acid alkaline-earth metal is water-soluble, adds the hydrofluoric acid that has diluted at leisure.Use the ultrasonic stirring device that the fluorine compounds that generated gelatinous precipitate or the solution of oxygen fluorine compounds or oxygen fluorine carbide are stirred, after the centrifugation, add methyl alcohol, after gelatinous methanol solution is stirred, remove anion and its transparence.Anion removed to treatment fluid transmitance under visible light reach more than 5%.This solution is coated on the magnetic, removes and desolvate.As NdFeB is that powder is made with Nd ₂Fe ₁₄B is the chilling powder of main structure, forms the Dy fluorine compounds on their surface.With the solution that has light transmission as described above with after above-mentioned NdFeB powder mixes, with the solvent evaporation of compound.Utilize 200～700 ℃ heat treatment and the chilling after the heat treatment, the crystal structure of fluorine compounds film becomes NdF ₃Structure, NdF ₂Structure etc.Utilize TEM to observe the magnetic cross section after the heat treatment.Bright-field is looked like to be shown among Fig. 3.In the bright-field picture, can see the tabular or lamina of white.The crystal particle diameter of parent phase is below 50nm, and the major axis of plate body is compared longer plate body with parent grain a lot, and minor axis length is and length below the parent grain equal extent.In addition, plate body and a plurality of parent grain are grown contiguously, and long axis direction is at random basically.Show that under the bright-field picture F (fluorine) and Nd (neodymium) divide exploring.The observation place is a bright-field, and the branch exploring of F, Nd all is identical place.The plate body that appears as white in the bright-field picture divides exploring as can be known from following F, Nd, is the high place of concentration of F and Nd.According to this result as can be known, plate body contains rare earth element and fluorine.Observed limits vision electron ray diffraction image, the result has the essential structure of terres rares fluorine compounds.Though its structure is with NdF ₂, NdF ₃Be essential structure, yet partly contain aerobic, thereby also might become the oxygen fluorine compounds.Only treatment fluid has been carried out heat treatment, it is configured to NdF as a result ₃Structure, the fluorine concentration of plate body is compared with the fluorine compounds of only being made by treatment fluid, and its fluorine concentration is lower.This explanation, in the heat treatment process after surface treatment, the fluorine compounds of magnetic periphery and magnetic reaction, the fluorine atom of periphery moves with the terres rares atom.Can infer according to The above results, the CONCENTRATION DISTRIBUTION of the rare earth element of the evolving path of plate body or plate body, oxygen and fluorine helps coercive force to increase.That is, utilize Dy or the segregation of Nd, the Nd of plate body or the segregation of Dy and fluorine in the evolving path that has formed plate body, the lattice match raising of the increase of anisotropy energy, crystal boundary, fluorine help the raising of magnetic characteristic to the reduction of parent phase.This kind can obtain that the raising of raising, the rectangularity of coercive force, the magnetic resistance after being shaped increase, the fluorine compounds of some effect of the raising of the cementability of the increase of the increase of the raising of the temperature dependent reduction of the temperature dependent reduction of coercive force, remanence, corrosion resistance, mechanical strength, heat conductivity, magnet are except DyF ₃In addition, also have LiF, MgF ₂, CaF ₂, ScF ₃, VF ₂, VF ₃, CrF ₂, CrF ₃, MnF ₂, MnF ₃, FeF ₂, FeF ₃, CoF ₂, CoF ₃, CuF ₂, CuF ₃, NiF ₂, ZnF ₂, AlF ₃, GaF ₃, SrF ₂, YF ₃, ZrF ₃, NdF ₃, AgF, InF ₃, SnF ₂, SnF ₄, BaF ₂, LaF ₂, LaF ₃, CeF ₂, CeF ₃, PrF ₂, PrF ₃, NdF ₂, SmF ₂, SmF ₃, EuF ₂, EuF ₃, GdF ₃, TbF ₃, TbF ₄, DyF ₂, NdF ₃, HoF ₂, HoF ₃, ErF ₂, ErF ₃, TmF ₂, TmF ₃, YbF ₃, YbF ₂, LuF ₂, LuF ₃, PbF ₂, BiF ₃Perhaps in these fluorine compounds, contain aerobic or carbon compound, the surface treatment of the solution that can utilize the solution that used the permeability with luminous ray or the part of CH base and fluorine is combined forms, and can see tabular fluorine compounds or oxygen fluorine compounds at crystal boundary or intragranular.For the fluorine compounds of having confirmed in the middle of them that magnetic characteristic improves, its structure summary sheet is shown in Table 1.

[table 1]

Table 1

Gd	GdF 3	NdF 3	NdF 2	NdOF	GdOF
						Tb	TbF 3	NdF 3	NdF 2	NdOF	TbOF
Dy	DyF 3	NdF 3	NdF 2	NdOF	DyOF
						Ho	HoF 3	NdF 3	NdF 2	NdOF	HoOF
Er	ErF 3	NdF 3	NdF 2	NdOF	ErOF
						Tm	TmF 3	NdF 3	NdF 2	NdOF	TmOF
Yb	YbF 2，YbF 2.37	NdF 3	NdF 2	NdOF	YbOF
						Lu	LuF 3	NdF 3	NdF 2	NdOF	LuOF

Except NdF ₂Structure and NdF ₃Beyond the structure, terres rares oxygen fluorine compounds and the oxygen fluorine compounds that constitute by the constituent of each treatment fluid have also been confirmed.Utilize auger analysis, in material, can see fluorine light element in addition sometimes, but to demagnetization curve not influence basically.In addition, even on the crystal boundary of part, the transition metal segregation is arranged, also can confirm the raising effect of above-mentioned magnetic characteristic.

＜embodiment 4 〉

At NdFeB is the surface coated gel of sintered magnet or the terres rares fluorine compounds solution with light transmission of colloidal sol shape.The thickness of the terres rares fluorine compounds after the coating is 1～10000nm.NdFeB is that sintered magnet is with Nd ₂Fe ₁₄B is the sintered magnet of principal phase, and the deterioration of the magnetic characteristic that is accompanied by processing grinding or oxidation generation can be seen in the surface of sintered magnet.In order to improve this kind magnetic characteristic deterioration, after will coating sintered magnet surface and drying, heat-treating under the temperature below the sintering temperature more than 500 ℃ through the terres rares fluorine compounds of luminous ray.The coating drying after soon, go out particle more than the following 1nm of 50nm from gel or colloidal sol shape terres rares fluorine compounds growth from solution, structure around the fluorine atom in the solution changes, become periodic structure by random configuration, and then, produce and the crystal boundary of sintered magnet or the reaction or the diffusion on surface by heating.The sintered magnet surface roughly form fluorine compounds comprehensively, before heating under the temperature more than 500 ℃, at the grain surface of the part on sintered magnet surface, the part of the part that rare earth element concentration is high is fluoridized in the dry back of coating.In the above-mentioned terres rares fluorine compounds, Dy, the Tb of their formation element of the conduct of Dy fluorine compounds or Tb, Ho fluorine compounds, Ho etc. spread along crystal boundary, thereby the deterioration of magnetic characteristic is improved, and the rectangularity of demagnetization curve improves.When heat treatment temperature reached more than 800 ℃, the mutual diffusion of fluorine compounds and sintered magnet further advanced, and can see Fe with the concentration more than the 10ppm in fluorine compound layer.Heat treatment temperature is high more, and then parent phase constitutes the tendency that the concentration of element in fluorine compound layer just has increase more.Under the situation that sintered magnet is bonding stackedly, to become with the fluorine compounds or the oxygen fluorine compounds that have improved the identical or different adhesive linkage of the fluorine compounds of magnetic characteristic because of diffusion after above-mentioned heat treatment, be coated with, stacked, by carrying out millimeter-wave irradiation, just only near the caking layer and sintered magnet is bonding.Fluorine compounds as adhesive linkage are (NdF such as Nd fluorine compounds _{2 -3}, Nd (OF) _1-3), by selecting the illuminate condition of millimeter wave, just can be in the temperature rising that suppresses sintering magnetic blow out centre portion, only optionally near the caking layer, thereby can suppress to be accompanied by the magnetic characteristic deterioration or the change in size of the sintered magnet of bonding generation.In addition, by using millimeter wave, the heat treatment time of selecting heating can be become below half of in the past heat treatment time, thereby be applicable to the mass production that can side by side improve magnetic characteristic with bonding process.Millimeter wave not only can be used for the bonding of sintered magnet, can also be used for the magnetic characteristic that the diffusion by coating material causes and improve, can realize by except fluorine compounds, also using oxide or dielectric losses such as nitride, the carbide material different with the NdFeB of parent phase as the function of adhesive linkage.Even, also can utilize heating to make it diffusion though do not use millimeter wave, by using millimeter wave like this fluorine compounds portion is optionally heated, just can be used for bonding, the joint of magnetic material and various metal material or oxide material.As the example of the condition of millimeter wave, at 28GHz, 1-10kW, Ar, N ₂Shone 1-30 minute in the atmosphere or in the vacuum or in other the inert atmosphere.Because by using millimeter wave, fluorine compounds or the fluorine compounds that contain aerobic are selectively heated, therefore just can not change the tissue of sintered body itself basically, and fluorine compounds are spread along crystal boundary, can prevent that fluorine compounds from constituting the diffusion of element to crystal grain inside, compare with the situation of merely heating, can obtain higher magnetic characteristic (high remanence, rectangularity improves, high coercive force, high-curie temperature, the low-heat demagnetization, highly corrosion resistant, high magnetic resistanceization, high strength, certain of low-thermal-expansion etc.), utilize the selection of millimeter wave condition and fluorine compounds, with common heat treatment phase ratio, can be with the formation element of fluorine compounds from the diffusion into the surface of sintered magnet to darker part, even can diffuse to the magnetic blow out centre portion of 10 * 10 * 10cm.What utilize that this kind gimmick obtains is that the magnetic characteristic of the sintered magnet that constitutes of 1～30 μ m is by crystal particle diameter, remanence is 1.0 to 1.6T, coercive force is 20～50kOe, and having heavy rare earth dvielement concentration contained in the rare-earth sintered magnet of equal magnetic characteristic, can to add NdFeB than in the past use heavy rare earth class be that the situation of magnetic is lower.In addition, if at least a fluorine compounds that contain alkali, alkali earths or rare earth element or oxygen fluorine compounds at sintered magnet remained on surface 1～100nm, then the magnetic resistance on sintered magnet surface uprises, even stackedly bondingly also can reduce the vortex flow loss, can realize that the loss in the high frequency magnetic field reduces.Owing to utilize this kind loss to reduce, can reduce the heating of magnet, therefore can reduce the use amount of heavy rare earth dvielement.Because utilizing fluorine compounds like this is solution-treated and the heat treatment that is right after thereafter, just can improve the characteristic of sintered magnet, can also reduce the use amount of heavy rare earth dvielement, therefore goes for whole application products of sintered magnet.Solutions employed can be guaranteed its part in the processing from the process that the circulation of sintered magnet is reclaimed, and also can extract from the process of the purification of Nd.Owing to carry out the diffusion of fluorine or heavy rare earth dvielement, therefore can promote the viscosity of solution reduction, activation fluorine atom increase, the structure optimization around the fluorine atom, the control of ionic bond, ionic composition the concentration management, handle atmosphere control, impurity component reduces, and can realize the continuous process that the manufacturing of full automatic treatment liquid, processing, thickness management, heat treatment, magnetic characteristic are estimated.By utilizing heat treatment the formation element in the solution is spread in sintered magnet, can improve the processing deterioration of sintered magnet, even under the situation of processing once more, can reduce the processing deterioration with comparing before the heat treatment also, even, also can only utilize heat treatments such as not having the surface-treated localized heating to recover magnetic characteristic waiting because of processing under the situation of deterioration slightly.By suitably selecting to constitute the fluorine of solution and other element, using this kind Solution Diffusion to handle and not only going for NdFeB is that sintered magnet, SmCo are sintered magnet or other magnet, can also be applicable to Fe system, FeCo system, the whole magnetic materials with crystal boundary such as oxide based, in purpose is not to be to improve magnetic characteristic, but increase resistance, improve intensity, improve corrosion resistance, improve under the situation of purposes such as character of optics, go for having in all the body materials, film, microparticle material at crystal boundary or interface.Because above-mentioned terres rares fluorine compounds are not powdery, viscosity is low, therefore can coat 1nm in the small hole of 100nm, so go for the raising of the magnetic characteristic of small magnet component, this magnet goes for commutating in the permanent magnet motor, disc type armature direct current machine, flat motor (flat motor), voice coil motor, stepping motor, Can-Stack motor, magnetic sensor, actuator, magnetic bearing etc. of type or brushless type.In addition, used Treatment Solution can also be used as various magnetic fluids by mixing with magnetic particle in the coating magnet that is applicable to coated media or arbitrary shape in the fluorine compounds processing.And near this magnet of fluorine segregation crystal boundary can form the diaphragm of resin, metal etc. according to purposes on the surface, can further improve reliability.

＜embodiment 5 〉

To the Fe that adds in the fluorine compounds solution that under visible light, has permeability more than the 1 atom %, make the gel or the colloidal sol shape Fe-fluorine compounds of bunch (cluster) that mixed Fe ion or Fe.This moment the Fe atom a part and fluorine compounds fluorine or combine with constituting element chemistry more than any one of alkali, alkali earths, Cr, Mn, V or rare earth element of fluorine compounds.By fluorine compounds or fluorine compounds presoma irradiation millimeter wave or microwave to this kind gel or colloidal sol shape, the chemically combined atom of more than one of participation fluorine atom and Fe atom and above-mentioned fluorine compounds formation element becomes many, formation is made of the fluorine compounds more than more than one ternary systems of forming of element Fe fluorine and above-mentioned fluorine compounds, utilize millimeter-wave irradiation, can synthesize the fluorine compounds of coercive force more than 10kOe.As a part or the substitute of Fe ion, also can add other transition metal ion.Utilize this kind gimmick, can as in the past, be used to obtain the dissolving, crushing process of Magnaglo and obtain ferromagnetic material, go in the various magnetic loops.When alkali, alkali earths, Cr, Mn, V or rare earth element with above-mentioned formation fluorine compounds are made as M, then because Fe-M-F is, Co-M-F is, the Ni-M-F based magnet can use gel or colloidal sol shape or solution shape fluorine compounds to obtain the high coercive force magnet of gel or collosol state, can be by coating on the various substrates that are difficult to dissolve because of millimeter-wave irradiation, and carry out millimeter-wave irradiation and make, therefore go for being difficult to carrying out in the magnet component of shape of machining.The structure of fluorine atom or M atom and composition are relevant with the coercive force of these materials, heat by using gel or colloidal sol, just can make the magnetic particle of nano particle state, and the fluorine in the nano particle or the segregation of M atom are relevant with high coercive force.Also have can obtain coercive force more than the 5kOe, the magnet of the characteristic of remanence more than 0.5T.And, even in this kind fluorine compounds magnet, sneak into atoms such as oxygen, carbon, nitrogen, boron, also seldom for the influence of magnetic characteristic.Can also utilize this kind material system to obtain to show the material of the characteristics of luminescence, can be used as the magneto-optical material is applied in optomagnetic purposes element etc., can make permanent magnet with the high coercive force material that contains 0.1% to 80% fluorine, go in optical element etc. with visible light permeability.The magnet that particularly contains the fluorine more than 10% is the material that shows permeability under specific wavelength, can make the material that contains 15% to 80% fluorine as the magnet of the permeability with visible light.

＜embodiment 6 〉

At the SmFeN of particle diameter 0.1～100 μ m is the fluorine compounds solution of the surface coated of magnetic through visible light.Fluorine compounds are compounds of the alkali, alkali earths or the rare earth element that contain more than one at least.With applied SmFeN is that magnetic inserts in the mould, with magnetic compression molding in the magnetic direction orientation, makes interim formed body in the magnetic field of 3-20kOe.Utilize millimeter-wave irradiation to heat and have anisotropic interim formed body, fluorine compounds are implemented the selectivity heating.Can suppress to be accompanied by that to add the SmFeN that pines for be the magnetic characteristic deterioration that the structure variation etc. of magnetic produces, fluorine compounds become adhesive, can make anisotropic magnet, can obtain the magnet that the SmFeN magnetic has been bondd with fluorine compounds.Be made as 0.1-3% by the volume that fluorine compounds are shared, just can obtain the SmFeN anisotropic magnet of remanence more than 1.0T.By form back dipping fluorine compounds liquid at interim formed body, heat-treating thereafter, just can improve magnetic characteristic.Though form Sm-Fe-N-F or Sm-Fe-N-O in the part, the reaction of utilization and fluorine compounds can be confirmed some effect that coercive force increases, rectangularity improves, remanence increases.At nitrogen such as SmFeN systems is under the situation of magnetic, is magnetic by making SmFeN to SmFe powder irradiation millimeter wave, compares with situations such as ammoniacal liquor nitrogenize in the past, and the increase of the coercive force due to the nitrogenize is more obvious, can obtain the above coercive force of 20kOe.Use millimeter wave and the way of its bonding can also be applicable to SmFeCo system as other ferrous material, Fe-Si system, Fe-C system, FeNi system, FeCo system, Fe-Si-B system or as in the SmCo system of Co magnetic material, CoFeSiB system, CoNiFe system, the AlCoNi system with fluorine compounds, can be applicable in soft magnetism powder, soft magnetic thin strip, soft magnetic compact, hard magnetic powder, hard magnetic strip, the hard magnetic formed body with not damaging magnetic characteristic, can also realize other metal based material bonding.

＜embodiment 7 〉

Add the particulate that contains the Fe more than the 1 atom % of particle diameter 1～100nm in seeing through the fluorine compounds solution of visible light, it is the gel or the colloidal sol shape Fe-fluorine compounds of particulate that making has mixed Fe.This moment microparticle surfaces the fluorine of a part and fluorine compounds of Fe atom or any one above element chemistry of alkali, alkali earths or the rare earth element of formation fluorine compounds combine.By fluorine compounds or fluorine compounds presoma irradiation millimeter wave or microwave to gel that contains this kind particulate or colloidal sol shape, the chemically combined atom of more than one of participation fluorine atom and Fe atom and above-mentioned fluorine compounds formation element becomes many, formation is made of the fluorine compounds more than more than one ternary systems of forming of element Fe fluorine and above-mentioned fluorine compounds, utilize millimeter wave or microwave irradiation can synthesize the fluorine compounds of coercive force more than 10kOe.Also can replace Fe and be particulate and add other transition metal particulate.Utilize this kind gimmick, just can as in the past, be used to obtain the dissolving, crushing process of Magnaglo and obtain ferromagnetic material, go in the various magnetic loops.When alkali, alkali earths or rare earth element with above-mentioned formation fluorine compounds are made as M, then because Fe-M-F is, Co-M-F is, the Ni-M-F based magnet can use to the comb of gel or colloidal sol shape or solution shape fluorine compounds interpolation particulate and send out the high coercive force magnet of acquisition, can be by coating on the various substrates and carry out millimeter-wave irradiation and make, therefore go for being difficult to carrying out in the magnet component of shape of machining.And, even in this kind fluorine compounds magnet, sneak into atoms such as oxygen, carbon, nitrogen, also seldom for the influence of magnetic characteristic.Insert above-mentioned fluorine compounds to use resist etc. to carry out the shape that pattern handles, heat-treating below the heat resisting temperature at resist after the drying with light transmission.If heat after removing resist in addition, then coercive force will increase again.Can inject in the space more than the 10nm, more than the thickness 1nm of magnet portion at interval or be coated with above-mentioned colloidal sol shape or gel fluorine compounds to resist, can carry out machining to the magnet of 3D shape, and do not use the gimmick of physics such as evaporation, sputter, and produce small-sized magnet.This kind Fe-M-F based magnet can pass through to adjust the concentration of F, and only absorbs the light of certain wavelengths.So this kind fluorine compounds can be used as the finish materials of parts such as optics or optical recorder or these parts and use.

＜embodiment 8 〉

In the fluorine compounds of permeability, add the particle of the rare earth element of containing of particle diameter 10～10000nm more than at least a with visible light.As a particle of particle, use with Nd ₂Fe ₁₄The particle that is configured to principal phase of B is coated above-mentioned particle surface with fluorine compounds.Be made as parameter by mixing ratio or coating condition with fluorine compounds solution and particle, just can change the coverage rate of particle surface, in coverage rate is to confirm that the coercive force due to the fluorine compounds increased effect at 1～10% o'clock, increasing effect except coercive force at 10～50% o'clock, the rectangularity that can also see demagnetization curve improves or Hk (magnetic field on the demagnetization curve during 90% remanence) increases (absolute value of magnetic field value increases), and the magnetic resistance after coverage rate is can confirm to be shaped in 50～100% o'clock increases in addition.Here said coverage rate is meant that the area of covering of the material that is coated with is with respect to the value of the surface area of particle.By use coverage rate be 1～10% particle in magnetic field after interim the shaping, heating is shaped under the temperature more than 800 ℃, just can obtain sintered magnet.The fluorine compounds that cover are the fluorine compounds that contain more than one rare earth elements at least.Owing to use the solution fluorine compounds, therefore can be along the interface of particle with stratiform or tabular coating fluorine compounds, even in particle, have concavo-convexly, also can be coated with stratiform along its surperficial shape.Coverage rate is the heat treatment after because of interim shaping the in the magnetic field of 1～10% particle, spreads along crystal boundary as the rare earth element of the part of stratiform fluorine compounds, and coercive force is compared increase with the situation that not have covering.And, be on the particle time when fluorine compounds being coated Fe, then there is not the part of the particle surface of coating material promptly to fluoridize.So, in coverage rate is 1～10% particle, be 1～10% even be formed with the area of the part of fluorine compounds, though 90% particle surface depends on the composition or the surface state of particle, but also can fluoridize, the magnetic characteristic at interface changes, and the magnetic resistance of particle surface increases.Because rare earth element is fluoridized easily, therefore after the such particle surface of the material that the terres rares concentration of particle surface is high was coated with gel or colloidal sol shape fluorine compounds, promptly fluoridized the part, and the magnetic resistance of particle surface uprises.When with the particles sintering of the high magnetic resistance of this kind, then the rare earth element of intragranular just combines with the fluorine of particle surface, become rare earth element near crystal boundary segregation structure, coercive force increases.That is, fluorine can be brought into play the capture effect of terres rares atom, and by suppressing the intragranular diffusion of rare earth element, rare earth element is segregation on crystal boundary, and coercive force increases, and intragranular rare earth element concentration is lowered, and can obtain high remanence.

＜embodiment 9 〉

In the fluorine compounds solution of permeability, add the particle of the rare earth element of containing of particle diameter 10～10000nm more than at least a with visible light.As a particle of particle, use with Nd ₂Fe ₁₄The particle that is configured to principal phase of B or become small magnet or heat treatment after become the powder of small magnet, fluorine compounds contact with the surface of above-mentioned particle or powder, the fluorine compounds coating solution that utilizes solvent etc. will be attached to the surface is removed.At the not residual as far as possible fluorine compounds that condensed of particle surface, the residual quantity of coating material is made as average coverage rate below 10%.So, average particle area more than 90% becomes the face (utilizing scanning electron microscopy can't see the fluorine compounds clearly that are coated with for 10,000 times) that does not form coating material, yet the part of the rare earth element of constituent particle is fluoridized in the part of this face, becomes the more layer of fluorine.It is because rare earth element combines with fluorine atom easily that the part of particle surface is fluoridized like this, is not having under the situation of rare earth element, is difficult to cause fluoridizing of surface.Under the situation that the part of rare earth element is fluoridized, owing to also combine with oxygen atom easily, therefore also have the situation that forms the oxygen fluorine compounds, constitute mutually by rare earth element in particle surface formation with the fluorine combination.Particle compression molding in magnetic field of using this kind to fluoridize is produced the anisotropy sintered magnet with its sintering thereafter.Can be that the interim formed body of 50～90% scope floods above-mentioned fluorine compounds solution also to the density after the compression molding in the magnetic field, use the presoma of fluorine compounds to cover the part on particle surface and particle crackle portion surface, utilize this kind impregnation process can comprise partially the fluorine compounds of 1～100nm being covered of crackle portion, help to realize some effect such as anisotropic additional of raising, the magnetic of minimizing, the intensity of reduction, the terres rares use amount of the increase of coercive force, the raising of rectangularity, high magnetic resistanceization, remanence.When sintering, can be attended by the diffusion of fluorine and rare earth element.Compare with the situation of not fluoridizing, the addition of heavy rare earth dvielement is many more, and the coercive force due to then fluoridizing increases just more for obvious.Can utilize and fluoridize the concentration that reduces for the necessary heavy rare earth dvielement of the sintered magnet that obtains identical coercive force.This can think that the heavy rare earth dvielement is near segregation fluoridizing mutually easily owing to utilize and to fluoridize, therefore produce the heavy rare earth dvielement near crystal boundary segregation structure, so form high coercive force.The scope of this kind heavy rare earth dvielement institute segregation is from the about 1～100nm of crystal boundary.

＜embodiment 10 〉

Use has the fluorine compounds solution coat of permeability of visible light on the oxide particle of the particle diameter 1～10000nm that contains more than one rare earth elements at least, heating or implement to utilize the heating of millimeter-wave irradiation in 800～1200 ℃ temperature range.Utilize heating to form the oxygen fluorine compounds partly.By use the solution that contains more than one rare earth elements at least as fluorine compounds solution, just can utilize the formation of oxygen fluorine compounds or fluorine compounds, improvement is as the magnetic characteristic of the barium ferrite or the ferrous acid strontium particle of oxide, can confirm the raising, the raising of remanence of rectangularity of raising, the demagnetization curve of coercive force.Particularly contain the fluorine compounds solution of the iron more than 1% by use, the increase effect of remanence is very big.Also can use sol gel process to make the oxide particle of above-mentioned oxygen fluorine compounds.

＜embodiment 11 〉

In fluorine compounds solution, add Co or Ni more than the 1 atom % with light transmission, make mixed Co, Ni ion or Co, Ni bunch gel or colloidal sol shape Co or Ni-fluorine compounds solution.This moment Co or Ni atom a part and fluorine compounds fluorine element or combine with constituting element chemistry more than any one of alkali, alkali earths or rare earth element of fluorine compounds.By fluorine compounds or fluorine compounds presoma irradiation millimeter wave or the microwave that has light transmission to this kind, the chemically combined atom of more than one of participation fluorine atom and Co or Ni atom and above-mentioned fluorine compounds formation element becomes many, formation is made of the fluorine compounds more than more than one ternary systems of forming of element Co or Ni fluorine and above-mentioned fluorine compounds, utilize millimeter-wave irradiation can synthesize the fluorine compounds of coercive force more than 10kOe.The transition metal ion that also can add other as a part or the substituent of Co or Ni ion.Utilize this kind gimmick, can as in the past, be used to obtain the dissolving, crushing process of Magnaglo and obtain ferromagnetic material, go in the various magnetic loops.When alkali, alkali earths or rare earth element with above-mentioned formation fluorine compounds are made as M, then because Co-M-F is, Co-M-F is, the Ni-M-F based magnet can use the solution shape fluorine compounds with light transmission to obtain high coercive force magnet or ferromagnetic powder, can be by coating on the various substrates that are difficult to dissolve and carry out millimeter-wave irradiation and make because of millimeter-wave irradiation, therefore go for being difficult to carrying out in the magnet component of shape of machining.And, even in this kind fluorine compounds magnet, sneak into atoms such as oxygen, carbon, nitrogen, also seldom for the influence of magnetic characteristic.

＜embodiment 12 〉

To the fluorine compounds that show permeability under visible light is the particulate that contains the Fe more than the 1 atom % that adds particle diameter 1～100nm in the solution, and it is the Fe-fluorine compounds of particulate that making has mixed Fe.This moment microparticle surfaces the Fe atom a part and fluorine compounds fluorine or combine with constituting element chemistry more than any one of alkali, alkali earths or rare earth element of fluorine compounds.By contain to this kind particulate or bunch low viscosity and the fluorine compounds of light transmission or fluorine compounds presoma irradiation millimeter wave or microwave, the chemically combined atom of more than one of participation fluorine atom and Fe atom and above-mentioned fluorine compounds formation element becomes many, Fe atom and rare earth element be by fluorine atom and combination, utilizes combining of fluorine atom and oxygen atom and Fe and rare earth element; Certain combination that perhaps utilizes rare earth element to combine with fluorine atom, oxygen atom and Fe atom, the magnetized part between the Fe atom becomes ferromagnetism.In addition, the magnetization of Yi Bufen Fe atom forms anti-ferromagnetic combination.Utilize millimeter wave or microwave irradiation to produce ferromagnetism, can synthesize the fluorine compounds that contain Fe of coercive force more than 10kOe in conjunction with favourable structure.Also can replace Fe and be particulate and add other transition metal particulate.That is, in the transition metals such as Cr, the Mn beyond Co, the Ni, V, also can utilize this kind gimmick, need not as in the past, be used to obtain the dissolving, crushing process of Magnaglo and obtain permanent magnet, go in the various magnetic loops.

＜embodiment 13 〉

Fluorine compounds to light transmission are the particulate that contains the Fe more than the 1 atom % that adds particle diameter 1～100nm in the solution, and it is the Fe-fluorine compounds of particulate that making has mixed Fe.This moment microparticle surfaces the Fe atom a part and fluorine compounds fluorine or combine with constituting element chemistry more than any one of alkali, alkali earths or rare earth element of fluorine compounds.By contain to this kind particulate or bunch low viscous fluorine compounds or fluorine compounds presoma irradiation millimeter wave or microwave, the chemically combined atom of more than one of participation fluorine atom and Fe atom and above-mentioned fluorine compounds formation element becomes many, Fe atom and rare earth element be by fluorine atom and combination, utilizes combining of fluorine atom and oxygen atom and Fe and rare earth element; Certain combination that perhaps utilizes rare earth element to combine with fluorine atom, oxygen atom and Fe atom, the magnetized part between the Fe atom becomes ferromagnetism, thereby has magnetic anisotropy.Because of in particulate, forming more phase (fluorine is 10～50%) mutually (Fe be 50～85%) and the rare earth element more phase (rare earth element be 20～75%) more of fluorine with Fe, the more layer of Fe will be responsible for magnetization, and the more phase of phase that fluorine is more or rare earth element then helps high coercive force.In addition, the magnetization of Yi Bufen Fe atom forms anti-ferromagnetic combination.Utilize millimeter wave or microwave irradiation to produce ferromagnetism, can synthesize the fluorine compounds of coercive force more than 10kOe in conjunction with favourable structure.Also can replace Fe and be particulate and add other transition metal particulate.Utilize this kind gimmick, can as in the past, be used to obtain the dissolving, crushing process of Magnaglo and obtained permanent magnet, can also realize the high energy productization that surface fluorination compound solution-treated and heat treatment by the ferrite ferromagnetic powder are produced, go in the various magnetic loops.

＜embodiment 14 〉

With Nd ₂Fe ₁₄B is that the NdFeB of principal phase is the terres rares fluorine compounds that the surface coated of sintered magnet has light transmission.The average film thickness of the terres rares fluorine compounds after the coating is 1～10000nm.NdFeB is the crystal particle diameter average out to 1-20 μ m of sintered magnet, is with Nd ₂Fe ₁₄B is the sintered magnet of principal phase, and the deterioration that is accompanied by the magnetic characteristic of processing or grinding and producing on the surface of sintered magnet can be seen on demagnetization curve.In order to improve this kind magnetic characteristic deterioration, increase is by the coercive force due near the rare earth element segregation the crystal boundary, improve the rectangularity of demagnetization curve, realize near the high magnetic resistanceization that magnet surface or crystal boundary are, the high-Curie-pointization that realization is brought by fluorine compounds, high strength, highly corrosion resistantization reduce the terres rares use amount, reduce magnetize magnetic field etc., with terres rares fluorine compounds solution coat after sintered magnet surface and drying, heat-treating under the temperature below the sintering temperature more than 500 ℃.After the coating drying, soon, bunch grow up to particle more than the following 1nm of 100nm from what terres rares fluorine compounds growth from solution went out, and then, produce and the crystal boundary of sintered magnet or the reaction or the diffusion on surface by heating.Be coated with dried fluorine compounds bunch owing to, therefore can not become surface, when observing particle, can't see the approximate ellipsoidal that has fillet or circular bunch with TEM with projection or acute angle without crushing process.Utilize heating, it is long that these particles close consor on the sintered magnet surface, meanwhile, causes diffusion along the crystal boundary of sintered magnet, perhaps causes counterdiffusion mutually with the formation element of sintered magnet.In addition, owing to the terres rares fluorine compounds of these bunches shape are coated the surface of sintered magnet, therefore roughly form fluorine compounds on the sintered magnet surface comprehensively, be coated with dry back before heating under the temperature below the sintering temperature more than 200 ℃, at the grain surface of the part on sintered magnet surface, the part of the part that rare earth element concentration is high is fluoridized.This is fluoridized phase, contains the growth when keeping matching partly with parent phase of fluoridizing of aerobic, this kind fluoridize mutually or oxygen fluoridize phase from outside coupling ground growth fluorine compounds that parent phase is seen mutually or oxygen fluorine compounds phase, because of the heavy rare earth dvielement this fluoridize phase, fluorine compounds mutually or the oxygen fluorine compounds mutually near segregation, and make the coercive force increase.The heavy rare earth dvielement is along the scope of the preferred wide 1～50nm of part of the concentrated band shape of crystal boundary, if this scope then can satisfy high remanence and high coercive force.Under the situation of utilizing this kind gimmick that Dy is concentrated along crystal boundary, the magnetic characteristic of the sintered magnet of gained is, remanence is 1.0 to 1.6T, coercive force is 20～50kOe, for heavy rare earth dvielement concentration contained in the rare-earth sintered magnet with equal magnetic characteristic, can add the situation low 10% to 80% that NdFeB is a magnetic than use heavy rare earth class in the past.Fe concentration in the fluorine compounds on above-mentioned sintered magnet surface is according to heat treatment temperature and difference, and when when heating more than 1000 ℃, then the above Fe below 5% of 10ppm spreads in fluorine compounds.Though Fe concentration reaches 50% near the crystal boundary of fluorine compounds, yet if mean concentration is more than 1% below 5%, to the magnetic characteristic not influence basically of sintered magnet integral body.

＜embodiment 15 〉

Fluorine compounds to gel or colloidal sol shape are the particulate that contains the Fe more than the 1 atom % that adds particle diameter 1～100nm in the solution, and it is the gel or the colloidal sol shape Fe-fluorine compounds of particulate that making has mixed Fe.This moment microparticle surfaces the Fe atom a part and fluorine compounds fluorine or combine with constituting element chemistry more than any one of alkali, alkali earths or rare earth element of fluorine compounds.By contain to this kind particulate or bunch gel or the fluorine compounds of colloidal sol shape or atmosphere that the fluorine compounds presoma is containing nitrogen under irradiation millimeter wave or microwave, the chemically combined atom of more than one of participation fluorine atom or nitrogen-atoms and Fe atom and above-mentioned fluorine compounds formation element becomes many, Fe atom and rare earth element be by fluorine atom and nitrogen-atoms and combination, utilizes combining of fluorine atom and oxygen atom and Fe and rare earth element; Certain combination that perhaps utilizes rare earth element to combine with fluorine atom, oxygen atom, nitrogen-atoms and Fe atom, the magnetized part between the Fe atom becomes ferromagnetism, thereby has magnetic anisotropy.Because of in particulate, forming more more phase (nitrogen is 3～20%) mutually (Fe be 50～85%) and the rare earth element more phase (rare earth element be 10～75%) more of phase (fluorine is 10～50%), nitrogen of fluorine with Fe, the more layer of Fe will be responsible for magnetization, and the more phase of phase that fluorine or nitrogen are more or rare earth element then helps high coercive force.Utilize the quaternary system (M is rare earth element or alkali, alkali earths element) of this kind Fe-M-F-N, the magnet that can obtain to have the magnetic characteristic of coercive force more than 10kOe.Utilization has partly mixed the solution of the micro mist that contains rare earth element in above-mentioned terres rares fluorine compounds solution, also can obtain identical effect.

＜embodiment 16 〉

In the fluorine compounds solution that shows visible light permeability, add the particulate that contains the Fe more than the 1 atom % of particle diameter 1～100nm, make the Fe-fluorine compounds bunch that mixed the Fe-B particulate.When mean particle dia surpasses 100nm, then through thereafter process will residual soft magnetism composition in inside the original characteristic of Fe, when less than 1nm, then oxygen will uprise with respect to the concentration of Fe, therefore is difficult to improve magnetic characteristic, so the particle diameter of preferred 1～100nm.This moment the Fe-B microparticle surfaces the Fe atom a part and fluorine compounds fluorine or combine with constituting element chemistry more than any one of alkali, alkali earths or rare earth element of fluorine compounds.By contain to this kind particulate or bunch gel or the fluorine compounds that comprise Fe-B of colloidal sol shape or fluorine compounds presoma irradiation millimeter wave or microwave, the chemically combined atom of more than one of participation fluorine atom or boron (B) atom and Fe atom and above-mentioned fluorine compounds formation element becomes many, Fe atom and rare earth element be by fluorine atom and combination, utilizes combining of fluorine atom and boron atom and Fe and rare earth element; Certain combination that perhaps utilizes rare earth element to combine with fluorine atom, oxygen atom, boron atom and Fe atom, the magnetized part between the Fe atom becomes ferromagnetism, thereby has magnetic anisotropy.Because of in particulate, forming more more phase (boron is 5～20%) mutually (Fe be 50～85%) and the rare earth element more phase (rare earth element be 10～75%) more of phase (fluorine is 10～50%), boron of fluorine with Fe, the more layer of Fe will be responsible for magnetization, and the more phase of phase that fluorine or boron are more or rare earth element then helps high coercive force.Utilize the quaternary system (M is rare earth element or alkali, alkali earths element) of this kind Fe-M-B-N, can obtain to have the magnet of the magnetic characteristic of coercive force more than 10kOe, by M being made as the heavy rare earth dvielement, then Curie temperature can be made as 400～600 ℃.

＜embodiment 17 〉

With Nd ₂Fe ₁₄B is that the NdFeB of principal phase is the surface of sintered magnet, and coating can grow up to the fluorine compounds bunch solution of terres rares fluorine compounds under the temperature more than 100 ℃.The average film thickness of the terres rares fluorine compounds after the coating is 1～10000nm.This kind bunch can not cause the crystal structure of body material fluorine compounds, and fluorine is periodically constructed with certain with rare earth element and combined.NdFeB is the crystal particle diameter average out to 1-20 μ m of sintered magnet, is with Nd ₂Fe ₁₄B is the sintered magnet of principal phase, and the deterioration that is accompanied by the magnetic characteristic of processing or grinding and producing on the surface of sintered magnet can be seen on demagnetization curve.In order to improve this kind magnetic characteristic deterioration, increase is by the coercive force due near the rare earth element segregation the crystal boundary, improve the rectangularity of demagnetization curve, realize near the high magnetic resistanceization that magnet surface or crystal boundary are, the high-Curie-pointization that realization is brought by fluorine compounds, high strength, highly corrosion resistantization, reduce the terres rares use amount, reduce magnetize magnetic field etc., after the terres rares fluorine compounds presoma of gel or colloidal sol shape being coated sintered magnet surface and drying, heat-treating under the temperature below the sintering temperature more than 300 ℃.Terres rares fluorine compounds bunch grow up to the particle shape more than the following 1nm of 100nm in the coating dry run, and then by heating, the crystal boundary of presoma or bunch generation of a part of fluorine compounds and sintered magnet or surperficial reaction or diffusion.Be coated with dried fluorine compounds particle if in the poly-temperature range of between particle, not joining, then because without crushing process, therefore can not become surface with projection or acute angle, when observing particle with TEM, approximate the oval or circular of fillet that have, in particle or particle surface can't see bunch, in profile, can't see discontinuous concavo-convex.Utilize heating, it is long that these particles close consor on the sintered magnet surface, meanwhile, causes diffusion along the crystal boundary of sintered magnet, perhaps causes counterdiffusion mutually with the formation element of sintered magnet.In addition, owing to the terres rares fluorine compounds of these bunches shape are coated the surface of sintered magnet, therefore roughly cover fluorine compounds on the sintered magnet surface comprehensively, the dry back of coating is at the grain surface of the part on sintered magnet surface, and the part of the part that rare earth element concentration is high is fluoridized.This fluoridizes mutually or contains the growth when keeping matching partly with parent phase of fluoridizing of aerobic, this kind fluoridize mutually or oxygen fluoridize phase from outside coupling ground growth fluorine compounds that parent phase is seen mutually or oxygen fluorine compounds phase, because of the heavy rare earth dvielement this fluoridize phase, fluorine compounds mutually or the oxygen fluorine compounds mutually in segregation, and make the coercive force increase.The heavy rare earth dvielement is along the scope of the preferred wide 0.1～100nm of part of the concentrated band shape of crystal boundary, if this scope then can satisfy high remanence and high coercive force.Using DyF _2-3Presoma utilize under the situation that this kind gimmick concentrates Dy along crystal boundary, the magnetic characteristic of the sintered magnet of gained is, remanence is 1.0 to 1.6T, coercive force is 20～50kOe, for heavy rare earth dvielement concentration contained in the rare-earth sintered magnet with equal magnetic characteristic, the situation that can be magnetic than use heavy rare earth class interpolation NdFeB in the past is lower, the fluorine compounds or the oxygen fluorine compounds that contain Nd in the growth of crystal boundary triple point, in the center of the thick sintered magnet of 1mm～10mm, also be part growth fluorine compounds or oxygen fluorine compounds at the crystal boundary triple point.Also can be by applying the magnetic field more than the 10kOe when the growth of this kind fluorine compounds or oxygen fluorine compounds, the direction of magnetization of heavy rare earth dvielement, fluorine compounds or oxygen fluorine compounds is unified, perhaps, increase coercive force by adding the combination of ferromagnetism.Fe concentration in the fluorine compounds on above-mentioned sintered magnet surface is according to heat treatment temperature and difference, and when when heating more than 1000 ℃, then the above Fe below 5% of 1ppm spreads in fluorine compounds.Though Fe concentration reaches 50% near the crystal boundary of fluorine compounds, yet if mean concentration is below 5%, to the magnetic characteristic not influence basically of sintered magnet integral body.

＜embodiment 18 〉

The SmCo alloy is utilized fusings such as high-frequency induction heating fusing, in inert gas, pulverize.Chippy powder diameter is 1-10 μ m.Surface coated fluorine compounds presoma (SmF at comminuted powder ₃Presoma) also dry, in magnetic field, utilize decompressor that coated powder is orientated, make the press-powder body.In the powder of press-powder body, import a plurality of bunches, add the fluorine compounds presoma by outside, and the part of bunch face is also covered with the fluorine compounds presoma from the press-powder body.With its sintering, chilling.Sintered body is made of two-phase at least, forms SmCo ₅And Sm ₂Co ₁₇Phase.Fluorine compounds begin to decompose when sintering, though in two-phase any, distribution is arranged all, more fluorine atom is present in SmCo ₅In, coercive force is compared increase with the situation of not adding the fluorine compounds presoma.In addition, as the coating effect of fluorine compounds presoma, can see some effect that high magnetic resistanceization, rectangularity improve, the demagnetization tolerance improves, mechanical strength improves.Aforesaid press-powder body is formed by Fe series structure height density ground, by be coated with the solution that contains fluorine on this high density press-powder formed body, heat-treats, and just can reduce the loss of tectosome.So, in the product that constitutes by sintered magnet and press-powder formed body, by side by side being heated to after the solution-treated more than 200 ℃, just can utilize fluorine or constitute other the diffusion of metallic element of solution, the magnetic characteristic that realizes sintered magnet improves and the loss minimizing of press-powder formed body.

＜embodiment 19 〉

Use is with Nd ₂Fe ₁₄Near the composition of B for the particle diameter of principal phase is the particle of 1 to 20 μ m, interim formed body that will drawing in magnetic field in inert gas or in the vacuum with 200 ℃ to 1000 ℃ temperature range heating after, dipping or be coated with fluorine compounds bunch solution.Utilize this processing, the fluorine compounds precursor solution will immerse along the magnetic interface of the inside of formed body, and the part at this interface is covered by the fluorine compounds presoma.Then will this impregnated or formed body of being coated with at the sintering temperature higher than above-mentioned heating-up temperature, then in order to improve coercive force heat treatment under the temperature lower than sintering temperature, the sintered body that obtains containing fluorine element and constitute rare earth element, alkali or the alkali earths element of element as presoma.The feature of this process is, before sintering, form terres rares enrichment phase in part or all of magnetic surface, not with its tight burning, and the gap of beyond the contact site of magnetic and magnetic, guaranteeing 1nm, utilizing dipping or coating that the fluorine compounds presoma is immersed and cover this gap, is the material that the part on the surface of the magnetic that is in formed body inside beyond formed body is the most surperficial covers the fluorine compounds presoma.Utilize this process, sintered body central part at 100mm also can be at magnetic surface coverage fluorine compounds, by in the formation element of fluorine compounds bunch, selecting Dy, Tb, Ho etc. to plant rare earth elements, just can make near the segregation crystal boundary of sintered body of heavy rare earth dvielement, realize increase, the rectangularity of coercive force raising, remanence increase, coercive force temperature coefficient or remanence temperature coefficient reduction, by some effect of the minimizing of the rotten magnetic characteristic deterioration that causes of processing.The segregation of above-mentioned heavy rare earth dvielement is from crystal boundary 1～100nm, depends on heat treatment temperature and changes, and at the distinguished point place of crystal boundary triple point and so on the tendency of widening is arranged.For the cyrystal boundary segregation of auxiliary heavy rare earth dvielement, and for the constructional disorder of the phase that contains fluorine that prevents crystal boundary etc., also can add Cu, Zr, Ni, Mo, Sn, Al, Zn, Ti, transition metals such as Nb, Co with the concentration below the 3 atom %.

＜embodiment 20 〉

By bunch solution of Fe fluorine compounds is mixed with the presoma of at least a fluorine compounds in containing alkali, alkali earths or rare earth element, and carry out dry heat and handle, just can form Fe-M-F (M is at least a element in alkali, alkali earths or the rare earth element) compound.Owing to be mixed with presoma, therefore the particle of growing in the dry heat processing procedure is very little, is 1-30nm, and fluorine compounds are grown in these nano particles.The fluorine compounds material of high coercive force can by with Fe be more than the 10 atom %, fluorine is that composition more than 1% forms the M enrichment and makes mutually on crystal boundary, and particularly by with Fe concentration more than 50 atom %, M is 5～30%, fluorine is that 1～20% grow fluorine enrichment phase, Fe enrichment reaches M enrichment phase mutually, growth fluorine enrichment phase or M enrichment phase just can obtain showing ferromagnetism and the coercive force powder more than 10kOe on crystal boundary.For additional anisotropy, by make the fluorine compounds growth in magnetic field, the Fe enrichment will be grown along magnetic direction mutually.In growth course,,, just there is not special problem as long as the skeleton of above-mentioned phase is not destroyed even sneak into hydrogen, oxygen, carbon, nitrogen, boron.In addition, in Fe-M-F (the M atom is more than one of transition metals such as Cr, Mn), with the M atom be more than the 5 atom %, the F atom be composition more than the 5 atom % from containing the growth from solution of bunch shape fluorine compounds etc., just can obtain high coercive force (coercive force is more than 5kOe).By in these compounds, having anisotropic arrangement, can see very high anisotropy for fluorine atom.Owing to using solution as described above, this kind ternary system magnet forms, therefore do not need the processing grinding operation, so can easily make the magnet of complicated shape, can also in a magnet, change anisotropic direction continuously, can be used for various rotating machineries, magnetic sensor, hard disk magnet component, magnetizing mediums.In addition, be made as less than 5 atom % by the concentration with the M atom, Fe-M-F ternary system alloy will become the high saturation magnetic flux density soft magnetic material, goes in the core material of various magnetic loops.In addition, can be the raising that the formation of oxygen fluorine compounds of the reaction of treatment fluid realizes magnetic characteristic or temperature characterisitic, the high frequency characteristics etc. of ferrite by having utilized ferrite particle and fluorine.In addition, can use fluorine is the magnetooptics effect that treatment fluid improves various magnetic materials, goes in isolator loop, the optical waveguide equimagnetic optical application machine.

＜embodiment 21 〉

At processing grinding with Nd ₂Fe ₁₄B structure is a sintered magnet as the NdFeB of principal phase, and is bonding and make under the situation of rotor with lamination electromagnetic steel plate, lamination amorphous or press-powder iron, utilizes processing lamination electromagnetic steel plate or press-powder iron such as mould in advance in the position of inserting magnet.Sintered magnet is being inserted under the situation of magnet insertion position, the gap of 0.01～0.5mm is being set between sintered magnet and lamination electromagnetic steel plate or press-powder iron.Comprise the various sintered magnets that insert the shape that comprises that annular or half-conical shape etc. are crooked in the magnet positions in gap to this kind, in this gap, inject the fluorine compounds solution of gel or colloidal sol shape or bunch shape, under the temperature more than 100 ℃, heat, sintered magnet and lamination electromagnetic steel plate, lamination amorphous or press-powder iron is bonding.At this moment, by under the temperature more than 200 ℃, heat-treating again, make rare earth element or fluorine to the sintered magnet diffusion into the surface, make of the diffusion into the surface of the formation element of fluorine compounds to lamination electromagnetic steel plate or press-powder iron, just can improve the magnetic characteristic (increase coercive force, raising rectangularity, raising demagnetization tolerance, lifting Curie temperature etc.) of sintered magnet, and make bonding firm.Can realize sintered magnet bending the improvement of magnetic characteristic of affected layer, also can in the surface and the diffusion layer as principal component in the crystal boundary of each magnetic material, contain light elements such as aerobic or carbon with fluorine or rare earth element.Near crystal boundary, because of on crystal boundary, having fluorine or oxygen, the segregation in 2 times to 1000 times scope of average 0.1 to 10nm grain boundary width of heavy rare earth dvielement, and coercive force is increased.Near the grain boundary width that contains fluorine the crystal boundary triple point becomes big, and fluorine and heavy rare earth dvielement pass crystal boundary and spread from the crystal boundary triple point.Be made as by Nd concentration and compare Nd parent phase ₂Fe ₁₄The rare earth element concentration of few 0 to the 10 atom % of the composition of B can utilize fluorine compounds to handle to replenish the heavy rare earth dvielement, therefore can obtain the above high remanence of 1.5T.The existing grain boundary width of fluorine is more than 1nm, and the coverage rate of the stratiform crystal boundary phase that contains fluorine of crystal boundary integral body is more than 10%, and the resistivity of sintered magnet reaches more than the 0.2m Ω cm.A part that is present in the fluorine atom in the crystal boundary combines with Nd or oxygen atom, Spin Interaction between the atomic spin in the spin-spin interaction of the atom in the crystal boundary and the parent phase on the crystal boundary face is impacted, increase by the magnetic field anisotropy energy due to the segregation of heavy rare earth dvielement, and fluorine or oxygen, the spin that atom had of the crystal boundary of Nd atom in mutually exerts an influence to the spin or the track of the parent phase lattice of contact crystal boundary face, and fluorine, oxygen, crystal boundaries such as Nd reduce concavo-convex under the atomic level of crystal boundary face mutually, suppress the generation of magnetic reversal, thereby coercive force or rectangularity are increased.In order to improve the magnetic characteristic of sintered magnet, can in above-mentioned fluorine compounds, contain rare earth element, and for realize the magnet magnetic characteristic beyond improving adhesive effect or the straightening or the loss of soft magnetism reduce, can use the fluorine compounds that contain rare earth element or alkali, alkali earths element.

＜embodiment 22 〉

At NdFeB is the surface coated gel of sintered magnet or the terres rares fluorine compounds solution with light transmission of colloidal sol shape.The thickness of the terres rares fluorine compounds after the coating is 1～10000nm.NdFeB is that sintered magnet is with Nd ₂Fe ₁₄B is as the sintered magnet of principal phase, and the deterioration of the magnetic characteristic that is accompanied by processing grinding or oxidation generation can be seen in the surface of sintered magnet.In order to improve this kind magnetic characteristic deterioration, after the sintered magnet surface being carried out acid treatment, cleaning, the terres rares fluorine compounds that see through luminous ray in the sintered magnet surface coated are solution and dry, are heat-treating under the temperature below the sintering temperature more than 200 ℃.Clean before the solution coat can also be used various solution or gimmicks such as sputter, reactive etching or ultrasonic waves for cleaning except acid treatment, preferably remove thicker oxide layer.If utilize making of high frequency such as millimeter wave to be used for carrying out localized heating, then can make heat treatment temperature lower more than 100 ℃ than common heat treatment temperature, can the shortening heat processing time.The coating drying after soon, become particle more than the following 1nm of 50nm from gel or colloidal sol shape terres rares fluorine compounds growth from solution, can see that the structure around the fluorine atom changes,, produce and the crystal boundary of sintered magnet or the reaction or the diffusion on surface by further heating.Owing to be not to use particle or powder, and be to use solution, and therefore can control equably and apply thickness and film thickness distribution, in material that requires cleannes or operation, can use above-mentioned solution, by sheltering before and after the solution coat, then be easy to only be coated on and want the part that is coated with.This kind painting process is owing to use solution, and therefore the processing as magnet used in the precise electronic machines such as voice coil motor is favourable.The situation that contains various CH bases or OH base in solution is also arranged, and soon state forms main construct different with the crystal structure after the heating after the state of solution or the coating.That is, being constructed to and the diverse main structure of the crystal structure of fluorine compounds powder of solution can utilize electron ray or X-ray diffraction spectrogram to detect as difference clearly, can detect very wide diffraction maximum.This explanation is compared with fluorine compounds completely, and local disorder takes place periodical configuration.Utilizing heating to remove after above-mentioned solution coat desolvates, roughly form fluorine compounds on the sintered magnet surface comprehensively, before the dry back of coating is with the heating of the temperature more than 500 ℃, fluoridize in the part of the high part of the grain surface rare earth element concentration of the part on sintered magnet surface.In the middle of the above-mentioned terres rares fluorine compounds, Dy, the Tb of their the formation element of conduct of Dy fluorine compounds or Tb, Ho fluorine compounds or their oxygen fluorine compounds, Ho etc. improve the deterioration of magnetic characteristic along the crystal boundary diffusion.When heat treatment temperature reached more than 800 ℃, then the step that diffuses into mutually of fluorine compounds and sintered magnet carried out, thereby the situation of seeing Fe in fluorine compound layer with the concentration more than the 1ppm is arranged.Heat treatment temperature is high more, and then parent phase constitutes the tendency that the concentration of element in fluorine compound layer just has increase more.Under the situation that sintered magnet is bonding stackedly, to become with the fluorine compounds or the oxygen fluorine compounds that have improved the identical or different adhesive linkage of the fluorine compounds of magnetic characteristic because of diffusion after above-mentioned heat treatment, be coated with, stacked, by carrying out millimeter-wave irradiation, just only near the caking layer and sintered magnet is bonding.Fluorine compounds as adhesive linkage are (NdF such as Nd fluorine compounds _2-3, Nd (OF) _1-3), by selecting the illuminate condition of millimeter wave, just can be in the temperature rising that suppresses sintering magnetic blow out centre portion, only optionally near the caking layer, thereby can suppress to be accompanied by the magnetic characteristic deterioration or the change in size of the sintered magnet of bonding generation.In addition, by using millimeter wave, the heat treatment time of selecting heating can be become below half of in the past heat treatment time, thereby be applicable to the mass production that can side by side improve magnetic characteristic with bonding process.Millimeter wave not only can be used for the bonding of sintered magnet, can also be used for the magnetic characteristic that the diffusion by coating material causes and improve, can realize by except fluorine compounds, also using oxide or dielectric losses such as nitride, the carbide material different with the NdFeB of parent phase as the function of adhesive linkage.Even, also can utilize heating to make it diffusion though do not use millimeter wave, by using millimeter wave like this fluorine compounds portion is optionally heated, just can be used for bonding, the joint of magnetic material and various metal material or oxide material.As the example of the condition of millimeter wave, at 28GHz, 1-10kW, Ar, N ₂Shone 1-30 minute in the atmosphere or in the vacuum or in other the inert atmosphere.Because by using millimeter wave, fluorine compounds or the fluorine compounds that contain aerobic are selectively heated, therefore just can not change the tissue of sintered body itself basically, and fluorine compounds are spread along crystal boundary, can prevent that fluorine compounds from constituting the diffusion of element to crystal grain inside, compare with the situation of merely heating, can obtain higher magnetic characteristic (high remanence, rectangularity improves, high coercive force, high-curie temperature, the low-heat demagnetization, highly corrosion resistant, certain of high magnetic resistanceization etc.), utilize the selection of millimeter wave condition and fluorine compounds, with common heat treatment phase ratio, can be with the formation element of fluorine compounds from the diffusion into the surface of sintered magnet to darker part, even can diffuse to the magnetic blow out centre portion of 10 * 10 * 10cm.Utilize the magnetic characteristic of the sintered magnet that this kind gimmick obtains to be, remanence is 1.0 to 1.6T, coercive force is 20～50kOe, for heavy rare earth dvielement concentration contained in the rare-earth sintered magnet with equal magnetic characteristic, can be that the situation of magnetic is lower than use heavy rare earth class interpolation NdFeB in the past.In addition, if at least a fluorine compounds that contain alkali, alkali earths or rare earth element or oxygen fluorine compounds at sintered magnet remained on surface 1～100nm, then the magnetic resistance on sintered magnet surface uprises, even stackedly bondingly also can reduce the vortex flow loss, can realize that the loss in the high frequency magnetic field reduces.Owing to utilize this kind loss to reduce, can reduce the heating of magnet, therefore can reduce the use amount of heavy rare earth dvielement.Because above-mentioned terres rares fluorine compounds are not powdery, viscosity is low, therefore can be applied to 1nm in the small hole of 100nm, improve so go for the magnetic characteristic of small magnet component, this magnet goes for commutating in the permanent magnet motor, disc type armature direct current machine, flat motor, voice coil motor, stepping motor, magnetic sensor, actuator, magnetic bearing, magnetic-resonance image diagnostic apparatus, electron tube, loud speaker etc. of type or brushless type.In addition, used Treatment Solution can also be used as various magnetic fluids, magnetic shielding material by mixing with magnetic particle in the coating magnet that is applicable to coated media or arbitrary shape in the fluorine compounds processing.

＜embodiment 23 〉

Contain RE ₂Fe _14-18(B, F) _1-3, RE ₂Fe _14-19F _1-3, RE ₂Fe _14-19(F, N) _1-3, RE ₂Fe _14-19(F, C) _0.1-2In RE (rare earth element) and iron and fluorine, utilizing the particle of the particle diameter 1-10000nm that the solution contain fluorine makes with millimeter-wave irradiation (output 1kW, 200 to 1,000 ℃) is the magnetic material with magnetic anisotropy, can be used for various magnetic loops.These particles have the concentration gradient of fluorine, in particle, can aspect anisotropy energy, see difference, the mutual-assistance magnetic region stabilisation of high anisotropy energy, be the material that forms by reaction mutually, can obtain to have reduced the magnetic material of the content of terres rares with local random configuration with colloidal sol that contains fluorine or rare earth element or gel etc.The concentration gradient of distance and fluorine is relevant between the magnetic material that this kind contains fluorine and terres rares-fluorine atom, in X-ray diffraction, can in the scope of 1.0-4.0 dust, see a plurality of diffraction maximums, can see the wide peak of half breadth more than 1 degree in the diffraction maximum before reaction, this peak changes because of heat treatment, forms in the process that half breadth narrows down.Utilize this kind colloidal sol or gel, the reaction of colloidal solution can form the RE-Fe-F system as various magnetic materials, RE-Fe-F-B system, RE-Co-F system, M-Fe-F system, M-Co-F system, RE-Mn-F system, RE-V-F system, the material (M is a transition metal) that RE-Cr-F system and they and oxide ferrite based material react, as the essential structure that does not contain metallic element, can be formed by the millimeter-wave irradiation of above-mentioned fluorine-containing solution has changed between the fluorine or fluoro-carbon, the nanotube in conjunction with angle of fluoro-oxygen etc. can obtain and various characteristics more than the carbon nano-tube equal extent.The magnetic material that above-mentioned solution is used for part of raw materials and makes since can be film to the body material, good aspect freedom shape, do not need manufacturing procedure, therefore be applicable to the mass production of various magnetic material application products.The magnetic material that can use the formation of this kind solution also can be a RE-M system of containing halogen element except fluorine compounds system, can utilize heat treatment change magnetic characteristics such as localized heating by growth from solution on substrate.In addition, in the magnetic material that utilizes these solution to make, the material system that shows magnetooptics characteristic, magneto resistance effect, piezoelectric effect, thermo-electromotive force, optomagnetic inhibition effect, fluorescent characteristic, magnetostrictive effect, magnetic field dependence fluorescent characteristic, magnetic cooling effect is arranged, gone for utilizing in the element of each feature, can be used for magneto-optical recorder, magnetic head, magnetizing mediums, energy conversion elements, optical element, optical fiber, colouring agent, glass material etc.

＜embodiment 24 〉

Contain RE ₂Fe _14-18(B, F) _1-3, RE ₂Fe _14-19F _1-3, RE ₂Fe _14-19(F, N) _1-3, RE ₂Fe _14-19(F, C) _0.1-2In RE (rare earth element) and iron and fluorine, utilize the solution contain fluorine, the solution that will contain fluorine uses rotation coating machine etc. to be coated on the substrate equably.Its thickness is 1-10000nm.Alternatively be coated with drying by solution that will contain rare earth element and the solution that contains fluorine, formation has the laminated body of some cycles, by this laminated body being carried out millimeter-wave irradiation (output 1kW, 200 to 1,000 ℃) produce the reaction at interface and the particle of the particle diameter 1-10000nm that makes is the magnetic material with magnetic anisotropy, can be used for various magnetic loops.These particles have the concentration gradient of fluorine, in particle, can aspect anisotropy energy, see difference, the mutual-assistance magnetic region stabilisation of high anisotropy energy, be the material that forms by reaction mutually, can reduce the content of terres rares with local random configuration with colloidal sol that contains fluorine or rare earth element or gel etc.The concentration gradient of distance and fluorine is relevant between the magnetic material that this kind contains fluorine and terres rares-fluorine atom, in X-ray diffraction, can in being spaced apart the scope of 1.0-10 dust, face see a plurality of diffraction maximums, can see the wide peak of half breadth more than 1 degree in the diffraction maximum before reaction, this peak changes because of heat treatment, forms in the process that half breadth narrows down.Utilize the laminationization of this kind colloidal sol or gel, colloidal solution and the reaction of stack membrane can make various magnetic materials, can form RE-Fe-F system, RE-Co-F system, M-Fe-F system, M-Co-F system, M-Ni-F system, RE-Fe-(B, F) be, the material (M is a transition metal) of RE-Mn-F system, RE-V-F system, RE-Cr-F system and they and the reaction of oxide ferrite based material, also can utilize stacked, the heat treated material of the plated film that is with other material.This kind solution is used for part of raw materials and makes, utilized the magnetic material of the variation of the crystal structure due to the heat treatment; Perhaps utilize localized heating such as millimeter wave, field effect, magnetic field effect and make material that the laminated body that formed by solution reacts owing to can be that film is to the body material, good aspect freedom shape, do not need manufacturing procedure, therefore be applicable to the mass production of various magnetic material application products, by between the magnetic phase of magnetizing mediums, forming fluorine-containing layer, then can improve the SN of magnetic recording.In addition, in the middle of the magnetic material that utilizes these solution to make, the material system that shows magnetooptics characteristic, magneto resistance effect, piezoelectric effect, thermo-electromotive force, optomagnetic inhibition effect, magnetic field dependence fluorescent characteristic, magnetic cooling effect is arranged, gone for utilizing in the element of each feature, can be used for magneto-optical recorder, magnetic head, magnetizing mediums, energy conversion elements, optical element etc.Replacing above-mentioned lamination process, and after utilizing diameter to be scattered in various particles in the solution,, also can realize equal effect by heat-treating less than the particle of lamination thickness.In the middle of these materials, the size of magnetic moment of distance between the adjacent atom that demonstrates fluorine and fluorine and the adjacent atom due to the angle and the variation that magnetic combines are also arranged, and the material that is reflected by above-mentioned various characteristics, but these characteristics depend on the structure with the interface of approaching local random configuration of the structure of solution and perfect crystal structure consumingly.Use above-mentioned fluorine compounds to form solution, (M is a metallic element having M-F, F is a fluorine) in the material of key or M-F-O key, M-F-C key or M-F-B key, the superconductivity effects that can utilize the acquisitions such as selection of periodicity, bond angle degree, the M element of key to cause greatly because of the electron affinity of fluorine atom, high-temperature superconductor can be realized, highfield generation magnet can be used for.

＜embodiment 25 〉

At NdFeB is the surface coated gel of sintered magnet or the terres rares fluorine compounds solution with light transmission of colloidal sol shape.The thickness of the terres rares fluorine compounds after the coating is 0.1～10000nm.NdFeB is that sintered magnet is with Nd ₂Fe ₁₄The basic crystal structure of B is as the sintered magnet of principal phase, and the deterioration of the magnetic characteristic that is accompanied by processing grinding or oxidation generation can be seen in the surface of sintered magnet.In order to improve this kind magnetic characteristic deterioration, after the sintered magnet surface coated sees through the terres rares fluorine compounds solution and drying of luminous ray, heat-treating under the temperature below the sintering temperature more than 500 ℃.After the coating drying, soon, from gel or colloidal sol shape terres rares fluorine compounds solution or colloidal solution, grow into the particle more than the 1nm, produce and the crystal boundary of sintered magnet or the reaction or the diffusion at interface in the low temperature next part below 200 ℃.Owing to be not to use particle or powder, and be to use solution, and therefore can control equably and apply thickness and film thickness distribution, in material that requires cleannes or operation, can use above-mentioned solution, by sheltering before and after the solution coat, then be easy to only be coated on and want the part that is coated with.This kind painting process is owing to use solution, and therefore the processing as magnet used in the precise electronic machines such as voice coil motor is favourable.Provide the application construction of voice coil motor among Fig. 4.The magnetic flux flow that has carried out solution-treated and improved the sintered magnet 12 of magnetic characteristic is crossed yoke 11.Constitute by moving coil 13 that links to each other with arm and copper pipe 14.Two sintered magnets 12 pass the space and flow through magnetic flux in the yokes 11 of central portion.In the keeping of magnetic flux density, require high coercive force, high remanence and high rectangle characteristic.It is near the segregation that forms fluorine segregation and metallic element solution coat and the crystal boundary of heat treatment in sintered magnet that these characteristics are utilized fluorine, utilize the reduction of magnet surface simultaneously, compare with the sintered magnet that does not use solution and can see that significantly magnetic characteristic is improved, in the sintered magnet 12 that is applied to voice coil loudspeaker voice coil, the raising of positioning accuracy or locating speed can be realized, the hard disk unit of high frequency or high speed, high record density can be realized.

＜embodiment 26 〉

Contain RE ₂Fe _14-18(B, F, O) _1-3, RE ₂Fe _14-19(F, O) _1-3, RE ₂Fe _14-19(F, N, O) _1-3, RE ₂Fe _14-19(F, C, O) _0.1-2In RE (rare earth element) and iron and fluorine, utilize the solution contain fluorine, the solution that will contain fluorine uses rotation coating machine etc. to be coated on the substrate equably.Its thickness is 1-10000nm.Alternatively be coated with drying by solution that will contain rare earth element and the solution that contains fluorine, formation has the laminated body of some cycles, by this laminated body being carried out microwave or millimeter-wave irradiation (output 1kW, 200 to 1,000 ℃) produce the reaction at interface and the particle of the particle diameter 1-10000nm that makes is the magnetic material with ferromagnetism or ferromagnetism and anti-ferromagnetic mixture, can be used for various magnetic loops.These particles have the concentration gradient of fluorine or oxygen or carbon, in particle, can see difference aspect anisotropy energy or the magnetization, the mutual-assistance magnetic region stabilisation of high anisotropy energy is the material that is formed by the reaction mutually with local random configuration with colloidal sol that contains fluorine or rare earth element or gel etc.The concentration gradient of distance and fluorine is relevant between the magnetic material that this kind contains fluorine and terres rares-fluorine atom, in X-ray diffraction, can in being spaced apart the scope of 1.0-10 dust, face see a plurality of diffraction maximums, can see the wide peak of half breadth more than 1 degree in the diffraction maximum before reaction, this peak changes because of heat treatment, forms in the process that half breadth narrows down.Utilize the laminationization of this kind colloidal sol or gel or colloidal solution and the reaction of stack membrane can make various magnetic materials, can form RE-Fe-F-O system, RE-Co-F-O system, M-Fe-F-O system, M-Co-F-O system, M-Ni-F-O system, RE-Fe-(B, F, O) be, the material (M is a transition metal) of RE-Mn-F-O system, RE-V-F-O system, RE-Cr-F-O system and they and the reaction of oxide ferrite based material, also can utilize stacked, the heat treated material of the plated film that is with other material.In addition, can utilize interpolation, can improve coercive force, or reduce ordering temperature the fluorine atom of the surface treatment of the ordered structure alloy that contains Pt etc.This kind solution is used for part of raw materials and makes, utilized the magnetic material of the variation of the crystal structure due to the heat treatment; Perhaps utilize localized heating such as millimeter wave, field effect, magnetic field effect and make material that the laminated body that formed by solution reacts owing to can be that film is to the body material, good aspect freedom shape, do not need manufacturing procedure, therefore be applicable to the mass production of various magnetic material application products.In addition, in the middle of the magnetic material that utilizes these solution to make, the material system that shows magnetooptics characteristic, magneto resistance effect, piezoelectric effect, thermo-electromotive force, optomagnetic inhibition effect, magnetic field dependence fluorescent characteristic, magnetic cooling effect is arranged, gone for utilizing in the element of each feature, can be used for magneto-optical recorder, magnetic head, magnetizing mediums, energy conversion elements, optical element etc.Replacing above-mentioned lamination process, and after utilizing diameter to be scattered in various particles in the solution,, also can realize equal effect by heat-treating less than the particle of lamination thickness.In the middle of these materials, the size of magnetic moment of distance between the adjacent atom that demonstrates fluorine and fluorine and the adjacent atom due to the angle and the variation that magnetic combines are also arranged, and the material that reflects by above-mentioned various characteristics, these characteristics depend on the structure with the interface of approaching local random configuration of the structure of solution and perfect crystal structure consumingly.Use above-mentioned fluorine compounds to form solution, (RE is a rare earth element having RE-F, F is a fluorine) in the material of key or RE-F-O key, RE-F-C key or RE-F-B key, the superconductivity effects that can utilize the acquisitions such as interpolation of selection, transition metal or alkali element of periodicity, bond angle degree, the RE element of key to cause greatly because of the electron affinity of fluorine atom, high-temperature superconductor can be realized, highfield generation magnet can be used for.In addition, owing to utilize the big character of electron affinity of fluorine atom, can change the electronic state density of fluorine atom periphery, the magnetic moment that therefore can confirm adjacent element increases or the variation of exchange and improved or the variation of each rerum natura (optical constant, resistance, thermal coefficient of expansion, photomagnetic effect, the freezing effect of magnetic, characteristic of semiconductor, fluorescent characteristic etc.) by its magnetic characteristic that causes.The optical characteristics such as fluorescent characteristic that utilization contains the above-mentioned material of fluorine depend on the character in magnetic field, can utilize optical characteristics to judge for magnetic state, can utilize optical characteristics or electrical characteristic to detect the kind and the position of magnetic pole, can in magnetic loops such as rotating machinery, be applied in the detection and control loop of position of magnetic pole.

＜embodiment 27 〉

Use contains the fluorine compounds treatment fluid of 1 to 50% Mn, coats the surface of the powder that contains at least a rare earth element.The crystal structure of the film that contains Mn and fluorine after the coating does not have the periodical configuration as body material manganese fluorine compounds, and interatomic distance has certain limit, and the half breadth at X-ray diffraction peak is below 10 degree more than 0.5 degree.The average diameter of powder is that 10nm is to 100 μ m.By to having carried out surface-treated powder irradiation millimeter wave, contain the layer heating of Mn, with powder generation local reaction.Powder and Mn fluorine compounds form conversion zone, form the compound that contains Mn.This compound exhibits that contains Mn goes out antiferromagnetism or ferromagnetism, can magnetically combine with powder and changes the magnetic characteristic of powder.In M-Mn-F (M is the metallic element beyond the Mn), by changing content, the crystal structure of Mn and F, can obtain ferromagnetism and remanence more than the 1.0T, have a material of the Curie temperature more than 100 ℃.By utilizing the F atom to change the state density of Mn, demonstrate ferromagnetism or antiferromagnetism, at M _0.01-80Mn _1-10F _1-20In (atom ratio), has the hard magnetic of being particularly suitable for properties of materials.Ferromagnetism is identical with antiferromagnetism, can coexist in alloy system, and the generation by near the anti-magnetic region the inhibition crystal boundary can realize the increase of coercive force.By adopting surface treatment, compare with powder inside, be easy near the powder peripheral part, improve the concentration of Mn and F,, form at peripheral part and to have anti-ferromagnetic layer, by with the magnetized magnetic of inside combine, also can increase coercive force.Fluorine compounds have the reduction effect that the oxygen of surface local oxidation is removed, and in various surface oxidation powder, body material, film etc., can heat-treat its reduction after forming fluoropolymer membrane on the surface.This moment is because by using millimeter wave only to carry out localized heating to fluoropolymer membrane, therefore the thermal impact of powder, body material, film inside can be made as minimumly and reduce, can be used for various reduction processes, by reducing the various characteristics that can increase substantially material.

＜embodiment 28 〉

For additional anisotropy, the NdFeB that interim shaping average grain diameter is 0.5 to 20 μ m in magnetic field is an alloyed powder.Magnetic field is more than the 5kOe, and stamping pressure is 0.5 to 3Ton/cm ²Pressing direction no matter be parallel with magnetic direction can or meet at right angles.Interim formed body is taken out from mould, demonstrate the solution that contains fluorine and rare earth element of the diffraction spectrogram of X-ray diffraction peak width below 20 degree more than 1 degree from the outer circumferential side infiltration of interim formed body.Utilize this impregnation process that the part on the magnetic surface in the interim formed body is covered with above-mentioned solution.With the solvent evaporation of this solution that covers, form the nuclear of fluorine compounds or oxygen fluorine compounds by solution, by further being heated, this nuclear makes it growth, and be alloy generation local reaction with NdFeB simultaneously.This kind reaction is accompanied by moving of rare earth element, carries out under from 200 to 300 ℃.The situation of reacting at its near interface after solution touches NdFeB to be powder is also arranged.Be accompanied by the reaction of moving of terres rares atom for this kind, the oxide layer on NdFeB powder surface is few more, and it is big more then to carry out degree.From the thickness of the fluorine compound layer of growth from solution or oxygen fluorine compound layer be 0.1nm to 100nm, best bed thickness average out to 1 to 20nm.Utilize this kind impregnation process,, all be easy to form fluorine compound layer at the central part of interim formed body regardless of the size of interim formed body.After compositions such as solvent among will this interim formed body are removed, heat-agglomerating in 900 to 1,200 ℃ temperature range in vacuum furnace etc.In order to improve agglutinating property, after removing, the solvent of interim formed body exerts pressure again, move by a part that makes powder, show the face that is not covered, thereby sintering is advanced by fluorine compounds.When the bed thickness of fluorine compounds on average surpassed 20nm, then agglutinating property reduced, and causes the undercapacity of sintered magnet.By NdFeB in sintering is powder and fluorine compounds or the reaction of oxygen fluorine compounds, carries out the diffusion of rare earth element, can see the segregation of heavy rare earth dvielement under the situation of having used the heavy rare earth dvielement, and coercive force increases.Can confirm near the segregation of heavy rare earth dvielement crystal boundary, fluorine is to the segregation of crystal boundary, oxygen is to the segregation of fluorine compounds, transition metal is to the segregation of fluorine segregation position, carbon is to the segregation of fluorine segregation position, the heavy rare earth dvielement that originally contains in the powder, oxygen, near some segregation of the segregation of carbon crystal boundary, except the increase of coercive force, can also confirm the reduction of the temperature coefficient of coercive force or remanence, the raising of the rectangularity of demagnetization curve, the reduction of magnet loss, the increase of remanence, the increase of energy product, the reduction of hot demagnetization rate, the reduction in magnetize magnetic field, raising to easy orientation rate, reduction that can not backheating demagnetization rate, the rising of Curie point, the recovery of the magnetic characteristic of processing deterioration layer, the raising of corrosion resistance, some effect of the raising of mechanical strength.The sintered magnet of 10 * 10 * 10cm that makes in the present embodiment be difficult to because of cut off, processing makes the magnetic characteristic deterioration, even in deterioration situation under, also can utilize 200 to 1,000 ℃ heat treatment to recover magnetic characteristic at an easy rate.In order to ensure reliability, also can form the diaphragm of metal-plated or resin-coating etc. on the surface of this sintered magnet.Above-mentioned impregnation process is the powder except going for NdFeB, can also be applicable in the alloy system powder such as Fe system, Fe-Si system, SmCo system, Fe-Si-B system, FeCoNi system, FeMn system, CrMn system, can realize that magnetic characteristic improves or loss reduces.

＜embodiment 29 〉

For additional anisotropy, in magnetic field interim shaping oxygen concentration below 2000ppm and average grain diameter be that the NdFeB of 0.5 to 20 μ m is an alloyed powder.Magnetic field is 3 to 15kOe, and stamping pressure is 0.5 to 3Ton/cm ²Pressing direction no matter be parallel with magnetic direction can or meet at right angles.Interim formed body is taken out from mould, permeate the solution that contains fluorine and rare earth element of display transparent from the outer circumferential side of interim formed body.Utilize this impregnation process that the part on the magnetic surface in the interim formed body is covered with above-mentioned solution.With the solvent evaporation of this solution that covers, form the nuclear of fluorine compounds or oxygen fluorine compounds by solution, by further being heated, this nuclear makes it growth, and be alloy generation local reaction with NdFeB simultaneously, grow fluorine compounds or oxygen fluorine compounds.This kind reaction is accompanied by move (diffusion) of rare earth element, carries out under from 200 to 300 ℃.The situation of reacting at its near interface after solution touches NdFeB to be powder is also arranged.Be accompanied by the reaction of moving of terres rares atom for this kind, the oxide layer on NdFeB powder surface is few more, and it is big more then to carry out degree.From the thickness of the fluorine compound layer of growth from solution or oxygen fluorine compound layer be 0.1nm to 100nm, best bed thickness average out to 1 to 20nm.Utilize this kind impregnation process,, all be easy to form fluorine compound layer at the central part of interim formed body regardless of the size of interim formed body.After compositions such as solvent among will this interim formed body are removed, in vacuum furnace etc. 900 to 1,200 ℃ temperature range heat-agglomerating.In order to improve agglutinating property, after removing, the solvent of interim formed body exerts pressure again, move by a part that makes powder, show the face that is not covered, thereby sintering is advanced by fluorine compounds.When the bed thickness of fluorine compounds on average surpassed 20nm, then agglutinating property reduced, and causes the undercapacity of sintered magnet.By NdFeB in sintering is powder and fluorine compounds or the reaction of oxygen fluorine compounds, carry out the diffusion of heavy rare earth dvielements such as rare earth element, particularly Dy, Ho, Tb, make near segregation crystal boundary of heavy rare earth dvielement, and the variation that utilizes the crystal boundary structure, coercive force increases.The segregation of heavy rare earth dvielement is by producing from utilizing dipping to be covered in the fluorine compounds or the oxygen fluorine compound layer that form the solution that contains fluorine and heavy rare earth dvielement on NdFeB powder surface, cause that partly these contain the diffusion of layer with the rare earth element of NdFeB powder of fluorine, heavy rare earth dvielement or fluorine also spread in this powder.The heavy rare earth dvielement of a part and fluorine atom form the such particle of intragranular precipitate to NdFeB particle diffusion inside.The crystal boundary of fluorine institute segregation is 0.1 to the width of 10nm, compares with the crystal boundary that does not contain fluorine, and grain boundary interfaces still less concavo-convex, the oxygen concentration that demonstrates crystal boundary portion is higher than the tendency of the oxygen concentration of intragranular.In addition, on the 1nm crystal boundary wide to 5nm, fluorine is to the segregation of crystal boundary central part, and growth has similar structure mutually with terres rares fluorine compounds or terres rares oxygen fluorine compounds partly.The interface of this crystal boundary and intragranular is seldom concavo-convex, when observing with TEM, then can in the lattice of the lattice of intragranular and crystal boundary, see the part matching, can also confirm certain orientation relationship, can think that this kind crystal boundary structure and coercive force increase closely related.Promptly, can confirm near the segregation of heavy rare earth dvielement crystal boundary, fluorine is to the segregation of crystal boundary, oxygen is to the segregation of fluorine compounds, transition metal is to the segregation of fluorine segregation position, carbon is to the segregation of fluorine segregation position, the heavy rare earth dvielement that originally contains in the powder, oxygen, near the segregation of carbon crystal boundary, fluorine and transition metal are to the segregation of crystal boundary, the light rare earth dvielement is to the segregation of crystal boundary central part or the concavo-convex minimizing of crystal boundary, because of the fluorine-containing heavy rare earth class CONCENTRATION DISTRIBUTION that forms with intragranular reaction mutually of crystal boundary, fluorine-containing lattice match or the orientation relationship with intragranular of crystal boundary, the formation of the fluorine-containing layer of intragranular, the formation of the fluorine-containing phase on the crystal boundary triple point, the crystal boundary triple point fluorine-containing with intragranular lattice match mutually or some of orientation relationship, except the increase of coercive force, can also confirm the reduction of the temperature coefficient of coercive force or remanence, the raising of the rectangularity of demagnetization curve, the reduction of magnet loss, the increase of remanence, the increase of energy product, the reduction of hot demagnetization rate, the reduction in magnetize magnetic field, raising to easy orientation rate, reduction that can not backheating demagnetization rate, the rising of Curie point, the recovery of the magnetic characteristic of processing deterioration layer, the raising of corrosion resistance, the raising of mechanical strength, the reduction of recoil permeability, the raising of crystal orientation, the increase of exchange, some effect of the control that anti-magnetic region is produced.

＜embodiment 30 〉

For additional anisotropy in sintering circuit, before sintering in magnetic field interim shaping oxygen concentration below 2000ppm and average grain diameter be the NdFeB alloyed powder of 0.5 to 20 μ m.Magnetic field is 3 to 15kOe, and stamping pressure is 0.5 to 3Ton/cm ²Pressing direction no matter be parallel with magnetic direction can or meet at right angles.Interim formed body is taken out from mould, permeate the solution that contains fluorine and rare earth element of display transparent from the outer circumferential side of interim formed body.Utilize this impregnation process that the part on the magnetic surface in the interim formed body is covered with above-mentioned solution.By to electromagnetic waves such as this interim formed body irradiation millimeter waves, the film heating that has been capped.This is because of variant aspect dielectric loss in layer that contains fluorine and the NdFeB based material, so can be in the heating that suppresses NdFeB self, only make the layer that contains fluorine cause that structure changes, can when preventing the deterioration of NdFeB, only make the layer heating that contains fluorine.Utilize irradiation, make the solvent evaporation of the solution that covers, form the nuclear of fluorine compounds or oxygen fluorine compounds by solution, by carrying out further prolonged exposure, nucleus growth be can see, with NdFeB alloy generation local reaction, fluorine compounds or oxygen fluorine compounds grown simultaneously.This kind reaction is accompanied by move (diffusion) of rare earth element, carries out under from 50 to 300 ℃.The situation of reacting at its near interface after the solution that contains ionic composition touches the NdFeB powder is also arranged.Be accompanied by the reaction of moving of terres rares atom for this kind, in electromagnetic wave irradiation, the oxide layer on NdFeB powder surface is few more, and it is big more then to carry out degree.From the fluorine compound layer of growth from solution or the thickness of oxygen fluorine compound layer is that 0.1nm is to 100nm, in order to obtain 1.0 to 1.6T high remanence, best bed thickness average out to 1 to 20nm.Utilize this kind impregnation process,, all be easy to form fluorine compound layer at the central part of interim formed body regardless of the size of interim formed body.After compositions such as solvent among will this interim formed body are removed, in vacuum furnace or utilize electromagnetic wave irradiation etc. 900 to 1,200 ℃ temperature range heat-agglomerating.In order to improve agglutinating property, after removing, the solvent of interim formed body exerts pressure again, move by a part that makes powder, show the face that is not covered, thereby sintering is advanced by fluorine compounds.When the bed thickness of fluorine compounds on average surpassed 50nm, then agglutinating property reduced, and causes the undercapacity of sintered magnet.By NdFeB in sintering is powder and fluorine compounds or the reaction of oxygen fluorine compounds, carry out the diffusion of heavy rare earth dvielements such as rare earth element, particularly Dy, Ho, Tb, make near segregation crystal boundary of heavy rare earth dvielement, and the variation that utilizes the crystal boundary structure, coercive force increases.The segregation of heavy rare earth dvielement is by producing from utilizing dipping to be covered in the fluorine compounds or the oxygen fluorine compound layer that form the solution that contains fluorine and heavy rare earth dvielement on NdFeB powder surface, cause that partly these contain the diffusion of layer with the rare earth element of NdFeB powder of fluorine, heavy rare earth dvielement or fluorine also spread in this powder.The heavy rare earth dvielement of a part and fluorine atom form the such particle of intragranular precipitate to NdFeB particle diffusion inside.Fluorine atom is 0.1 to 10nm width with the crystal boundary of the institute of the concentration more than 10ppm segregation, compares less than the crystal boundary of the concentration of 10ppm with fluorine atom, and grain boundary interfaces still less concavo-convex, the oxygen concentration that demonstrates crystal boundary portion is higher than the tendency of the oxygen concentration of intragranular.In addition, on the 1nm crystal boundary wide to 5nm, to the segregation of crystal boundary central part, growth has similar structure mutually with terres rares fluorine compounds or terres rares oxygen fluorine compounds to fluorine partly with the concentration more than 2 times of intragranular.The interface of this crystal boundary and intragranular is seldom concavo-convex in the part of the segregation that can see fluorine atom, when observing with TEM, then can in the lattice of the lattice of intragranular and crystal boundary, see the part matching, can also confirm certain orientation relationship, can think that this kind crystal boundary structure and coercive force increase closely related.Promptly, can confirm near the segregation of heavy rare earth dvielement crystal boundary, fluorine is to the segregation of crystal boundary, oxygen is to the segregation of fluorine compounds, transition metal is to the segregation of fluorine segregation position, carbon is to the segregation of fluorine segregation position, the heavy rare earth dvielement that originally contains in the powder, oxygen, near the segregation of carbon crystal boundary, fluorine and transition metal are to the segregation of crystal boundary, the light rare earth dvielement is to the segregation of crystal boundary central part or the concavo-convex minimizing of crystal boundary, because of the fluorine-containing heavy rare earth class CONCENTRATION DISTRIBUTION that forms with intragranular reaction mutually of crystal boundary, fluorine-containing lattice match or the orientation relationship with intragranular of crystal boundary, the formation of the fluorine-containing layer of intragranular, the formation of the fluorine-containing phase on the crystal boundary triple point, the crystal boundary triple point fluorine-containing with intragranular lattice match or orientation relationship mutually, some of increase that replaces the anisotropy energy of the NdFeB cause by fluorine atom, except the increase of coercive force, can also confirm the reduction of the temperature coefficient of coercive force or remanence, the raising of the rectangularity of demagnetization curve, the reduction of magnet loss, the increase of remanence, the increase of energy product, the reduction of hot demagnetization rate, the reduction in magnetize magnetic field, raising to easy orientation rate, reduction that can not backheating demagnetization rate, the rising of Curie point, the recovery of the magnetic characteristic of processing deterioration layer, the raising of corrosion resistance, some effect of the raising of mechanical strength.Utilize the relevant structure of this kind fluorine atom or rare earth element to change, can realize that body material Sintered NdFeB is that surface treatment, the body material sintering SmCo of alloy is the high magnetic characteristic of rare-earth sintered magnet such as alloy, can realize that the magnetic characteristic that is caused by diffusion between the rare earth element of ferrite magnet improves, Fe is the high magnetic resistanceization of soft magnetic material.The millimeter wave equifrequent is that 10 to 200GHz electromagnetic wave irradiation can only make the surface element heating in not carrying out the NdFeB sintered body of fluorine compounds solution-treated, near the diffusion of the terres rares atom the crystal boundary due to the utilization heating etc., can recover magnetic characteristic, also material that can dielectric losses such as fluorine compounds is different is as adhesive linkage, and the magnetic characteristic recovery effects ground that has affected layer concurrently is bonding with body material NdFeB.

＜embodiment 31 〉

At Co ₂The crystal boundary of MSi (transition metals beyond the Co such as M=Fe, Mn, Cr) utilizes the coated heat of fluorine compounds solution to handle the compound that growth contains fluorine, forms high magneto-resistive layer in crystal boundary portion.The thickness of high magneto-resistive layer is 0.1 to 10nm, also can form the conversion zone of a part of element that contains Co, M or Si near crystal boundary.By utilize the layer that solution-treated and heat treatment will contain fluorine to make high magneto-resistive layer at this kind crystal boundary, will show magneto resistance effect, by from the electrode stream overcurrent, just can detect the resistance variations that depends on magnetic field.In order to form fluorine compounds and to manifest magneto resistance effect in this kind crystal boundary portion, importantly can not make except the Co based material that becomes parent phase, the magnetic characteristic generation deterioration that also has Fe system, Ni system or NiFe system, PtMn system, FePt based material, fluorine compounds and reaction generation thereof are best mutually for this reason, can utilize the crystal boundary diffusion to form high magneto-resistive layer in crystal boundary portion at an easy rate, can confirm magneto resistance effect.The formed layer that contains fluorine is MxFy (M is alkali, alkali earths, terres rares and transition metal, and F is a fluorine, and x and y are integer), or is NxFyOz (M is alkali, alkali earths, terres rares and transition metal, and F is a fluorine, and O is an oxygen, and x, y and z are integer).These compounds that contain fluorine can use soln usings such as gel, colloidal sol, colloidal solution to handle and heat treatment forms.If desired, also can mix the powder that contains fluorine, but have the way of the powder of roughly the same crystal structure, on level and smooth substrate, be difficult to be controlled in 10 to 50% with the distribution of 0.1 to 100nm thickness scope with thickness for mixing with the body material.Different therewith, under the situation of solution-treated, owing to do not have the crystal structure identical with the body material, viscosity is also very low, therefore can use rotation coating machine etc. to control film thickness distribution at an easy rate and be coated with, can in various pattern treatment process or photo-mask process, use.Except crystal boundary, on the interface of laminated material, also can similarly utilize the fluorine compounds solution-treated to form high magneto-resistive layer,, can make the ferromagnetism tunnel juntion.Therefore fluorine compounds owing to can be produced on the element that has the magnetooptics characteristic beyond the magnetic field because of rayed changes its electrical property.That is, can be produced on the different element of rayed tunnel current that magnetic field utilizes specific wavelength in addition, go in the magnetic head or medium of magnetic recording system, optical/magnetic recording device.Utilize the high character of dielectric loss of fluorine based compound, can be with the heating due to the electromagnetic wave irradiation, Co system, Fe system, Ni system or NiFe system, PtMn system, FePt based material are optionally heated with the near interface that has formed the layer that contains fluorine compounds, oxygen fluorine compounds on the interface, can realize the growth to regular phase, the magnetic region structure control that causes by the heating magnetize or bias field control, change, form the local magnetic anisotropy control that causes etc. by the selectivity diffusion layer by the abnormal mutually local magnetic characteristic that causes of selectivity.This kind localized variation can confirm in area 0.5 * 0.5nm that the thickness of essential fluorine-containing layer is more than the 0.1nm.This kind utilized the Local Heating Process of dielectric loss of fluorine-containing layer except going for magnetic recording media, magnetic head, Magnetooptic recording medium, optical element, X-ray detector, can also be applicable in the operation, battery material, optical wavelength conversion element, the foreign material engaging process that comprises the joint of nano particle, nano-pattern processing procedure, grinding step etc. of the heating process, liquid crystal or the Plasma Display that comprise semi-conductive diffusing procedure.

＜embodiment 32 〉

The formation treatment fluid of terres rares fluoride or alkaline-earth metal fluoride coat film is after acetic acid terres rares or acetic acid alkaline-earth metal are dissolved in the water, and adds at leisure that the hydrofluoric acid that diluted forms.Solution to the fluorine compounds that generated gelatinous precipitate or oxygen fluorine compounds or oxygen fluorine carbide uses the ultrasonic stirring device to stir, and after the centrifugation, adds methyl alcohol, after stirring gelatinous methanol solution, removes anion and with its transparence.The anion of treatment fluid is removed, reached more than 10% until transmitance under the visible light.This solution is coated on the magnetic, removes and desolvate.As NdFeB is that powder is made with Nd ₂Fe ₁₄B is the chilling powder of main structure, uses above-mentioned solution to form the Dy fluorine compounds on their surface.After solution that will have light transmission and above-mentioned NdFeB powder, with the solvent evaporation of mixture.In the NdFeB powder, also can contain transition metal or light element.Utilize 200～700 ℃ heat treatment and the chilling after the heat treatment, the crystal structure of fluorine compounds film becomes NdF ₃Or NdF ₂Structure or oxygen fluorine compounds etc.The crystal particle diameter of parent phase is 10 to 1000nm, and the major axis of plate body is a lot of greater than having of parent grain, and minor axis length is and length below the parent grain equal extent.In addition, plate body and a plurality of parent grain are grown contiguously, have anisotropy at long axis direction, and plate body contains rare earth element and fluorine.The anisotropy of plate body can by utilize in the magnetic field growth due to the cooling along magnetic direction, stress application and form plate body or only add when the heating along the electromagnetic wave of specific direction irradiation millimeter wave along specific direction.The fluorine compounds of magnetic periphery and magnetic reaction in the heat treatment process after surface treatment, the fluorine atom of periphery moves with the terres rares atom, forms to have anisotropic plate body.The CONCENTRATION DISTRIBUTION of the rare earth element of the evolving path of plate body or plate body, oxygen and fluorine helps coercive force to increase, and has added anisotropy, consequently, can make anisotropic magnet.For adding anisotropy, and can obtain that the raising of raising, the rectangularity of coercive force, the magnetic resistance after being shaped increase, the fluorine compounds of some effect of the raising of the cementability of the raising of the increase of the raising of the temperature dependent reduction of the temperature dependent reduction of coercive force, remanence, corrosion resistance, mechanical strength, heat conductivity, magnet, except DyF ₃Or DyF ₂In addition, also have LiF, MgF ₂, CaF ₂, ScF ₃, VF ₂, VF ₃, CrF ₂, CrF ₃, MnF ₂, MnF ₃, FeF ₂, FeF ₃, CoF ₂, CoF ₃, CuF ₂, CuF ₃, NiF ₂, ZnF ₂, AlF ₃, GaF ₃, SrF ₂, YF ₃, ZrF ₃, NdF ₃, AgF, InF ₃, SnF ₂, SnF ₄, BaF ₂, LaF ₂, LaF ₃, CeF ₂, CeF ₃, PrF ₂, PrF ₃, NdF ₂, SmF ₂, SmF ₃, EuF ₂, EuF ₃, GdF ₃, TbF ₃, TbF ₄, DyF ₂, NdF ₃, HoF ₂, HoF ₃, ErF ₂, ErF ₃, TmF ₂, TmF ₃, YbF ₃, YbF ₂, LuF ₂, LuF ₃, PbF ₂, BiF ₃The oxygen fluorine compounds or the fluorocarbon that perhaps contain aerobic or carbon in these fluorine compounds can utilize the solution that used the permeability with luminous ray or the surface treatment of solution that the part of CH base and fluorine is combined forms.Have the anisotropic magnetic of this kind by use, can make remanence and be 1.0 to 1.5T, coercive force is 10 to 35kOe binding magnet or compression molding inorganic bond magnet, can under 20 to 200 ℃ ambient temperature, use.

＜embodiment 33 〉

At FeSiB or FeCuSiB, FeCuNbSiB is to use the part of solution on the powder surface that contains more than one transition metals and contain fluorine to form the layer that contains fluorine on the chilling powder.Utilize the solvent that heat treatment will contain the layer of fluorine to remove.Before solvent was removed, solution had the half breadth below 20 degree more than 0.5 degree in X-ray diffraction, utilize heat treatment, and this diffraction maximum width or half breadth narrow down gradually.If heat treatment temperature is more than 300 ℃, then the part of the fluorine atom on powder surface is to the powder diffusion inside.Utilize the diffusion of this fluorine, compare the crystal growth that can suppress due to the heat treatment with the situation that fluorine does not spread, average grain diameter is made as 1 to 100nm, can confirm the increase of permeability, the reduction of coercive force, high magnetic resistanceization; Perhaps because of in the segregation of the fluorine due to the heat treatment that has utilized magnetic field, make it to have anisotropy to the shape of crystal grain also given anisotropic raising, some effect such as increase of the saturation flux density that causes by the reduction effect of fluorine.The initial magnetic permeability of this kind soft magnetic material is 10000 to 300000, and the loss of 10kHz (0.1T) is 0.1 to 5W/kg, goes in transformer, rotating machinery, the reactor etc.

＜embodiment 34 〉

At body material NdFeB is the surface coated gel of sintered magnet or the terres rares fluorine compounds solution with light transmission of colloidal sol shape.The thickness of the terres rares fluorine compounds after the coating is 10～10000nm.NdFeB is that sintered magnet is to contain Nd ₂Fe ₁₄The magnet of the structure of B can be seen the deterioration that is accompanied by the magnetic characteristic that processing grinding or oxidation produce in the part on the surface of sintered magnet.In order to improve this kind magnetic characteristic deterioration, will be that solution coat is in sintered magnet surface and dry, heat treatment under the temperature below the sintering temperature more than 200 ℃ through the terres rares fluorine compounds of luminous ray.If utilize the localized heating of millimeter wave, then can be with near the optionally heating fluorine compounds, heat treatment temperature can be lower more than 100 ℃ than common heat treatment temperature, can also the shortening heat processing time.Soon, be particle more than the following 1nm of 100nm after the coating drying, can see that the structure around the fluorine atom changes, be accompanied by structure and change and produce and the crystal boundary of sintered magnet or the reaction or the diffusion on surface by gel or the solution growth of colloidal sol shape terres rares fluorine compounds.Owing to be not to use particle or powder, and be to use solution, therefore can control equably and apply thickness and film thickness distribution, can in material that requires cleannes or operation, use above-mentioned solution, can only coat at an easy rate by sheltering and want the part that is coated with in the solution coat front and back.Therefore this kind painting process is favourable as the processing of used magnet in precise electronic machines such as voice coil motor owing to use solution.The situation that contains various CH bases or OH base in solution is also arranged, and soon state becomes main construct different with the crystal structure after the heating after the state of solution or the coating.That is, the master of solution is constructed to and the diverse main structure of the crystal structure of fluorine compounds powder, can be in electron ray or X-ray diffraction spectrogram detects as difference very clearly, can detect wide diffraction maximum.This explanation is compared with fluorine compounds completely, and periodical configuration is subjected to partially scrambling.Solvent utilization after above-mentioned solution coat heating is removed, roughly form fluorine compounds on the sintered magnet surface comprehensively, after the coating drying, before heating under the temperature more than 300 ℃, fluoridize in the part of the high part of the grain surface rare earth element concentration of the part on sintered magnet surface.In the middle of the above-mentioned terres rares fluorine compounds,, along the crystal boundary diffusion, the deterioration of magnetic characteristic is improved as their Dy, Tb, the Ho etc. of formation element for Dy fluorine compounds or Tb, Ho fluorine compounds or their oxygen fluorine compounds.When heat treatment temperature reached more than 800 ℃, then the step that diffuses into mutually of fluorine compounds and sintered magnet carried out, thereby has the situation of seeing Fe in fluorine compound layer with the concentration more than the 1ppm.Have heat treatment temperature high more, then parent phase constitutes the tendency that the concentration of element in fluorine compound layer just increases more.The magnetic characteristic of sintered magnet is, remanence is 1.4 to 1.6T, coercive force is 20～50kOe, and having heavy rare earth dvielement concentration contained in the rare-earth sintered magnet of equal magnetic characteristic, can to add NdFeB than in the past use heavy rare earth class be that the situation of magnetic is lower.With near the TEM the typical crystal boundary (TEM) as being shown among Fig. 5.Using TbF as fluorine compounds solution is solution, and the sintered body cross-section for after handling at the Sintered NdFeB magnet surface coated heat of 10 * 10 * 5mm is shown near the picture the crystal boundary in (a).In order to compare, the cross-section with the Sintered NdFeB magnet of fluorine compounds solution-treated not is shown in (b).(a) and (b) all are near the pictures the crystal boundary triple point, and the lower right side is the crystal boundary triple point.(a) it is wideer to compare the width of crystal boundary with (b), has detected neodymium, oxygen in crystal boundary portion.(a) crystal boundary and Nd in ₂Fe ₁₄The interface of B parent phase is very clear, and (b) near the crystal boundary triple point crystal boundary portion and interface clear unlike (a), can in crystal boundary, see disorder significantly in the part of representing with arrow, the matching at interface is poor.The definition of this kind crystal boundary also is that to have carried out a side of the magnet that fluorine compounds handle more clear in other place, and the disorder of crystal boundary still less.The place is also identical at the crystal boundary triple point, and parent phase is more more clear than the interface of parent phase and neodymium oxides with the interface of oxygen fluorine compounds or fluorine compounds.This can think because, fluorine is fixed (catching) in crystal boundary with rare earth element or oxygen, and is relevant with the effect that has parent phase reduction.The fluorine system that this kind reduces the disorder of crystal boundary handles because therefore the generation of the anti-magnetic region that can prevent to produce from crystal boundary can confirm the raising of the coercive force of magnet, the raising of rectangularity, the raising of energy product, the improvement of demagnetization rate, the improvement of the magnetic characteristic deterioration due to the affected layer, the reduction of heavy rare earth dvielement use amount, some effect such as reduction of loss.

＜embodiment 35 〉

Made the formation treatment fluid of terres rares fluoride or alkaline-earth metal fluoride coat film as followsly.

(1) for the high salt of solubility in water, for example the situation of La adds lanthanum acetate or lanthanum nitrate 4g in the 100mL water, uses oscillator or ultrasonic stirring device fully to dissolve.

(2) dilution of equivalent that add to generate the chemical reaction of LaFx (x=1-3) at leisure is 10% hydrofluoric acid.

(3) solution to the LaFx (x=1-3) that generated gelatinous precipitate uses the ultrasonic stirring device to stir more than 1 hour.

(4) after rotating speed centrifugation, abandon supernatant, add the methyl alcohol of roughly the same amount with 4000～6000r.p.m.

(5) stir the methanol solution that contains gelatinous LaF bunch and after fully becoming suspension-turbid liquid, use the ultrasonic stirring device to stir more than 1 hour.

(6) repeat the operation 3～10 times of (4) and (5), until detecting less than anion such as acetic acid ion or nitrate ions.

(7), become the LaFx of transparent haply colloidal sol shape for the situation of LaF system.Used the methanol solution of LaFx as treatment fluid as 1g/5mL.

(8) organo-metallic compound beyond the de-carbon of interpolation table 2 in above-mentioned solution.

The formation treatment fluid of other used terres rares fluoride or alkaline-earth metal fluoride coat film also can be used with above-mentioned essentially identical operation and form, even to the Dy shown in the table 2, Nd, La, Mg fluorine is to add various elements in the treatment fluid, the diffraction spectrogram of any solution also all with fluorine compounds or oxygen fluorine compounds or inconsistent with REnFm (RE is terres rares or alkali earths element, and n, m are positive number) expression with the compound that adds element.If the scope of the content of the interpolation element of table 2, then can not change the structure of solution greatly.Solution or the diffraction spectrogram of the dried film of solution is made of a plurality of peaks that comprise the diffraction maximum of half breadth more than 1 degree.This explanation is added between element and the fluorine or the interatomic distance between the metallic element is different from REnFm, and crystal structure also is different from REnFm.Because half breadth is more than 1 degree, therefore above-mentioned interatomic distance is not to be certain value as common metallic crystal, but has certain distribution.The reason that forms this kind distribution is, around the atom of above-mentioned metallic element or fluorine element, dispose other atom, this atom mainly is hydrogen, carbon, oxygen, apply external energy by heating to wait, atoms such as these hydrogen, carbon, oxygen are easy to move, structure changes, and flowability also changes.Colloidal sol shape or gelatinous X-ray diffraction spectrogram are made of the peak of half breadth greater than 1 degree, and utilize heat treatment can see that structure changes, thereby can see above-mentioned REnFm or REn (F, O) part of the diffraction spectrogram of m.Interpolation element shown in the table 2 does not have the long period structure in solution.It is narrower that the diffraction maximum of this REnFm and the diffraction maximum of above-mentioned colloidal sol or gel are compared half breadth.Make the coating film thickness homogenization for the flowability that improves solution, can see at least that in the diffraction spectrogram of above-mentioned solution a peak with the half breadth more than 1 degree is very important.Peak and the diffraction spectrogram of REnFm or the peak of oxygen fluorine compounds that also can comprise the above half breadth of this kind 1 degree.Under the situation of the diffraction spectrogram below the main diffraction spectrogram or 1 that only observes REnFm or oxygen fluorine compounds is spent in the diffraction spectrogram of solution, be not the solid phase of colloidal sol or gel owing in solution, be mixed with, therefore mobile poor, be difficult to be coated with equably.

(9) with bulk (10 * 10 * 10mm of NdFeB sintered body ³) to be immersed in LaF be that coat film forms in the treatment fluid, this bulk is carried out the methyl alcohol of solvent and remove under the decompression of 2～5torr.

(10) operation with (9) repeated 1 to 5 time, at heat treatment 0.5-5 from 400 ℃ to 1100 ℃ temperature range hour.

(11) apply pulsed magnetic field more than the 30kOe along the anisotropic orientation that in (10), has formed the anisotropic magnet of surface-coated film.

This magnetize formed body is clamped between magnetic pole with direct current M-H loop line analyzer, makes that to apply direction consistent for rise magnetic direction and the magnetic field of formed body, by apply magnetic field between magnetic pole, measured demagnetization curve.The magnetize formed body is being applied in the pole piece of field pole, using the FeCo alloy, magnetized value is to use identical shaped pure Ni sample and pure Fe sample to proofread and correct.

Consequently, the coercive force of bulk that has formed the NdFeB sintered body of terres rares fluoride coat film increases, under un-added situation, Dy, Nd, La and Mg fluoride or oxyfluoride segregation sintered magnet in, coercive force has increased by 30%, 25%, 15% and 10% respectively.Utilize the coated heat that does not add solution to handle the coercive force that increases like this in order further to increase, the interpolation element that table 2 is such uses organo-metallic compound to add in each fluoride aqueous solution.When the coercive force with the situation of not adding solution is benchmark, then utilize in the solution shown in the table 2 and add element, the coercive force of sintered magnet further increases, and distinguishes that these add the increase that elements help coercive force.The result of coercive force increment rate is shown in the table 2.Add near can the removing of element in the solution to and see short scope structure,, constitute element along the crystal boundary of sintered magnet with solution and spread then by heat-treating because of solvent.These add element and demonstrate the tendency that constitutes the part segregation of element with solution near crystal boundaries.Spread in sintered magnet so the interpolation element shown in the table 2 is accompanied by at least a element of fluorine, oxygen and carbon, stay near the crystal boundary.The composition that shows the sintered magnet of high coercive force demonstrates the concentration height that constitutes the element of fluoride aqueous solution at the magnet peripheral part, becomes the tendency of low concentration in magnetic blow out centre portion.This is because it is also dry to contain the fluoride aqueous solution that adds element in the coating of the outside of sintered magnet bulk, grows and contains fluoride or the oxygen fluoride that adds the short scope structure of having of element, and spread along near the crystal boundary.That is, in the sintered magnet bulk, can see the concentration gradient of at least a element of the interpolation element shown in fluorine and the table 2 from outer circumferential side.The oxygen fluoride that contains the element of table 2 in the most surperficial formation of sintered magnet bulk; Perhaps contain the element of table 2 and the oxygen fluoride of carbon; The oxygen fluoride that perhaps contains the constituent of at least a element of element of table 2 and at least a sintered magnet.The superficial layer of this kind is except guaranteeing corrosion resistance, essential layer also for the magnetic characteristic that improves sintered magnet, and resistance also is higher than the principal phase of sintered magnet.Content is consistent basically with the scope with light transmission of solution in the solution of the interpolation element of table 2, further increase concentration, also can make solution, can increase coercive force, under the situation of element shown in interpolation table 2 in certain of the fluoride that contains more than one rare earth elements at least, oxide or the oxygen fluoride of slip shape, compare with un-added situation, can confirm to obtain the raising of magnetic characteristics such as high coercive force.Be made as under the situation more than 100 times of table 2 adding concentration of element, the structure that constitutes the fluoride of solution changes, the distribution of adding element in the solution becomes inhomogeneous, can see the tendency of the elemental diffusion that hinders other, be difficult to make add element along cyrystal boundary segregation to magnet bulk inside, can see the increase of coercive force in the part.Interpolation element shown in the table 2 act as following certain.1) near segregation and reduce interface energy crystal boundary.2) lattice match of raising crystal boundary.3) defective of minimizing crystal boundary.4) promote the crystal boundary diffusion of rare earth element etc.5) improve near the magnetic anisotropy energy of crystal boundary.6) will with the interface smoothing of fluoride or oxygen fluoride.Their result is, can utilize some effect of the reduction of the reducing of rising, magnetize magnetic field, coercive force or the temperature dependent reduction of remanence of increase, the Curie temperature of increase, the energy product of raising, the remanence of the rectangularity of the coating of the solution of the interpolation element that has used table 2, increase that diffusion heat treatments is seen coercive force, demagnetization curve, the raising of corrosion resistance, the increase of resistivity, hot demagnetization rate.In addition, the CONCENTRATION DISTRIBUTION of the interpolation element shown in the table 2 demonstrates and sees that on an average concentration from the tendency that the sintered magnet periphery reduces to inside, demonstrates the tendency that reaches high concentration in crystal boundary portion.The width of crystal boundary has different tendencies with place away from the crystal boundary triple point near the crystal boundary triple point, near the bigger tendency of the side's width crystal boundary triple point is arranged.Interpolation element shown in the table 2 easily from crystal boundary mutually or the end of crystal boundary, crystal boundary towards intragranular ground in the somewhere segregation of the periphery (crystal boundary side) of intragranular.Can confirm that additive in the solution of raising of magnetic characteristic of above-mentioned magnet is the element in Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Zr, Nb, Mo, Pd, Ag, In, Sn, Hf, Ta, W, Ir, Pt, Au, Pb, Bi that is selected from table 2 or the atom that the comprises whole transition metals numbering 18 to 86, can see concentration gradient at least a element in the middle of them and fluorine in sintered magnet.These add element owing to add thermal diffusion after using solution-treated, therefore distribute different with the composition that adds the element in the sintered magnet in advance to, near the crystal boundary of fluorine institute segregation, reach high concentration, (apart from the average 1000nm in crystal boundary center with interior distance) can see the elements segregation of adding in advance near the crystal boundary of the reduced in segregation of fluorine, shows average concentration gradient to inside from the magnet bulk is the most surperficial.Adding concentration of element is under the situation of low concentration in solution, can confirm by forming concentration gradient or concentration difference.Adding the interpolation element like this in solution, after utilizing heat treatment to improve the characteristic of sintered magnet after the coating on the magnet bulk, the feature of sintered magnet is as follows.1) can be from sintered magnet the most surperficial to the element of internally seeing table 2 or comprise the concentration gradient of element of atom numbering 18 to 86 of transition metal or average concentration difference.2) element of the table 2 that can see with fluorine or comprise near the part of the segregation of element crystal boundary of the atom numbering 18 to 86 of transition metal is arranged a lot.3) crystal boundary mutually in fluorine concentration height, fluorine concentration is low in the outside of crystal boundary phase, can see the fluorine concentration difference near, can see the elements segregation of the element of table 2 or atom numbering 18 to 86, and can see average concentration gradient or concentration difference to inside from magnet bulk surface.4) at the most peripheral fluorine of the sintered magnet bulk that has been coated with solution or magnetic iron powder or ferromagnetism powder and to add the concentration of element the highest, can be from the outside the magnetic body towards internally seeing the concentration gradient or the concentration difference of adding element.5) the interpolation element of table 2 or formation comprise at least a in the element of solution of element of atom numbering 18 to 86 from the surface towards internally having concentration gradient, seeing the outside by the near interface of the magnet of solution growth and fluoropolymer membrane or from magnet at the interface, fluorine concentration maximum, the fluoride of near interface contains aerobic or carbon, helps certain of highly corrosion resistant, high resistance or high magnetic characteristic.In this fluoropolymer membrane, can detect more than interpolation element shown in the table 2 or atom numbering 18 to 86 element at least a or two, near the evolving path of the fluorine of magnet inside, contain a lot of above-mentioned interpolation elements, can see some effect of reduction of the reducing of rising, magnetize magnetic field, coercive force or the temperature dependent reduction of remanence, the raising of corrosion resistance, the increase of resistivity, hot demagnetization rate of increase, Curie temperature of increase, energy product of raising, remanence of rectangularity of increase, the demagnetization curve of coercive force.The concentration difference of above-mentioned interpolation element can be confirmed the sample analysis after the sintering bulk is cut from surface lateral inside by EDX (energy dispersive X-ray) analysis or EPMA analysis, the icp analysis etc. that utilize TEM.Can utilize the EDX or the EELS of TEM to analyze the situation of adding the element generation segregation of the atom numbering 18 to 86 in the solution at (in the segregation position 2000nm apart from fluorine atom, in the preferred 1000nm) near the fluorine atom.Is 1.1 to 1000 near the interpolation element of the segregation fluorine atom with being present in ratio apart from the interpolation element of the position more than the segregation position 2000nm of fluorine atom inner position more than distance magnet surface 100 μ m, preferably more than 2.At the above-mentioned ratio of magnet surface more than 2.For above-mentioned interpolation element, be along the crystal boundary part of segregation or which kind of state of the part of segregation discontinuously all exists continuously, might not be segregation on whole crystal boundary, and become discontinuous easily at the central side of magnet.In addition, not segregation and sneak into parent phase fifty-fifty of a part of adding element.The interpolation element of atom numbering 18 to 86 has near the tendency of the concentration minimizing of segregation fluorine segregation position to inside from the surface of sintered magnet, because this CONCENTRATION DISTRIBUTION is compared with magnet inside, demonstrating the higher tendency of coercive force near the surface.Above-mentioned magnetic characteristic is improved effect and is not only in the sintered magnet bulk and can obtains, even be that the solution shown in the magnetic powder surface use table 2 forms the film that contains fluorine and add element at NdFeB, also can utilize diffusion heat treatments to obtain identical effect.So, just can be by after the NdFeB powder is shaped in magnetic field temporarily, to sintering behind the solution of interim formed body dipping table 2, or be that powder is after powder mixes with the NdFeB that is untreated by carry out surface-treated NdFeB at the solution with use table 2, interim be shaped and sintering is made sintered magnet in magnetic field.In this kind sintered magnet, the CONCENTRATION DISTRIBUTION of adding the solution constituent of element etc. in fluorine or the solution is homogeneous on an average, yet because of near the concentration of the interpolation element of table 2 the evolving path of fluorine atom is higher on an average, so the magnetic characteristic raising.

[table 2]

Table 2

＜embodiment 36 〉

A kind of rare earth element permanent magnet, be by in R-Fe-B system (R is a rare earth element) sintered magnet from diffusion into the surface G composition (G be from transition metal and rare earth element, select respectively more than one element or more than one the element of from transition metal and alkaline-earth metal element, selecting respectively) and fluorine atom get, have with following formula (1) or (2)

R _aG _bT _cA _dF _eO _fM _g(1)

(R·G) _a+bT _cA _dF _eO _fM _g(2)

(here, R is selected from the rare earth element one or more, M was present in to remove 2 families beyond the rare earth element to the element beyond C and the B removed of 116 families in the sintered magnet before coating contains the solution of fluorine, G be from transition metal and rare earth element, select respectively more than one element or more than one the element of from transition metal and alkaline-earth metal element, selecting respectively, R and G also can contain identical element, do not contain under the situation of identical element at R and G, with formula (1) expression, contain at R and G under the situation of identical element and represent with formula (2).T is selected among Fe and the Co one or both, A is selected among B (boron) and the C (carbon) one or more, a-g calculates with the atom % of alloy, and a, b are 10≤a≤15,0.005≤b≤2 under the situation of formula (1), under the situation of formula (2) 10.005≤a+b≤17,3≤d≤15,0.01≤e≤4,0.04≤f≤4,0.01≤g≤11, remainder are c.) sintered magnet of composition of expression, it is characterized in that, as at least aly distributing that it constitutes the F of element and transition metal to contain the mode that concentration uprises on an average towards magnet surface from magnetic blow out centre, and the encirclement in this sintered magnet by (R, G) ₂T ₁₄In the crystal boundary portion around the A cube of brilliant main phase grain that constitutes, the concentration of contained G/ (R+G) is on an average greater than the concentration of G/ in the main phase grain (R+G) in the crystal boundary, and in the depth areas of distance magnet surface at least 10 μ m, the oxygen fluoride, fluoride or the carbon oxygen fluoride that have R and G in crystal boundary portion, near the magnet top layer coercive force is higher than inside, one of its feature is, can see the concentration gradient of transition metal from the surface of sintered magnet towards the center, can utilize the example of following gimmick to make.

The terres rares fluoride that added transition metal or the formation treatment fluid of alkaline-earth metal fluoride coat film have been made as followsly.

(1) for the high salt of solubility in water, for example the situation of Dy adds acetic acid dysprosium or dysprosium nitrate 4g in the 100mL water, uses oscillator or ultrasonic stirring device fully to dissolve.

(2) dilution of equivalent that add to generate the chemical reaction of DyFx (x=1-3) at leisure is 10% hydrofluoric acid.

(3) solution to the DyFx (x=1-3) that generated gelatinous precipitate uses the ultrasonic stirring device to stir more than 1 hour.

(4) after with 4000～6000 rotating speed centrifugation, abandon supernatant, add the methyl alcohol of roughly the same amount.

(5) stir the methanol solution that contains gelatinous DyF bunch and after fully becoming suspension-turbid liquid, use the ultrasonic stirring device to stir more than 1 hour.

(6) repeat the operation 3～10 times of (4) and (5), until detecting less than anion such as acetic acid ion or nitrate ions.

(7), become the DyFx of transparent haply colloidal sol shape for the situation of DyF system.Used the methanol solution of DyFx as treatment fluid as 1g/5mL.

(8) organo-metallic compound beyond the de-carbon of interpolation table 2 in above-mentioned solution.

The formation treatment fluid of other used terres rares fluoride or alkaline-earth metal fluoride coat film also can be used with above-mentioned essentially identical operation and form, even to the Dy shown in the table 2, Nd, La, the Mg fluorine is to add various elements in the treatment fluid, the diffraction spectrogram of any solution is also all with (RE is terres rares or alkali earths element with REnFm, n, m is a positive number) or REnFmOpCr (RE is terres rares or alkali earths element, O is an oxygen, C is a carbon, F is a fluorine, n, m, p, r is a positive number) fluorine compounds or the oxygen fluorine compounds or inconsistent of expression with the compound that adds element.If the scope of the content of the interpolation element of table 2, then can not change the structure of solution greatly.Solution or with the diffraction spectrogram of the dried film of solution by comprising that a plurality of peaks of half breadth more than 1 degree constitute.This explanation is added between element and the fluorine or the interatomic distance between the metallic element is different from REnFm, and crystal structure also is different from REnFm.Because half breadth is more than 1 degree, therefore above-mentioned interatomic distance is not to be certain value as common metallic crystal, but has certain distribution.The reason that forms this kind distribution is, atom with other around the atom of above-mentioned metallic element or fluorine element has carried out the configuration different with above-claimed cpd, this atom mainly is hydrogen, carbon, oxygen, apply external energy by heating to wait, atoms such as these hydrogen, carbon, oxygen are easy to move, structure changes, and flowability also changes.Colloidal sol shape or gelatinous X-ray diffraction spectrogram are made of the peak of half breadth greater than 1 degree, and utilize heat treatment can see that structure changes, thereby can see above-mentioned REnFm or REn (F, O) part of the diffraction spectrogram of m.Can think that the interpolation element shown in the table 2 does not have the long period structure in solution.It is narrower that the diffraction maximum of this REnFm and the diffraction maximum of above-mentioned colloidal sol or gel are compared half breadth.Make the coating film thickness homogenization for the flowability that improves solution, can see at least that in the diffraction spectrogram of above-mentioned solution a peak with the half breadth more than 1 degree is very important.Peak and the diffraction spectrogram of REnFm or the peak of oxygen fluorine compounds that also can comprise the above half breadth of this kind 1 degree.Under the situation of the diffraction spectrogram below the main diffraction spectrogram or 1 that only observes REnFm or oxygen fluorine compounds is spent in the diffraction spectrogram of solution, because be mixed with in solution is not the solid phase of colloidal sol or gel, therefore mobile variation, however can see the increase of coercive force.

(9) with bulk (10 * 10 * 10mm of NdFeB sintered body ³) to be immersed in DyF be that coat film forms in the treatment fluid, this bulk is carried out the methyl alcohol of solvent and remove under the decompression of 2～5torr.

(10) operation with (9) repeated 1 to 5 time, at heat treatment 0.5-5 from 400 ℃ to 1100 ℃ temperature range hour.

(11) apply pulsed magnetic field more than the 30kOe along the anisotropic orientation that in (10), has formed the anisotropic magnet of surface-coated film.

This magnetize formed body with the clamping of direct current M-H loop line analyzer, is made that to apply direction consistent for rise magnetic direction and the magnetic field of formed body, by apply magnetic field between magnetic pole, measured demagnetization curve.The magnetize formed body is being applied in the pole piece of field pole, using the FeCo alloy, magnetized value is to use identical shaped pure Ni sample and pure Fe sample to proofread and correct.

Consequently, the coercive force of bulk that has formed the NdFeB sintered body of terres rares fluoride coat film increases, and the sintered magnet when not adding is compared, and by using the interpolation treatment fluid of transition metal, coercive force further increases.The coercive force that utilizes the coated heat that does not add solution to handle like this and increase further increases explanation, and these add the increase that element helps coercive force.Add near can the removing of element in the solution to and see short scope structure,, constitute element along the crystal boundary of sintered magnet with solution and spread then by heat-treating because of solvent.These add element and demonstrate the tendency that constitutes the part segregation of element with solution near crystal boundaries.The composition that shows the sintered magnet of high coercive force demonstrates the concentration height that constitutes the element of fluoride aqueous solution at the magnet peripheral part, becomes the tendency of low concentration in magnetic blow out centre portion.This is because it is also dry to contain the fluoride aqueous solution that adds element in the coating of the outside of sintered magnet bulk, grows and contains fluoride or the oxygen fluoride that adds the short scope structure of having of element, and spread along near the crystal boundary.That is, in the sintered magnet bulk, can see the concentration gradient of at least a element of the interpolation element shown in fluorine and the table 2 from outer circumferential side.Content is consistent basically with the scope with light transmission of solution in the solution of the interpolation element of table 2, further increases concentration, also can make solution.Under the situation of the element that in certain of the fluoride that contains more than one rare earth elements at least, oxide or the oxygen fluoride of slip shape, adds atom numbering 18 to 86, compare with un-added situation, can confirm to obtain the raising of magnetic characteristics such as high coercive force.Add acting as of element following certain.1) near segregation and reduce interface energy crystal boundary.2) lattice match of raising crystal boundary.3) defective of minimizing crystal boundary.4) promote the crystal boundary diffusion of rare earth element etc.5) improve near the magnetic anisotropy energy of crystal boundary.6) will with the interface smoothing of fluoride or oxygen fluoride.7) anisotropy of raising rare earth element.8) oxygen is removed from parent phase.9) Curie temperature of raising parent phase.Their result is, can see some effect of reduction of the reducing of rising, magnetize magnetic field, coercive force or the temperature dependent reduction of remanence, the raising of corrosion resistance, the increase of resistivity, hot demagnetization rate of increase, Curie temperature of increase, energy product of raising, remanence of rectangularity of increase, the demagnetization curve of coercive force.In addition, the CONCENTRATION DISTRIBUTION that comprises the transition metal of the interpolation element shown in the table 2 demonstrates and sees that on an average concentration from the tendency that the sintered magnet periphery reduces to inside, demonstrates the tendency that reaches high concentration in crystal boundary portion.The width of crystal boundary has different tendencies with place away from the crystal boundary triple point near the crystal boundary triple point, near the bigger tendency that reaches high concentration of the side's width crystal boundary triple point is arranged.Transition metal add element easily from crystal boundary mutually or the end of crystal boundary, crystal boundary towards intragranular ground in the somewhere segregation of the periphery (crystal boundary side) of intragranular.These add element owing to add thermal diffusion after using solution-treated, therefore distribute different with the composition that adds the element in the sintered magnet in advance to, near the crystal boundary of fluorine or the segregation of rare earth element institute, reach high concentration, near the crystal boundary of the reduced in segregation of fluorine, can see the elements segregation of adding in advance, show average concentration gradient to inside from the magnet bulk is the most surperficial.Adding concentration of element is under the situation of low concentration in solution, can confirm by forming concentration gradient or concentration difference.Adding the interpolation element like this in solution, after utilizing heat treatment to improve the characteristic of sintered magnet after the coating on the magnet bulk, the feature of sintered magnet is as follows.1) can be from the most surperficial to the concentration gradient of internally seeing transition metal or average concentration difference.2) can see near the segregation of transition metal crystal boundary with fluorine.3) crystal boundary mutually in fluorine concentration height, fluorine concentration is low in the outside of crystal boundary phase, can see the fluorine concentration difference near, can see the segregation of transition metal, and can see average concentration gradient or concentration difference to inside from magnet bulk surface.4) contain the fluoride layer or the oxygen fluoride layer of transition metal, fluorine and carbon in the superficial growth of sintered magnet bulk.

＜embodiment 37 〉

A kind of rare earth element permanent magnet, be by in R-Fe-B system (R is a rare earth element) sintered magnet from diffusion into the surface G composition (G be from transition metal and rare earth element, select respectively more than one element or more than one the element of from transition metal and alkaline-earth metal element, selecting respectively) and fluorine atom get, have with following formula (1) or (2)

R _aG _bT _cA _dF _eO _fM _g(1)

(R·G) _a+bT _cA _dF _eO _fM _g(2)

(here, R is selected from the rare earth element one or more, M was present in to remove 2 families beyond the rare earth element to the element beyond C and the B removed of 116 families in the sintered magnet before coating contains the solution of fluorine, G be from transition metal and rare earth element, select respectively more than one element or more than one the element of from transition metal and alkaline-earth metal element, selecting respectively, R and G also can contain identical element, do not contain under the situation of identical element at R and G, with formula (1) expression, contain at R and G under the situation of identical element and represent with formula (2).T is selected among Fe and the Co one or both, A is selected among B (boron) and the C (carbon) one or more, a-g calculates with the atom % of alloy, and a, b are 10≤a≤15,0.005≤b≤2 under the situation of formula (1), under the situation of formula (2) 10.005≤a+b≤17,3≤d≤15,0.01≤e≤4,0.04≤f≤4,0.01≤g≤11, remainder are c.) sintered magnet of composition of expression, it is characterized in that, as at least aly distributing that it constitutes the F of element and semimetallic elements or transition metal to contain the mode that concentration uprises on an average towards magnet surface from magnetic blow out centre, and the encirclement in this sintered magnet by (R, G) ₂T ₁₄During crystal boundary portion around the A cube of brilliant main phase grain that constitutes or sintered magnet are the most surperficial, the concentration of contained G/ (R+G) is on an average greater than the concentration of G/ in the main phase grain (R+G) in the crystal boundary, and in the depth areas of distance magnet surface at least 1 μ m, the oxygen fluoride, fluoride or the carbon oxygen fluoride that have R and G in crystal boundary portion, near the magnet top layer coercive force is higher than inside, one of its feature is, can see the concentration gradient of transition metal from the surface of sintered magnet towards the center, can utilize the example of following gimmick to make.

The terres rares fluoride that added transition metal or the formation treatment fluid of alkaline-earth metal fluoride coat film have been made as followsly.

(1) for the high salt of solubility in water, for example the situation of Dy adds acetic acid dysprosium or dysprosium nitrate 4g in the 100mL water, uses oscillator or ultrasonic stirring device fully to dissolve.

(2) dilution of equivalent that add to generate the chemical reaction of DyFx (x=1-3) at leisure is 10% hydrofluoric acid.

(3) solution to the DyFx (x=1-3) that generated gelatinous precipitate uses the ultrasonic stirring device to stir more than 1 hour.

(4) after with 4000～6000 rotating speed centrifugation, abandon supernatant, add the methyl alcohol of roughly the same amount.

(5) stir the methanol solution contain gelatinous DyF system or DyFC system, DyFO system bunch and after fully becoming suspension-turbid liquid, use the ultrasonic stirring device to stir more than 1 hour.

(6) repeat the operation 3～10 times of (4) and (5), until detecting less than anion such as acetic acid ion or nitrate ions.

(7), become the DyFx that contains C or O of transparent haply colloidal sol shape for the situation of DyF system.Used the methanol solution of DyFx as treatment fluid as 1g/5mL.

(8) organo-metallic compound beyond the de-carbon of interpolation table 2 in above-mentioned solution.

The formation treatment fluid of other used terres rares fluoride or alkaline-earth metal fluoride coat film also can be used with above-mentioned essentially identical operation and form, even to containing Dy, Nd, La, the fluorine of rare earth element such as Mg or alkali earths element is to add various elements in the treatment fluid, the diffraction spectrogram of any solution is also all with (RE is terres rares or alkali earths element with REnFm, n, m is a positive number) or REnFmOpCr (RE is terres rares or alkali earths element, O is an oxygen, C is a carbon, F is a fluorine, n, m, p, r is a positive number) fluorine compounds or the oxygen fluorine compounds or inconsistent of expression with the compound that adds element.Their solution or can to observe the diffraction spectrogram of the dried film of solution with a plurality of peaks of half breadth more than 1 degree be the X-ray diffraction spectrogram of main peak.This explanation is added between element and the fluorine or the interatomic distance between the metallic element is different from REnFm, and crystal structure also is different from REnFm.Because half breadth is more than 1 degree, therefore above-mentioned interatomic distance is not to be certain value as common metallic crystal, but has certain distribution.The reason that forms this kind distribution is, atom with other around the atom of above-mentioned metallic element or fluorine element has carried out the configuration different with above-claimed cpd, this atom mainly is hydrogen, carbon, oxygen, apply external energy by heating to wait, atoms such as these hydrogen, carbon, oxygen are easy to move, structure changes, and flowability also changes.Colloidal sol shape or gelatinous X-ray diffraction spectrogram are by comprising that the diffraction spectrogram of half breadth greater than the peak of 1 degree constitutes, and changes and utilize heat treatment to see and construct, thereby can see above-mentioned REnFm, REn (F, C, O) part of the diffraction spectrogram of m (ratio of O is arbitrarily for F, C).It is narrower that these diffraction maximums and the diffraction maximum of above-mentioned colloidal sol or gel are compared half breadth.Make the coating film thickness homogenization for the flowability that improves solution, can see at least that in the diffraction spectrogram of above-mentioned solution a peak with the half breadth more than 1 degree is very important.

(9) with bulk (10 * 10 * 10mm of NdFeB sintered body ³), the interim formed body of NdFeB or NdFeB be magnetic to be immersed in DyF be that coat film forms in the treatment fluid, this bulk is carried out the methyl alcohol of solvent and remove under the decompression of 2～5torr.

(10) operation with (9) repeated 1 to 5 time, at heat treatment 0.5-5 from 400 ℃ to 1100 ℃ temperature range hour.

(11) apply pulsed magnetic field more than the 30kOe along in (10), having formed the sintered magnet of surface-coated film or anisotropic orientation that NdFeB is magnetic.

This magnetize formed body is clamped between magnetic pole with direct current M-H loop line analyzer, makes that to apply direction consistent for rise magnetic direction and the magnetic field of formed body, by apply magnetic field between magnetic pole, measured demagnetization curve.The magnetize formed body is being applied in the pole piece of field pole, using the FeCo alloy, magnetized value is to use identical shaped pure Ni sample and pure Fe sample to proofread and correct.

Consequently, the coercive force of bulk that has formed the NdFeB sintered body of terres rares fluoride coat film increases, and the sintered magnet when not adding is compared, and by using the interpolation treatment fluid of transition metal, coercive force further increases.Coercive force or the rectangularity utilizing the coated heat that does not add solution to handle like this and increase further increase explanation, and these add the increase that element helps coercive force.Add near can the removing of atom site in the solution to and see short scope structure,, constitute element along the crystal boundary of sintered magnet with solution and spread then by heat-treating because of solvent.These add element and demonstrate the tendency that constitutes the part segregation of element with solution near crystal boundaries.The composition that shows the sintered magnet of high coercive force demonstrates the concentration height that constitutes the element of fluoride aqueous solution at the magnet peripheral part, becomes the tendency of low concentration in magnetic blow out centre portion.This is because it is also dry to contain the fluoride aqueous solution that adds element in the coating of the outside of sintered magnet bulk, grows and contains fluoride or the oxygen fluoride that adds the short scope structure of having of element, and spread along near the crystal boundary.That is, in the sintered magnet bulk, can see the concentration gradient or the concentration difference of at least a element of the interpolation element of transition metal shown in fluorine and the table 2 or semimetallic elements from outer circumferential side.In certain of the fluoride that contains a kind of rare earth element at least, oxide or the oxygen fluoride of slip shape, adding under the situation of transition metal, compare with un-added situation, can confirm to obtain the raising of magnetic characteristics such as high coercive force, yet add in the solution of the transparency under the situation of transition metal or semimetallic elements, it is more obvious that magnetic characteristics such as coercive force increase effect are improved effect.Under the situation of not using rare earth element or alkali earths element, by making the fluoride aqueous solution that contains interpolation element as shown in table 2, coat on the magnetic, can see that also magnetic characteristic improves effect.Add acting as of element following certain.1) near segregation and reduce interface energy crystal boundary.2) lattice match of raising crystal boundary.3) defective of minimizing crystal boundary.4) promote the crystal boundary diffusion of rare earth element etc.5) improve near the magnetic anisotropy energy of crystal boundary.6) will with the interface smoothing of fluoride or oxygen fluoride.7) anisotropy of raising rare earth element.8) oxygen is removed from parent phase.9) Curie temperature of raising parent phase.10) combine with other element of segregation in crystal boundary and change the electronic structure of crystal boundary.Their result is, can see some effect of reduction of the reducing of rising, magnetize magnetic field, coercive force or the temperature dependent reduction of remanence, the raising of corrosion resistance, the increase of resistivity, hot demagnetization rate of increase, Curie temperature of increase, energy product of raising, remanence of rectangularity of increase, the demagnetization curve of coercive force.Add in the solution and the transition metal of diffusion add element or semimetallic elements easily from crystal boundary mutually or the end of crystal boundary, crystal boundary towards intragranular ground in the somewhere segregation of the periphery (crystal boundary side) of intragranular.These add element owing to add thermal diffusion after using solution-treated, therefore distribute different with the composition that adds the element in the sintered magnet in advance to, near the crystal boundary of fluorine or the segregation of rare earth element institute, reach high concentration, near the crystal boundary of the reduced in segregation of fluorine, can see the elements segregation of adding in advance, show average concentration gradient to inside from the magnet bulk is the most surperficial, even add the segregation place segregation irrespectively of element and fluorine, also can improve magnetic characteristic.Adding concentration of element be under the situation of low concentration in solution, can be by analyzing the sample that relatively the magnet bulk has been cut, and formation concentration gradient or concentration difference confirm.Adding the interpolation element like this in solution, after utilizing heat treatment to improve the characteristic of sintered magnet after the coating on the magnet bulk, the feature of sintered magnet is as follows.1) can with fluoride as the solution of principal component in from the concentration gradient of the most surperficial at least a element that is numbered 18 to 86 element to atoms such as internally seeing transition metal or semimetallic elements or average concentration difference, concentration has the tendency that reduces to inside from magnet portion surface.2) can see transition metal or near the segregation of semimetallic elements magnet portion crystal boundary of adding in the solution with fluorine.3) crystal boundary mutually in fluorine concentration height, fluorine concentration is low in the outside of crystal boundary phase, can see the fluorine concentration difference near, can see that sometimes transition metal etc. adds elements segregation, can see average concentration gradient or concentration difference from magnet bulk surface to inside.4) contain the fluoride layer of transition metal, fluorine and carbon or contain the oxygen fluorine compounds or the fluoride of the element of atom numbering 18 to 86 in the most surperficial grown in thickness of sintered magnet with 1 to 10000nm.The element of this atom numbering 18 to 86 can be in the concentration difference of seeing from the most surperficial depth direction towards inside more than the 10ppm.This layer that contains fluorine contains the formation element of some sintered magnet, and these superficial layers can utilize to grind to wait and remove in final products, yet preferably as being used to guarantee that the diaphragm former state of corrosion resistance is residual.5) concentration gradient of the interpolation element that adds in advance before solution-treated is different with the concentration gradient of the element that adds in solution-treated, the former depends on the average concentration gradient of the principal component of fluoride aqueous solutions such as fluorine, and the latter's concentration analysis can be seen dependence at least a element of the formation element of fluoride aqueous solution and concentration analysis.

＜embodiment 38 〉

As NdFeB is that powder is made with Nd ₂Fe ₁₄B is main chilling powder, forms fluorine compounds on their surface.Form DyF on chilling powder surface ₃Situation under, as raw material with Dy (CH ₃COO) ₃Use H ₂HF is added in the O dissolving.Utilize the interpolation of HF can form the DyF of gelatin-like ₃XH ₂O.With its centrifugation, remove and desolvate.The terres rares fluoride concentration of collosol state is at 10g/dm ³More than, optical path length is that the transmitance of 1cm is more than 5% under the 700nm wavelength of this treatment fluid.Have to this kind and to add at least a compound or the solution that contains transition metal or semimetallic elements in the solution of light transmission.X-ray diffraction peak after the interpolation is very wide, and the half breadth of diffraction maximum is 1 to 10 degree, has flowability.This solution is mixed with above-mentioned NdFeB powder.With the solvent evaporation of mixture, utilize heating that hydrate water is evaporated.Utilize 500～800 ℃ heat treatment to distinguish, the crystal structure of fluorine compounds film is by containing the NdF that adds element ₃Structure, NdF ₂Formations such as structure or oxygen fluoride.The Nd of Dy in the evolving path in magnetic or the segregation of Nd, plate body or the segregation of Dy and fluorine, can also see the interpolation elements segregation, the raisings of the ferromagnetism combination that causes to the reduction of parent phase, by the diffusion of iron in fluoride because of the raising of the lattice match of the increase of anisotropy energy, crystal boundary, fluorine etc., magnetic characteristic improves.In order to reduce the use amount of heavy rare earth dvielement, the surface treatment of fluoride aqueous solution of semimetallic elements or transition metal and diffusion have thereafter been added by utilization, make near at least a segregation crystal boundary of semimetallic elements or transition metal, can be the increase of seeing coercive force in the magnetic just at NdFeB, the raising of the rectangularity of demagnetization curve, the increase of remanence, the increase of energy product, the rising of Curie temperature, reducing of magnetize magnetic field, the temperature dependent reduction of coercive force or remanence, the raising of corrosion resistance, the increase of resistivity, some effect of the reduction of hot demagnetization rate can be improved the binding magnet magnetic, the above-mentioned magnetic characteristic of hot forming anisotropic magnet powder and hot forming anisotropy sintered magnet.

＜embodiment 39 〉

A kind of rare earth element permanent magnet, be by in R-Fe-B system (R is a rare earth element) sintered magnet from diffusion into the surface G composition (G be from metallic element (remove 3 families beyond the rare earth element to the metallic element of 11 families or 2 families, 12 families to 16 families C and the element beyond the B select at least a) and rare earth element in the element selected) and fluorine atom get, have with following formula (1) or (2)

R _aG _bT _cA _dF _eO _fM _g(1)

(R·G) _a+bT _cA _dF _eO _fM _g(2)

(here, R is selected from the rare earth element one or more, M was present in to remove 2 families beyond the rare earth element to the element beyond C and the B removed of 116 families in the sintered magnet before coating contains the solution of fluorine, G (removes metallic element or 2 families of rare earth element 3 families in addition to 11 families from metallic element, element beyond C and the B is removed by 12 to 16 families) and rare earth element in more than one the element selected respectively, R and G also can contain identical element, do not contain at R and G under the situation of identical element with formula (1) expression, contain at R and G under the situation of identical element and represent with formula (2).T is selected among Fe and the Co one or both, A is selected among B (boron) and the C (carbon) one or more, a-g calculates with the atom % of alloy, and a, b are 10≤a≤15,0.005≤b≤2 under the situation of formula (1), under the situation of formula (2) 10.005≤a+b≤17,3≤d≤15,0.01≤e≤4,0.04≤f≤4,0.01≤g≤11, remainder are c.) sintered magnet of composition of expression, it is characterized in that, as at least aly distributing that it constitutes the F of element and metallic element (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families) to contain the mode that concentration uprises on an average towards magnet surface from magnetic blow out centre, and the encirclement in this sintered magnet by (R, G) ₂T ₁₄In the crystal boundary portion around the A cube of brilliant main phase grain that constitutes, the concentration of contained G/ (R+G) is on an average greater than the concentration of G/ in the main phase grain (R+G) in the crystal boundary, and in the depth areas of distance magnet surface at least 1 μ m, the oxygen fluoride that has R and G in crystal boundary portion, fluoride or carbon oxygen fluoride, near the magnet top layer coercive force is higher than inside, one of its feature is, can see the concentration gradient or the concentration difference of metallic element (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families) from the surface of sintered magnet towards the center, can utilize the example of following gimmick to make.

The terres rares fluoride that added metallic element (remove 3 families beyond the rare earth element to the metallic element of 11 families or 2 families, 12 families to 16 families remove element beyond C and the B) or the formation treatment fluid of alkaline-earth metal fluoride coat film have been made as followsly.

(1) for the high salt of solubility in water, for example the situation of Dy adds acetic acid dysprosium or dysprosium nitrate 1-10g in the water of 100mL, uses oscillator or ultrasonic stirring device fully to dissolve.

(2) dilution of equivalent that add to generate the chemical reaction of DyFx (x=1-3) at leisure is 10% hydrofluoric acid.

(3) solution to the DyFx (x=1-3) that generated gelatinous precipitate uses the ultrasonic stirring device to stir more than 1 hour.

(4) after rotating speed centrifugation, abandon supernatant, add the methyl alcohol of roughly the same amount with 4000～6000r.p.m.

(5) stir the methanol solution contain gelatinous DyF system or DyFC system, DyFO system bunch and after fully becoming suspension-turbid liquid, use the ultrasonic stirring device to stir more than 1 hour.

(6) repeat the operation 3～10 times of (4) and (5), until detecting less than anion such as acetic acid ion or nitrate ions.

(7), become the DyFx that contains C or O of transparent haply colloidal sol shape for the situation of DyF system.Used the methanol solution of DyFx as treatment fluid as 1g/5mL.

(8) in above-mentioned solution, add the organo-metallic compound of at least a element contain metallic element (remove 3 families beyond the rare earth element to the metallic element of 11 families or 2 families, 12 families to 16 families remove element beyond C and the B).

Other used terres rares fluoride, the formation treatment fluid of alkaline-earth metal fluoride or 2 family's metal fluoride coat films also can be used with above-mentioned essentially identical operation and form, even to the fluorine that contains 2 family's metallic elements is to add various elements in the treatment fluid, the diffraction spectrogram of any solution is also all with (RE is a terres rares with REnFm, 2 family's metallic elements or alkali earths element, n, m is a positive number) or REnFmOpCr (RE is a terres rares, 2 family's metallic elements or alkali earths element, O is an oxygen, C is a carbon, F is a fluorine, n, m, p, r is a positive number) fluorine compounds or the oxygen fluorine compounds or inconsistent of expression with the compound that adds element.Their solution or can to observe the diffraction spectrogram of the dried film of solution with the peak of half breadth more than 1 degree be the X-ray diffraction spectrogram of main peak.This explanation is added between element and the fluorine or the interatomic distance between the metallic element is different from REnFm, and crystal structure also is different from REnFm.Because half breadth is more than 1 degree, therefore above-mentioned interatomic distance is not to be certain value as common metallic crystal, but has certain distribution.The reason that forms this kind distribution is, atom with other around the atom of above-mentioned metallic element or fluorine element has carried out the configuration different with above-claimed cpd, this atom mainly is hydrogen, carbon, oxygen, apply external energy by heating to wait, atoms such as these hydrogen, carbon, oxygen are easy to move, structure changes, and flowability also changes.Colloidal sol shape or gelatinous X-ray diffraction spectrogram are made of the peak of half breadth greater than 1 degree, and utilize heat treatment can see that structure changes, thereby can see above-mentioned REnFm, REn (F, C, O) m or REn (F, the part of diffraction spectrogram O).It is narrower that these diffraction maximums and the diffraction maximum of above-mentioned colloidal sol or gel are compared half breadth.Make the coating film thickness homogenization for the flowability that improves solution, can see at least that in the diffraction spectrogram of above-mentioned solution a peak with the half breadth more than 0.5 degree is very important.

(9) with bulk (100 * 100 * 100mm of NdFeB sintered body ³), the interim formed body of NdFeB or NdFeB be magnetic to be immersed in DyF be that coat film forms in the treatment fluid, this bulk is carried out the methyl alcohol of solvent and remove under the decompression of 2～5torr.

(10) operation with (9) repeated 1 to 5 time, at heat treatment 0.5-5 from 400 ℃ to 1100 ℃ temperature range hour.

(11) apply pulsed magnetic field more than the 30kOe along in (10), having formed the sintered magnet of surface-coated film or anisotropic orientation that NdFeB is magnetic.

This magnetize formed body is clamped between magnetic pole with direct current M-H loop line analyzer, makes that to apply direction consistent for rise magnetic direction and the magnetic field of formed body, by apply magnetic field between magnetic pole, measured demagnetization curve.The magnetize formed body is being applied in the pole piece of field pole, using the FeCo alloy, magnetized value is to use identical shaped pure Ni sample and pure Fe sample to proofread and correct.

Consequently, the coercive force of bulk that has formed the NdFeB sintered body of terres rares fluoride coat film increases, compare with the sintered magnet under the situation about not using after additive contains the coating diffusion of the terres rares fluoride treatment fluid of only attaching most importance to of solution, by using metallic element (remove 3 families beyond the rare earth element to the metallic element of 11 families or 2 families, 12 families to 16 families remove element beyond C and the B) to add treatment fluid, the rectangularity of coercive force or demagnetization curve further increases.Coercive force or the rectangularity utilizing the coated heat that does not add solution to handle like this and increase further increase explanation, and these add the increase that element helps coercive force.Add near can the removing of element in the solution to and see short scope structure,, constitute element along the crystal boundary of sintered magnet with solution and spread then by heat-treating because of solvent.The part of these metallic elements (remove 3 families beyond the rare earth element to the metallic element of 11 families or 2 families, 12 families to 16 families remove element beyond C and the B) demonstrates the tendency that constitutes the part segregation of element with solution near crystal boundary.The composition that shows the sintered magnet of high coercive force demonstrates the concentration height that constitutes the element of fluoride aqueous solution at the magnet peripheral part, becomes the tendency of low concentration in magnetic blow out centre portion.This is because it is also dry to contain the fluoride aqueous solution that adds element in the coating of the outside of sintered magnet bulk, grows and contains fluoride or the oxygen fluoride that adds the short scope structure of having of element, and spread along near the crystal boundary.That is, in the sintered magnet bulk, can see the concentration gradient or the concentration difference of at least a element of fluorine and metallic element (remove 3 families beyond the rare earth element to the metallic element of 11 families or 2 families, 12 families to 16 families remove element beyond C and the B) from outer circumferential side to inside.In certain of the fluoride that contains more than one rare earth elements at least, oxide or the oxygen fluoride of the slip shape that constitutes to comminuted powder, added under the situation of transition metal by fluoride, compare with un-added situation, can confirm to obtain the raising of magnetic characteristics such as high coercive force, yet add in the solution of the transparency under the situation of transition metal or semimetallic elements, it is more obvious that magnetic characteristics such as coercive force increase effect are improved effect.In addition, utilizing evaporation or sputter to form under the situation of the film that contains heavy rare earth dvielements such as Dy, by hybrid transition metal element in vapor deposition source or remove 3 families beyond the rare earth element the element of removing beyond C and the B and carry out evaporation or sputter to the metallic element of 11 families or 2 families, 12 families to 16 families, compare with the rare earth element of only attaching most importance to, can improve magnetic characteristic, and solution-treated one side's effect is more obvious.This be because, transition metal or semimetallic elements disperse equably with atomic level in fluoride aqueous solution, thereby transition metal in the fluoride films or semimetallic elements are disperseed equably to lack the scope structure, and these elements can constitute elemental diffusion with solution such as fluorine at low temperatures and spread along crystal boundary.Metallic element (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families) add acting as of element following certain.1) near segregation and reduce interface energy crystal boundary.2) lattice match of raising crystal boundary.3) defective of minimizing crystal boundary.4) promote the crystal boundary diffusion of rare earth element etc.5) improve near the magnetic anisotropy energy of crystal boundary.6) will with the interface smoothing of fluoride, oxygen fluoride or carbon oxygen fluoride.7) anisotropy of raising rare earth element.8) oxygen is removed from parent phase.9) Curie temperature of raising parent phase.10) can reduce the use amount of rare earth element.That is, utilize the use of adding element, when comparing, then heavy rare earth dvielement use amount can be reduced 1 to 50% with identical coercive force.11) the thickness formation with 1 to 10000nm contains oxygen fluoride or the fluoride that adds element on sintered magnet bulk surface, helps corrosion resistance to improve or high magnetic resistanceization.Promote to add in advance the elements segregation in the sintered magnet.13) oxygen of parent phase is spread to crystal boundary, demonstrate reduction, or add element and combine with oxygen and parent phase is reduced.14) regularization of promotion crystal boundary phase.A part add element stay in crystal boundary mutually in.15) growth of the phase that contains fluorine of inhibition crystal boundary triple point.16) make the CONCENTRATION DISTRIBUTION of heavy rare earth dvielement on crystal boundary and the parent phase interface or fluorine atom precipitous.17) because of fluorine or carbon or oxygen and interpolation elemental diffusion, near the liquid phase formation temperature the crystal boundary reduces.18) because of the cyrystal boundary segregation of fluorine or interpolation element, the magnetic moment of parent phase increases.19) promote the low temperature crystal boundary of heavy rare earth dvielement to spread, can suppress parent phase terres rares height in addition and contain the growth that phase or boride etc. reduce the phase of remanences.Their result is, can see some effect of raising of reduction, corrosion resistance of the reducing of rising, magnetize magnetic field, coercive force or the temperature dependent reduction of remanence, the raising of corrosion resistance, the increase of resistivity, hot demagnetization rate of increase, Curie temperature of increase, energy product of raising, remanence of rectangularity of increase, the demagnetization curve of coercive force.Add in the solution and the metallic element of diffusion (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families) easily from crystal boundary mutually or the end of crystal boundary, crystal boundary towards intragranular ground in the periphery (crystal boundary side) of intragranular, and the somewhere segregation of the near interface of the fluoride of magnet surface.These add element owing to add thermal diffusion after using solution-treated, therefore distribute different with the composition that adds the element in the sintered magnet in advance to, near the crystal boundary of the principal component institute segregation of fluorine or fluoride aqueous solution, reach high concentration, in the crystal boundary of the reduced in segregation of fluorine, can see the elements segregation of adding in advance, from the most surperficial average concentration gradient or the concentration difference of showing to inside of magnet bulk, in solution, adding the interpolation element like this, after utilizing heat treatment to improve the characteristic of sintered magnet after the coating on the magnet bulk, the feature of sintered magnet is as follows.1) can see the concentration gradient of metallic element (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families) or average concentration difference to inside from the most surperficial, concentration has the tendency that reduces to inside from magnet portion surface.2) can see with fluorine and add near the segregation of solution metal element (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families) magnet portion crystal boundary to.3) crystal boundary mutually in fluorine concentration height, fluorine concentration is low in the outside of crystal boundary phase, can see the fluorine concentration difference near, sometimes the segregation of metallic element (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families) be can see, and can average concentration gradient or concentration difference be seen to inside from magnet bulk surface.4) contain the layer of metallic element (remove beyond the rare earth element 2 families to the element beyond C and the B removed of 116 families), fluorine and carbon in the superficial growth of sintered magnet.5) concentration gradient of the interpolation element that adds in advance before solution-treated is different with the concentration gradient of the element that adds in solution-treated, the former depends on the concentration gradient of the principal component of fluoride aqueous solutions such as fluorine, and at least a element of the formation element of the latter and fluoride aqueous solution can be seen strong correlation relation or correlation in the concentration analysis.

＜embodiment 40 〉

Made the formation treatment fluid of terres rares fluoride or alkaline-earth metal fluoride coat film as followsly.

(1) for the high salt of solubility in water, for example the situation of Nd adds acetic acid neodymium or neodymium nitrate 4g in the water of 100mL, uses oscillator or ultrasonic stirring device fully to dissolve.

(2) add generation NdF at leisure _xC _yThe dilution of the equivalent of the chemical reaction of (x, y are positive number) is 10% hydrofluoric acid.

(3) to having generated the NdF of gelatinous precipitate _xC _yThe solution of (x, y are positive number) uses the ultrasonic stirring device to stir more than 1 hour.

(4) after rotating speed centrifugation, abandon supernatant, add the methyl alcohol of roughly the same amount with 4000～6000r.p.m.

(5) stir the methanol solution contain gelatinous NdFC system bunch and after fully becoming suspension-turbid liquid, use the ultrasonic stirring device to stir more than 1 hour.

(6) repeat the operation 3～10 times of (4) and (5), until detecting less than anion such as acetic acid ion or nitrate ions.

(7), become the NdF of transparent haply colloidal sol shape for the situation of NdFC system _xC _y(x, y are positive number).Used NdF as treatment fluid _xC _y(x, y are positive number) is the methanol solution of 1g/5mL.

(8) organo-metallic compound beyond the de-carbon of interpolation table 2 in above-mentioned solution.

Used terres rares fluoride or alkaline-earth metal fluoride with other also can be used and above-mentioned essentially identical operation formation as the formation treatment fluid of the coat film of principal component, even to Dy as shown in table 2, Nd, La, Mg fluorine is to add various elements in the element of treatment fluid, alkali earths element or 2 families, the diffraction spectrogram of any solution also all with fluorine compounds or oxygen fluorine compounds or inconsistent with REnFmCp (RE is terres rares or alkali earths element, and n, m, p are positive number) expression with the compound that adds element.Their solution or the diffraction spectrogram of the dried film of solution is made of a plurality of peaks of half breadth more than 1 degree.This explanation is added between element and the fluorine or the interatomic distance between the metallic element is different from REnFmCp, and crystal structure also is different from REnFmCp.Because half breadth is more than 1 degree, therefore above-mentioned interatomic distance is not to be certain value as common metallic crystal, but has certain distribution.The reason that forms this kind distribution is, around the atom of above-mentioned metallic element or fluorine element, dispose other atom, this atom mainly is hydrogen, carbon, oxygen, apply external energy by heating to wait, atoms such as these hydrogen, carbon, oxygen are easy to move, structure changes, and flowability also changes.Colloidal sol shape or gelatinous X-ray diffraction spectrogram are made of the peak of half breadth greater than 1 degree, and utilize heat treatment can see that structure changes, thereby can see above-mentioned REnFmCp or REn (F, C, O) part of the diffraction spectrogram of m (ratio of C is arbitrarily for F here, O).Can think that the major part of the interpolation element shown in the table 2 does not have the long period structure in solution.It is narrower that the diffraction maximum of this REnFmCp and the diffraction maximum of above-mentioned colloidal sol or gel are compared half breadth.Make the coating film thickness homogenization for the flowability that improves solution, can see at least that in the diffraction spectrogram of above-mentioned solution a peak with the half breadth more than 0.5 degree is very important.Peak and the diffraction spectrogram of REnFmCp or the peak of oxygen fluorine compounds that also can contain the above half breadth of this kind 1 degree.Under the situation of the diffraction spectrogram below the main diffraction spectrogram or 1 that only observes REnFmCp or oxygen fluorine compounds is spent in the diffraction spectrogram of solution, be not the solid phase of colloidal sol or gel owing to mix in solution, therefore flowability is poor, very difficult coating equably.

(9) with bulk (10 * 10 * 10mm of NdFeB sintered body ³) to be immersed in NdF be that coat film forms in the treatment fluid, this bulk is carried out the methyl alcohol of solvent and remove under the decompression of 2～5torr.

(10) operation with (9) repeated 1 to 5 time, at heat treatment 0.5-5 from 400 ℃ to 1100 ℃ temperature range hour.

(11) apply pulsed magnetic field more than the 30kOe along the anisotropic orientation that in (10), has formed the anisotropic magnet of surface-coated film.

This magnetize formed body is clamped between magnetic pole with direct current M-H loop line analyzer, makes that to apply direction consistent for rise magnetic direction and the magnetic field of formed body, by apply magnetic field between magnetic pole, measured demagnetization curve.The magnetize formed body is being applied in the pole piece of field pole, using the FeCo alloy, magnetized value is to use identical shaped pure Ni sample and pure Fe sample to proofread and correct.

Consequently, the coercive force of bulk that has formed the NdFeB sintered body of terres rares fluoride coat film increases, compare with un-added situation, in the sintered magnet of Dy, Nd, La and Mg carbon fluoride or the segregation of carbon oxyfluoride, coercive force increases by 40%, 30%, 25% and 20% respectively.To utilize the coated heat that does not add solution to handle and the coercive force of increase like this in order further increasing, to use organo-metallic compound to add in each fluoride aqueous solution interpolation element as shown in table 2.When the coercive force with the situation of not adding solution was benchmark, the coercive force of sintered magnet further increased, thereby distinguished that these add the increase that elements help coercive force.Add near can the removing of element in the solution to and see short scope structure,, constitute element along the crystal boundary of sintered magnet or various defective with solution and spread then by heat-treating because of solvent.These add element and demonstrate the tendency that constitutes the part segregation of element with solution near crystal boundaries.Interpolation element shown in the table 2 spreads in sintered magnet with at least a element of fluorine, oxygen and carbon, and its part stays near the crystal boundary.The composition that shows the sintered magnet of high coercive force demonstrates the concentration height that constitutes the element of carbon fluoride solution at the magnet peripheral part, becomes the tendency of low concentration in magnetic blow out centre portion.This be because, contain the carbon fluoride solution and the drying of adding element in the coating of the outside of sintered magnet bulk, growth contains fluoride, carbon oxygen fluoride, carbon fluoride or the oxygen fluoride that adds the short scope structure of having of element, and spreads near crystal boundary, crackle portion or defective.CONCENTRATION DISTRIBUTION from the surface of sintered magnet to inside is shown in Fig. 5 to Fig. 8.Fig. 5 is the situation of unmixed transition metal in fluoride aqueous solution, and the fluorine on surface is more than Dy, and the inner fluorine content of sintered magnet is less than Dy.This is because contain fluoride or the oxygen fluoride of Nd or Dy near surface growth.Can also see the concentration gradient of carbon, carbon fluoride or carbon oxygen fluoride are grown partly at the sintered magnet near surface.Transition metal is made as M and has measured CONCENTRATION DISTRIBUTION, the results are shown in Fig. 6 in Figure 10.The transition metal or 2 families of removing rare earth element demonstrate the tendency that reduces to inside from the sintered magnet surface to the element M of removing beyond C and the B of 116 families, demonstrate the tendency identical with carbon or fluorine.The Dy of heavy rare earth dvielement is different with the surface in inside with the ratio of fluorine, demonstrates in the more tendency of surperficial fluorine.Fig. 7 is that the fluorine on surface is compared the bigger sintered magnet of concentration gradient at inner fluorine about equally with the concentration of Dy with Dy.For carbon or comprise the CONCENTRATION DISTRIBUTION of transition metal of the element of table 2, from outside thoughtful inside can see that concentration reduces.The CONCENTRATION DISTRIBUTION of Fig. 8 is to see minimum and the situation that forms conversion zone between fluoride and parent phase in the Dy CONCENTRATION DISTRIBUTION.Minimum portion in Dy concentration detects a lot of Nd, owing to produced the exchange reaction of Nd and Dy, therefore becomes CONCENTRATION DISTRIBUTION as shown in Figure 8.For fluorine, carbon, transition metal can from outside thoughtful inside see that concentration reduces, and, the situation that reaches minimum or great CONCENTRATION DISTRIBUTION is arranged also because of the influence of conversion zone.The tendency of CONCENTRATION DISTRIBUTION as shown in Figure 5 to Figure 8 not only can see in sintered magnet, and is also can see in magnetic or the powder that contains rare earth element at NdFeB, can confirm the raising of magnetic characteristic.Concentration gradient or the concentration difference of 3 families that in the sintered magnet bulk, can from the outer circumferential side to inside, see fluorine and comprise the interpolation element shown in the table 2 to the metallic element of 11 families or 2 families, 12 families at least a element of the element of 16 families.Content is consistent basically with the scope with light transmission of solution in the solution of these elements, even further increase concentration, also can make solution, can increase coercive force, in certain of the fluoride that contains more than one rare earth elements at least, oxide, carbon fluoride, carbon oxygen fluoride or the oxygen fluoride of slip shape, adding under the situation of removing the element beyond the B of 3 families to the metallic element of 11 families or 2 families, 12 families to 16 families, compare with un-added situation, can confirm to obtain the raising of magnetic characteristics such as high coercive force.Among Fig. 9 or Figure 10, the zone that increase though in the CONCENTRATION DISTRIBUTION of Dy, can see inner along with trend, however become low concentration at the sintered magnet central part, or in the zone that is deeper than 0.1 μ m, reach certain basically.Be made as under the situation more than 1000 times of table 2 adding concentration of element, the structure that constitutes the fluoride of solution changes, the distribution of in solution, the adding element heterogeneity that becomes, can see the tendency of the elemental diffusion that hinders other, be difficult to make the interpolation element to arrive magnet bulk inside, can see the increase of coercive force partly along cyrystal boundary segregation.The interpolation element except that B of 3 families to the metallic element of 11 families or 2 families, 12 families to 16 families act as following certain.1) near segregation and reduce interface energy crystal boundary.2) lattice match of raising crystal boundary.3) defective of minimizing crystal boundary.4) promote the crystal boundary diffusion of rare earth element etc.5) improve near the magnetic anisotropy energy of crystal boundary.6) will with the interface smoothing of fluoride or oxygen fluoride.7) by at the most surperficial above-mentioned interpolation element that contains excellent corrosion resistance, growth has the phase of fluorine concentration gradient, contains iron and oxygen, improves the stability (connecting airtight property) as diaphragm.Part at this superficial layer can be seen twin crystal.Their result is, coating, the diffusion heat treatments of the solution that adds element used in utilization, can see some effect of reduction of the reducing of rising, magnetize magnetic field, coercive force or the temperature dependent reduction of remanence, the raising of corrosion resistance, the increase of resistivity, hot demagnetization rate of increase, Curie temperature of increase, energy product of raising, remanence of rectangularity of increase, the demagnetization curve of coercive force.In addition, the CONCENTRATION DISTRIBUTION of removing interpolation element B beyond of 3 families to the metallic element of 11 families or 2 families, 12 families to 16 families demonstrates the tendency that reduces on an average to inside from the sintered magnet periphery, demonstrates in crystal boundary portion or the most surperficial tendency that reaches high concentration.The width of crystal boundary has different tendencies with place away from the crystal boundary triple point near the crystal boundary triple point, width is wideer near the crystal boundary triple point, average grain boundary width is 0.1 to 20nm, in 1 times to 1000 times distance of grain boundary width, add a part of segregation of element, the concentration of the interpolation element of this segregation demonstrates the tendency that reduces fifty-fifty from the magnet surface to inside, have fluorine in the part of crystal boundary phase.In addition, add element easily from crystal boundary mutually or the end of crystal boundary, crystal boundary towards intragranular ground in the somewhere segregation of the periphery (crystal boundary side) of intragranular.Can confirm additive in the solution of raising of magnetic characteristic of above-mentioned magnet and be the element in Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Zr, Nb, Mo, Pd, Ag, In, Sn, Hf, Ta, W, Ir, Pt, Au, Pb, Bi that is selected from table 2 or the atom that the comprises whole transition metals numbering 18 to 86, at least a element in the middle of them and fluorine can be in sintered magnet from the outer thoughtful inside of magnet and from the crystal boundary to the intragranular, see concentration gradient fifty-fifty.Near the crystal boundary with 3 families of intragranular to the metallic element of 11 families or 2 families, 12 families to 16 families the concentration gradient of removing the interpolation element beyond the B or concentration difference from magnet outside thoughtfully central portion change fifty-fifty, demonstrate the tendency that reduces more the closer to magnetic blow out centre, if diffusion is fully, then near comprising the crystal boundary of fluorine, can see the concentration difference that is accompanied by the interpolation element that adds elements segregation.These add element owing to add thermal diffusion after using solution-treated, therefore distribute different with the composition that adds the element in the sintered magnet in advance to, near the crystal boundary of fluorine institute segregation, reach high concentration, near the crystal boundary of the reduced in segregation of fluorine, can see the elements segregation of adding in advance, show average concentration gradient to inside from the magnet bulk is the most surperficial.Adding concentration of element be under the situation of low concentration in solution, can see concentration difference with magnetic blow out centre portion in that magnet is the most surperficial, can confirm by the concentration difference of formation concentration gradient or crystal boundary and intragranular.Adding the interpolation element like this in solution, after utilizing heat treatment to improve the characteristic of sintered magnet after the coating on the magnet bulk, the feature of sintered magnet is as follows.1) can from sintered magnet comprise with the conversion zone of the layer that contains fluorine the most surperficial to the element of internally seeing table 2 or comprise the concentration gradient of element of atom numbering 18 to 86 of transition metal or average concentration difference.2) element of the table 2 that can see with fluorine or carbon, oxygen or comprise near the part of the segregation of element crystal boundary of the atom numbering 18 to 86 of transition metal is arranged a lot.3) crystal boundary mutually in fluorine concentration height, fluorine concentration is low in the outside of crystal boundary phase (crystal grain peripheral part), in 1000 times of the grain boundary width that can see the fluorine concentration difference, the element of table 2 or the elements segregation of atom numbering 18 to 86 be can see, and can average concentration gradient or concentration difference be seen to inside from magnet bulk surface.4) at the most peripheral fluorine of the sintered magnet bulk that has been coated with solution or magnetic iron powder or ferromagnetism powder and to add the concentration of element the highest, can be from the outside the magnetic body towards internally seeing the concentration gradient or the concentration difference of adding element.5) the most surperficial with 10% coverage rate, thick 1 to 10000nm layer of the preferred element that forms the element that contains fluorine, carbon, oxygen, iron and table 2 or atom numbering 18 to 86 more than 50% helps that corrosion resistance improves, the recovery of the magnetic characteristic of affected layer etc.6) the interpolation element of table 2 or formation contain at least a in the element of solution of element of atom numbering 18 to 86 have concentration gradient from the surfaces to inside, seeing the outside by the near interface of the magnet of solution growth and fluoropolymer membrane or from magnet at the interface, fluorine concentration maximum, the fluoride of near interface contains the element of aerobic, carbon or atom numbering 18 to 86, helps certain of this corrosion resistance, high resistance or high magnetic characteristic.In this fluoropolymer membrane, can detect more than interpolation element shown in the table 2 or atom numbering 18 to 86 element at least a or two, near the evolving path of the fluorine of magnet inside, contain a lot of above-mentioned interpolation elements, can see coercive force increase, demagnetization curve rectangularity raising, remanence increase, energy product increase, Curie temperature the reducing of rising, magnetize magnetic field, diffusion temperature reduction, to the growth of grain boundary width suppress, to growth inhibiting some effect of the nonmagnetic layer of crystal boundary portion.The concentration difference of above-mentioned interpolation element can be confirmed the sample analysis after the sintering bulk is cut from surface lateral inside by EDX (energy dispersive X-ray) analysis or EPMA analysis, the auger analysis etc. that utilize TEM.Can utilize the EDX or the EELS of TEM to analyze the situation of adding the element generation segregation of the atom numbering 18 to 86 in the solution at (in the segregation position 5000nm apart from fluorine atom, in the preferred 1000nm) near the fluorine atom.Is 1.1 to 1000 near the interpolation element of the segregation fluorine atom with being present in ratio apart from the interpolation element of the position more than the segregation position 2000nm of fluorine atom inner position more than distance magnet surface 100 μ m, preferably more than 2.At the above-mentioned ratio of magnet surface more than 2.For above-mentioned interpolation element, be along the crystal boundary part of segregation or which kind of state of the part of segregation discontinuously all exists continuously, might not be segregation on whole crystal boundary, and become discontinuous easily at the central side of magnet.In addition, not segregation and sneak into parent phase fifty-fifty of a part of adding element.The tendency that the ratio that the interpolation element of atom numbering 18 to 86 spreads in from the surface of sintered magnet to the oriented parent phase in inside or near the concentration of segregation fluorine segregation position reduce, reason owing to this CONCENTRATION DISTRIBUTION, compare with magnet inside, demonstrating the higher tendency of coercive force near the surface.Above-mentioned magnetic characteristic is improved effect and is not only in the sintered magnet bulk and can obtains, even at NdFeB is that magnetic powder or SmCo are that magnetic or Fe are that the solution shown in the magnetic surface use table 2 forms the film that contains fluorine and add element, also can utilize diffusion heat treatments to obtain the improvement of Hard Magnetic characteristic or the effects such as increase of magnetic resistance.In addition, can be by after the NdFeB powder be shaped in magnetic field temporarily, interim formed body dipping is contained metallic element or 2 families of 3 families to 11 families, 12 families sintering and after the part on magnetic surface forms the film that contains additive and fluorine to the solution of removing the element beyond C and the B of 16 families, or by use being contained metallic element or 2 families of 3 families to 11 families, it is that powder is after powder mixes with the NdFeB that is untreated that 12 families have carried out surface-treated NdFeB to the solution of removing the element beyond C and the B of 16 families, in magnetic field, after interim the shaping, carry out sintering and make sintered magnet.In this kind sintered magnet, the CONCENTRATION DISTRIBUTION of adding the solution constituent of element etc. in fluorine or the solution is homogeneous on an average, yet because of higher on an average near the concentration of removing element C and B beyond of the 3 families the evolving path of fluorine atom to the metallic element of 11 families or 2 families, 12 families to 16 families, so magnetic characteristic improves.Plant thus and contain the crystal boundary that contains fluorine that the solution of removing element C and B beyond of 3 families to the metallic element of 11 families or 2 families, 12 families to 16 families forms and in segregation portion, contain 0.1 to 60 atom % on an average, the fluorine of preferred 1 to 20 atom %, can utilize the concentration of adding element to form non magnetic, ferromagnetism or antiferromagnetism, combine with the magnetic of particle by strengthening or weakening ferromagnetic particles, just can control magnetic characteristic.Can use the fluoride aqueous solution that has added organo-metallic compound to make the hard magnetic material by solution, can to obtain by Fe, the Co of the rare earth element of 1～20 atom %, 50～95 atom %, Ni, Mn, at least a element of Cr, 20 ℃ the coercive force that the fluorine of 0.5～1.5 atom % constitutes be the magnetic material of 0.5MA/m as forming.Remove element beyond C and the B even in the magnetic material of above-mentioned composition, contain carbon or oxygen and 3 families partly to the metallic element of 11 families or 2 families, 12 families to 16 families, also can satisfy 0.5MA/m, go in the various magnetic loops,, therefore not necessarily need manufacturing procedure owing to use solution.

(utilizing on the industry possibility)

The present invention is in order to improve the heat resistance of the Fe based magnet that comprises that R-Fe (R is rare earth element) is, the part at crystal boundary or intragranular in Fe based magnet material forms the tabular phase that contains fluorine. The above-mentioned magnetic characteristic that helps mutually the Fe based magnet that contains fluorine improves. Magnet with the phase that contains fluorine can be used for the magnet of the characteristic of various magnetic loops couplings and use the magnet motor etc. of above-mentioned magnet. In this kind magnet motor, comprise that the driving of hybrid vehicle is used, starter is used, electric motor driven power steering is used.

Claims (17)

1. a magnet is the magnet that is made of the magnetic that contains iron and rare earth element,

Form a plurality of fluorine compound layers or oxygen fluorine compound layer in the inside of above-mentioned magnetic,

Above-mentioned fluorine compound layer or oxygen fluorine compound layer have the bigger major axis of average grain diameter than the crystal grain of above-mentioned magnetic.

2. magnet according to claim 1, wherein, the average grain diameter of the crystal grain of above-mentioned magnetic below the above 50nm of 10nm,

The major axis of above-mentioned fluorine compound layer or oxygen fluorine compound layer is below the above 500nm of 50nm.

3. magnet according to claim 1, wherein, the major axis of above-mentioned fluorine compound layer or oxygen fluorine compound layer is the size below 20 times more than 2 times of minor axis.

4. magnet according to claim 1, wherein, above-mentioned fluorine compound layer or oxygen fluorine compound layer contain at least a in alkali element, alkali earths element and the rare earth element.

5. magnet according to claim 1, wherein, above-mentioned fluorine compound layer or oxygen fluorine compound layer contain iron and constitute the rare earth element of above-mentioned magnetic.

6. magnet according to claim 1, wherein, above-mentioned fluorine compound layer or oxygen fluorine compound layer contain aerobic and carbon.

7. magnet according to claim 1, wherein, above-mentioned magnetic with NdFeB as principal component.

8. a sintered magnet is the sintered magnet that contains iron and rare earth element,

Form a plurality of fluorine compound layers or oxygen fluorine compound layer in the inside of above-mentioned sintered magnet,

The major axis of above-mentioned fluorine compound layer or oxygen fluorine compound layer is below the above 500nm of 50nm.

9. a magnet is the magnet that will contain the magnetic compression molding of iron and rare earth element and constitute,

Form a plurality of fluorine compound layers or oxygen fluorine compound layer in the inside of above-mentioned magnetic,

Above-mentioned fluorine compound layer or oxygen fluorine compound layer have the bigger major axis of average grain diameter than the crystal grain of above-mentioned magnetic.

10. magnet according to claim 9, wherein, the average grain diameter of the crystal grain of above-mentioned magnetic below the above 50nm of 10nm,

The major axis of above-mentioned fluorine compound layer or oxygen fluorine compound layer is below the above 500nm of 50nm.

11. magnet according to claim 9, wherein, the major axis of above-mentioned fluorine compound layer or oxygen fluorine compound layer is the size below 20 times more than 2 times of minor axis.

12. magnet according to claim 9, wherein, above-mentioned fluorine compound layer or oxygen fluorine compound layer contain at least a in alkali element, alkali earths element and the rare earth element.

13. magnet according to claim 9, wherein, above-mentioned fluorine compound layer or oxygen fluorine compound layer contain iron and constitute the rare earth element of above-mentioned magnetic.

14. magnet according to claim 9, wherein, above-mentioned fluorine compound layer or oxygen fluorine compound layer contain aerobic and carbon.

15. magnet according to claim 9, wherein, above-mentioned magnetic with NdFeB as principal component.

16. magnet according to claim 9, wherein, above-mentioned a plurality of fluorine compound layers of separating out or oxygen fluorine compound layer have major axis respectively on different directions.

17. the processing method of a magnet, the processing method of above-mentioned magnet be included on the magnetic coating fluorine compounds be first operation of solution and after first operation heating magnetically body and remove second operation that above-mentioned fluorine compounds are the solvent of solution,

Above-mentioned magnetic contains iron and rare earth element,

Above-mentioned fluorine compounds are that solution is the fluorine compounds of dispersion gel shape in alcoholic solvent and the solution that constitutes.

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