CN101896300B - Powder and method for producing the same - Google Patents

Powder and method for producing the same Download PDF

Info

Publication number
CN101896300B
CN101896300B CN2008801199246A CN200880119924A CN101896300B CN 101896300 B CN101896300 B CN 101896300B CN 2008801199246 A CN2008801199246 A CN 2008801199246A CN 200880119924 A CN200880119924 A CN 200880119924A CN 101896300 B CN101896300 B CN 101896300B
Authority
CN
China
Prior art keywords
powder
apatite
metal powder
minutes
silicon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2008801199246A
Other languages
Chinese (zh)
Other versions
CN101896300A (en
Inventor
金井仁子
丸山钢志
粕谷圭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Denko Materials Co ltd
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN101896300A publication Critical patent/CN101896300A/en
Application granted granted Critical
Publication of CN101896300B publication Critical patent/CN101896300B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/08—Metallic powder characterised by particles having an amorphous microstructure

Abstract

Disclosed is a powder which includes metal particles, apatite layers covering the metal particles, and silica fine particles adhered to the metal particles or the apatite layers. This powder enables annealing at high temperatures without causing fracture of an insulating layer during production of a dust core. Consequently, a dust core having sufficiently high permeability while maintaining insulating properties of the insulating layer can be obtained by using this powder.

Description

Powder and preparation method thereof
Technical field
The present invention relates to a kind of powder that is suitable as the material powder of the dust core that hangs down iron loss.
Background technology
Transformer, motor, generator, loudspeaker, induction heater, various brakes etc. have a lot of products that utilize electromagnetism at our periphery.For their high performance, miniaturization, necessary raising is as the performance of the magnetic core of the press-powder formed body of soft magnetic material.
Said magnetic core is, in the past, alternatively laminated the film and the insulating barrier of a plurality of silicon steel, through making (electromagnetic steel plate) with the mould punching press.But these methods are not suitable for making miniaturization and complex-shaped product, existing problems aspect minimizing eddy-current loss.
To such problem, in recent years, as to having excellent formability, and can the low-cost magnetic core of making, the method that the soft magnetic metal powder compression molding is obtained dust core is attracted attention by the people, and carries out various exploitations.
Such dust core needs to strengthen magnetic density, to increase permeability.Particularly, being used for the magnetic core of motor, be in alternating magnetic field, to use mostly, but iron loss is big, and energy conversion efficiency is poor, therefore requires iron loss little (low iron loss).
In the said iron loss, comprise magnetic hystersis loss, eddy-current loss, remaining loss, wherein, magnetic hystersis loss and eddy-current loss are the problem main cause.
Aspect dust core, the increase of magnetic hystersis loss is, when making dust core at the compression molding soft magnetic metal powder, applied on soft magnetic metal powder that huge processing strain caused.Thereby, in order to reduce magnetic hystersis loss effectively, after compression molding, resulting formed body is implemented annealing, remove the strain that is applied to the soft magnetic metal powder metal powder, its annealing temperature allegedly is preferably more than 600 ℃.
On the other hand, in order to reduce eddy-current loss effectively, use insulating materials to coat soft magnetic metal powder.But, for the insulating materials that uses, anneal in order to reduce magnetic hystersis loss as beforely, then because the hear resistance of insulating materials is low, cause decomposing, insulating properties significantly reduces.Thereby taking into account the reduction of eddy-current loss and the reduction of magnetic hystersis loss is very large problem.
In order to solve above-mentioned problem, develop a kind of insulating materials of excellent heat resistance here.Particularly, use iron powder, then can make the dust core inexpensive, that magnetic density is high, so carry out various research and development as soft magnetic metal powder.For example, in the documents 1, a kind of method that adopts silicon dioxide granule as the insulating coating of excellent heat resistance has been proposed.In above-mentioned document, disclose a kind of by the preparation method of the metal dust of SiO 2 powder covering; Phosphoric acid iron powder of handling and the suspension that contains silicon dioxide granule are implemented in the surface to be mixed; Through dry this amalgam, the metal dust that preparation is covered by SiO 2 powder.
But; Desire uses the above-mentioned iron powder that is covered by silicon dioxide granule to make under the situation of dust core; In order to obtain between the metal powder cohesive force fully, need annealing temperature be brought up to than near the higher temperature (for example more than 800 ℃) of temperature 600 ℃ in the conventional operation.Yet annealing temperature is too high, because the Curie temperature of iron is 769 ℃, so have the tendency of the magnetic characteristic that reduces dust core.
In addition; Following method is disclosed in documents 2: on the surface of soft magnetic metal powder, form oxide skin(coating) and insulating barrier; Through under reducing atmosphere, hot conditions, combining intensive treatment, thereby on the surface of soft magnetic metal powder, form the excellent individual layer of insulating properties.
Patent documentation 1: the spy opens flat 9-180924 communique
Patent documentation 2: the spy opens the 2007-194273 communique
Summary of the invention
The problem that invention will solve
If use the soft magnetic metal powder that obtains according to above-mentioned patent documentation 2 disclosed method manufacturings, the dust core of excellent heat resistance can be provided.But, using this method, the required cost of energy of annealing is high in technology, can not be suitable for a large amount of productions again, has the soft magnetic metal powder of the overlay film of excellent heat resistance so consider the simpler method preparation of utilization.
In addition,, on soft magnetic metal powder, form thin as far as possible and large-scale insulating barrier,, still do not know both easy and low cost method at present though this is an effective method in order to increase magnetic density.
The present invention accomplishes in view of above-mentioned existing in prior technology problem; Its purpose is to provide a kind of soft magnetic metal material powder; Aspect dust core, the reduction and the eddy-current loss that both can have both magnetic hystersis loss reduce, and can have both low iron loss and high flux density again.
Solve the method for problem
The present invention provides a kind of powder in order to solve above-mentioned problem, and it comprises metal powder, covers the apatite layer of said metal powder, attached to the silicon dioxide granule on said metal powder or the said apatite layer.
According to the present invention, cover metal powder with apatite layer, and, on metal powder or apatite layer, adhere to silicon dioxide granule, thus form on the metal powder surface can be anti-the insulating coating of annealing temperature more than 600 ℃.The effect that adopts dependency structure and structure thereof to bring is, obtains based on the inventor's following discovery: in order to reduce magnetic hystersis loss, formation can tolerate that the good hear resistance dielectric film of annealing temperature is effective more than 600 ℃.
In the present invention, said apatite layer preferably contains the perhaps compound shown in (I-b) of formula (I-a).
Ca 10(PO 4) 6X 2 (I-a)
Ca (10-(m×n)/2)M n(PO 4) 6X 2 (I-b)
(in the formula, M be that to give cationic atom or former subgroup, m be the cationic valence mumber that gives of M, n for surpass 0 and be 5 below, X is the perhaps former subgroup of atom that gives univalent anion.)
In addition, said silicon dioxide granule is preferably the silicon dioxide granule through the organic group surface modification.
Further, said silicon dioxide granule through the organic group surface modification, be preferably use formula (II) perhaps compound shown in (III) carry out the silicon dioxide granule of surface modification.
R 1 nSi(OR 2) 4-n (II)
R 1 nSiX 4-n (III)
(in the formula, n is 1～3 integer, R 1And R 2Expression any monovalent organic radical group, X represent halogen).
In addition, said metal powder is preferably the powder of soft magnetic material.
Powder of the present invention is suitable as the powder that dust core is used.
In addition, the present invention also provides a kind of preparation method of powder, and this method may further comprise the steps:
First step covers metal powder with apatite;
Second step is adhered to SiO 2 powder on the metal powder that in said first step, obtains surface or the apatite surface;
Third step; The powder that will in said second step, obtain; Implement precuring 350 ℃ of following temperature, the apatite layer that obtains comprising said metal powder, cover said metal powder, attached to the powder of the silicon dioxide granule on said metal powder or the apatite layer.
As the said metal powder that provides to said first step, the preferred metal powder of handling through phosphoric acid that uses.
The invention effect
Powder of the present invention is by apatite layer and have the insulating barrier covering of adhering to silica above that, and this insulating barrier has excellent insulating properties and hear resistance.Thereby, when making dust core, under the situation of not destroying insulating barrier, can implement annealing at high temperature.Therefore, can prepare the sufficiently high dust core of insulating properties, magnetic capacity that has kept insulating barrier.
Description of drawings
Fig. 1 be illustrated in the hydroxyapatite that obtains among the embodiment 1 cover iron powder section SEM (SEM) as photo (multiplying power: 2500 times).
Fig. 2 is illustrated in the photo (multiplying power: 50000 times) of SEM picture that the hydroxyapatite that obtains among the embodiment 1 covers the section of iron powder.
Fig. 3 is illustrated in the nano silicon that obtains among the embodiment 1 to adhere to the photo (multiplying power: 1000 times) of SEM picture that hydroxyapatite covers the section of iron powder.
Fig. 4 is illustrated in the nano silicon that obtains among the embodiment 1 to adhere to the photo (multiplying power: 100000 times) of SEM picture that hydroxyapatite covers the section of iron powder.
The specific embodiment
First mode of the present invention is a kind of powder, and it comprises metal powder, covers the apatite layer of said metal powder, attached to the silicon dioxide granule on said metal powder or the said apatite layer.Below, each the structure important document to powder of the present invention describes in regular turn.
(metal powder)
About employed metal powder in the present invention; So long as the metal powder that has ferromagnetism and the high saturation magnetic flux metric density is shown gets final product; Do not receive special restriction, specifically, for example can enumerate soft magnetic materials such as iron powder, silicon-steel powder, Sendust powder, amorphous powder, Permendur powder, soft ferrite powder, amorphous magnetic alloy powder, nanocrystal magnetic alloy powder and perm iron-nickel alloy powder; These can use separately, also can mix two or more uses.Wherein, consider, be preferably iron powder from ferromagnetism and cheap aspect.
In addition, in iron powder, from saturation flux density or permeability equimagnetic excellent, the aspect that compressibility is excellent is considered, is preferably straight iron powder especially.As such straight iron powder, specifically, for example can enumerate atomized iron powder, reduced iron powder and electrolytic iron powder etc., for example can enumerate the 300NH of Kobe Steel Ltd's manufacturing etc.
In addition, as metal powder,, can use the powder that contained element was carried out adjustment in that the magnetic characteristic of compressibility or dust core etc. is not produced in the scope of bad influence.Specifically, for example, add P elements, perhaps, can add elements such as cobalt, nickel, manganese, chromium, molybdenum, copper in order to improve magnetic characteristic for the oxidation that prevents metal powder.
As the particle diameter of metal powder,, can perhaps require characteristic suitably to determine according to the purposes of dust core though there is not special qualification.In general, can be from the particle of 1 μ m～300 mu m ranges, suitably selecting through SEM observable particle sizes such as (SEM).When particle diameter is 1 μ m when above, when making dust core, have the tendency of easy shaping, when particle diameter is 300 μ m when following, the eddy current that can suppress dust core increases, and has the tendency of easy coating apatite layer.In addition, as average grain diameter (the average aggregate particle size of trying to achieve through sieve method), be preferably 50～250 μ m.
As metal powder, its shape is had no particular limits, can use spherical or block powder, perhaps implemented the flat powder of flat processing according to known preparation method or machining.
(apatite layer)
Cover the apatite layer of powder surface of the present invention, have effect as the insulating coating of said metal powder.From above viewpoint, apatite layer is preferably the structure of film that said metal powder surface coverage is become stratiform.
Apatite layer is meant, the layer that is made up of the material with apatite structure.The material with apatite structure of apatite layer, its preference particularly, can be enumerated the perhaps compound shown in (I-b) of formula (I-a).
Ca 10(PO 4) 6X 2(I-a)
Ca (10-(m×n)/2)M n(PO 4) 6X 2(I-b)
(in the formula, M be that to give cationic atom, m be the cationic valence mumber that gives of M, n for surpass 0 and be 5 below, X is the perhaps former subgroup of atom that gives univalent anion.)
In said general formula (I-b), give cationic atom M, being preferably can be by the substituted metal of calcium.Related metal; Particularly; Can enumerate ionic radius and be 0.80～1.40
Figure 639553DEST_PATH_GPA00001151437600011
metal; For example, can enumerate sodium, magnesium, potassium, calcium, scandium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, strontium, yttrium, zirconium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, platinum, gold, mercury, thallium, lead, bismuth etc.M can be for a kind of or two or more in the said general formula (I-b).In addition, in above-mentioned general formula (I-b), the scope of n is preferably above below 0 and 2.5, more preferably above below 0 and 1.0 for surpassing below 0 and 5.At above-mentioned general formula (I-a) and (I-b), be preferably hydroxyl (OH) and halogen element (F, Cl, Br, I etc.), more preferably hydroxyl and fluorine as X.When X is hydroxyl, excellent to the coating of metal dust, so preferred; When X is fluorine atom, excellent to the intensity aspect, so preferred.
As the material of the formation apatite structure of apatite layer, when manufacturing dust core, consider from the aspect that insulating properties, hear resistance and mechanical characteristic are excellent, be preferably by the compound shown in the above-mentioned general formula (I-a), especially preferably use hydroxyapatite (Ca 10(PO 4) 6(OH) 2) or fluorine-based apatite (Ca 10(PO 4) 6F 2).
In powder of the present invention, " metal powder is covered by apatite layer " is meant, the state that at least a portion of said metal powder is covered by apatite layer.From then stating " metal powder that is covered by apatite ", be not meant the situation that metal powder is covered by apatite fully, also can be the situation that the part of metal powder is exposed.On the other hand, with regard to the degree that metal powder is covered by apatite layer, coverage rate is high more, and the silica of stating after then adheres to more easily, and finally, bending strength improves, so preferably.Particularly, metal powder is preferably more than 90% by the apatite layer covered surfaces, has more preferably covered more than 95%, and further preferred all (roughly 100%) covers.
In powder of the present invention, said apatite layer, its thickness is preferably 10nm～1000nm, more preferably 20nm～500nm.When thickness more than 10nm, then have the tendency of the insulation effect of obtaining, when thickness below 1000nm, have the trend that improves density.
As the method that on said metal powder, forms apatite layer; Can enumerate following method; Make according to the rules ratio contain calcium ion or and then contain the ion that gives cationic atom or former subgroup M in the said general formula (1-b) the aqueous solution, with the reactant aqueous solution that contains phosphate ion, the method that the material that forms apatite structure is separated out on the metal powder surface.In order to prepare layer, need the liquid property of reaction solution be controlled at neutral to alkalescence zone (more than the pH=6.0) with apatite structure.Need to prove, when reaction solution is acidic region, separate out the calcium phosphate layer except the material that forms apatite structure sometimes.
Separate out as apatite layer under the situation of hydroxyapatite, for example, can enumerate, use the method for calcium nitrate aqueous solution and ammonium dihydrogen phosphate aqueous solution.The stoichiometric composition of the hydroxyapatite that obtains thus is Ca 10(PO 4) 6(OH) 2, but major part is an apatite structure, even if non-stoichiometric structure, as long as can keep its structure, for example, its part becomes Ca 10-Z(HPO 4) Z(PO 4) 6-Z(OH) 2-Z(0＜Z≤1,1.50≤Ca/P (atomic molar ratio)＜1.67) also can.
As the addition of said apatite layer raw material, with respect to the metal powder of 100 mass parts, be preferably 0.1～1.0 mass parts, more preferably 0.4～0.8 mass parts further is preferably 0.5～0.7 mass parts.When addition is 0.1 mass parts when above, has the tendency that obtains fully than resistance when manufacturing dust core.In addition, the insulating barrier of the powder that obtains becomes evenly, the effect of the insulating properties that can fully improve.When addition is 1.0 mass parts when following, when making dust core, has the tendency that can prevent that formed body density from reducing.The quality of apatite layer is calcium (and metal M) amount to be carried out quantitative methods obtain through the prepared powder that obtains is carried out elementary analysis.
(silicon dioxide granule)
As the silicon dioxide granule that in powder of the present invention, uses, can use present known silicon dioxide granule widely, specifically; Can enumerate; Aerosil, cataloid etc., but consider from maneuverable aspect, be preferably cataloid.Shape about silica has no particular limits.
As the particle diameter of silicon dioxide granule, can use the silica of all size, but consider film forming, most preferably use silicon dioxide granule with the following particle diameter of sub-micron.Specifically, the average primary particle diameter of silicon dioxide granule is preferably below the 50nm, more preferably below the 30nm, further is preferably below the 20nm.
And then aggegation does not preferably take place and is scattered here and there in silicon dioxide granule in organic solvent.Thereby,, can utilize organic group that silica particle surface is carried out modification in order to improve the dispersiveness of silicon dioxide granule.As such organic group, for example can enumerate the alkyl of cyclohexyl, phenyl, benzyl, phenethyl, C1～C6 (carbon number is 1～6) etc.
As the method for silica particle surface being carried out modification through above-mentioned organic group, can use following method, make the silane compound that in molecular structure, has above-mentioned organic group, with the method for the surface reaction of above-mentioned silicon dioxide granule.Thereby, when being prepared into dust core, can improve bending strength, also can improve according to situation and compare resistance.
As such silane compound, particularly, can use the alkoxy silane of formula (II) expression or the halogenated silanes compound of formula (III) expression.
R 1 nSi(OR 2) 4-n (II)
R 1 nSiX 4-x (III)
(in the formula, n is 1～3 integer, R 1And R 2For organic group, the X of monovalence is halogen.)
At said general formula (II) and (III), as R 1Can enumerate, hope the organic group of modification on silicon dioxide granule, specifically, can enumerate the alkyl of cyclohexyl, phenyl, benzyl, phenethyl, C1～C6 (carbon number is 1～6) etc.In addition, as R 2, can enumerate the organic group of monovalence, specifically, can enumerate methyl, ethyl etc.In addition, as X, can enumerate chlorine, bromine, iodine etc.
As the alkoxy silane shown in the above-mentioned general formula (II); Specifically; For example can enumerate trimethoxy silane classes such as MTMS, ethyl trimethoxy silane, n-pro-pyl trimethoxy silane, isopropyl trimethoxy silane, normal-butyl trimethoxy silane, tert-butyl trimethoxy silane, n-pentyl trimethoxy silane, n-hexyl trimethoxy silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, benzyl trimethoxy silane, phenethyl trimethoxy silane;
Triethoxysilicane alkanes such as MTES, ethyl triethoxysilane, n-pro-pyl triethoxysilane, isopropyl triethoxysilane, ne-butyltriethoxysilaneand, tert-butyl group triethoxysilane, n-pentyl triethoxysilane, n-hexyl triethoxysilane, cyclohexyl triethoxysilane, phenyl triethoxysilane, benzyl triethoxysilane, phenethyl triethoxysilane;
Dimethoxy silanes such as dimethyldimethoxysil,ne, ethyl-methyl dimethoxy silane, methyl n-pro-pyl dimethoxy silane, isopropyl methyl dimethoxy silane, n-butylmethyldimethoxyforane, methyl-t-butyldimethoxysilane, methyl n-pentyl dimethoxy silane, n-hexyl methyl dimethoxysilane, cyclohexyl methyl dimethoxy silane, aminomethyl phenyl dimethoxy silane, benzyl methyl dimethoxysilane, phenethyl methyl dimethoxysilane;
Diethoxy silane classes such as dimethyldiethoxysilane, ethyl-methyl diethoxy silane, methyl n-pro-pyl diethoxy silane, isopropyl methyl diethoxy silane, normal-butyl methyldiethoxysilane, methyl tertbutyl diethoxy silane, methyl n-pentyl diethoxy silane, n-hexyl methyldiethoxysilane, cyclohexyl methyl diethoxy silane, aminomethyl phenyl diethoxy silane, benzyl methyldiethoxysilane, phenethyl methyldiethoxysilane etc.
In addition; As halogenated silanes compound by above-mentioned general formula (III) expression; Specifically; For example can enumerate trichlorosilane classes such as methyl trichlorosilane, ethyl trichlorosilane, n-propyltrichlorosilan, isopropyl trichlorosilane, normal-butyl trichlorosilane, tert-butyl group trichlorosilane, n-pentyl trichlorosilane, n-hexyl trichlorosilane, cyclohexyl trichlorosilane, phenyl trichlorosilane, benzyl trichlorosilane, phenethyl trichlorosilane;
Dichlorosilane classes such as dimethyldichlorosilane, ethyl-methyl dichlorosilane, methyl n-pro-pyl dichlorosilane, isopropyl methyl dichlorosilane, normal-butyl dimethyl dichlorosilane (DMCS), methyl tertbutyl dichlorosilane, methyl n-pentyl dichlorosilane, n-hexyl dimethyl dichlorosilane (DMCS), cyclohexyl methyl dichlorosilane, dichloromethyl phenylsilane, benzyl dimethyl dichlorosilane (DMCS), phenethyl dimethyl dichlorosilane (DMCS) etc.
Above-mentioned silane compound can be distinguished independent use or make up two or more uses.
The surface modification of silicon dioxide granule is, in the dispersion liquid of silicon dioxide granule, adds said alkoxysilane compound containing trialkylsilyl group in molecular structure or said halogenated silanes compound usually, carries out through stirring method.At this moment, the silicon dioxide granule with respect to count 1 weight portion with solid constituent preferably adds 0.4～0.6 weight portion.When addition is 0.6 weight portion when following, the silane compound that is added just can not unreacted and residual, when addition is 0.4 weight portion when above, can fully obtain the modified effect for the organic group of silicon dioxide granule.Need to prove that said silicon dioxide granule can be scattered in the water, also can be scattered in the organic solvent.
In addition,, carry out the modified-reaction of organic group rapidly, preferably use acid catalysts such as inorganic acid, organic acid, acid-exchange resin with the condition of gentleness on silica particle surface.In this case, especially preferably use hydrochloric acid, nitric acid, acetate, citric acid, formic acid, ethanedioic acid etc.Generally speaking, acid can make deterioration in characteristics with said apatite reaction, and therefore, aspect high from volatility, that be difficult for remaining in the system is considered, is more preferably hydrochloric acid and acetate.As the addition of said acid catalyst, solid constituent 1 weight portion with respect to silicon dioxide granule is preferably 0.05～0.1 weight portion.
Above-mentioned modified-reaction in order to prevent the aggegation of silicon dioxide granule, is preferably under 0～50 ℃ of the temperature and carries out, and more preferably carries out under 10～40 ℃.In addition, said silicon dioxide granule preferably is dispersed in the organic solvents such as isopropyl alcohol, poly glycol monomethyl ether acetic acid esters, toluene, xylenes.
(preparation method)
The preparation method of powder of the present invention may further comprise the steps: cover metal powder and form the first step of the metal powder that covered by apatite layer (below, be called the metal powder that is covered by apatite) with apatite; Second step of adhering to SiO 2 powder on the metal powder of the metal powder that is covered by apatite that in said first step, obtains or the said apatite layer; The powder that will in said second step, obtain; Implement precuring 350 ℃ of following temperature, the apatite layer that obtains comprising said metal powder, cover said metal powder, attached to the third step of the powder of the silicon dioxide granule on said metal powder or the apatite layer.
(phosphoric acid of metal powder is handled)
In addition,, consider, preferably use the metal powder of handling through phosphoric acid from the aspect of the oxidation that can prevent metal powder as the metal powder of supplying with first step.In the preparation method of powder of the present invention, can this phosphoric acid be set before first step and handle, perhaps, can use the commercially available powder of handling as through phosphoric acid of metal powder.Phosphoric acid is handled and can be carried out through present known method.
(formation of apatite layer)
On said metal powder, form the method for apatite layer; As top explanation; Can enumerate following method: through containing calcium ion (and as required; The ion that cationic atom or former subgroup M are provided except that calcium ion) the aqueous solution, with the reaction of the aqueous solution that contains phosphate ion, the method that apatite is separated out on the metal powder surface.Specifically, can enumerate following method, in flask, add the aqueous solution and metal powder, splash into the aqueous solution while stirring as source of phosphoric acid as the calcium source.In addition, also can use following method, in flask, add entry and metal powder, stir on the limit, simultaneously or order splash into said as the calcium source the aqueous solution and as the aqueous solution of source of phosphoric acid.Under the situation that order splashes into, it is in proper order for can splash into wherein any one earlier.
As the calcium source,, have no particular limits so long as water miscible calcium compound gets final product.Specifically, for example can enumerate the calcium salt of organic acid calcium salts such as the calcium salt of inorganic acids such as the calcium salt of inorganic bases such as calcium hydroxide, calcium nitrate, calcium acetate, organic base etc.As said source of phosphoric acid, can enumerate phosphate such as phosphoric acid, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate.
In order to obtain the layer of apatite structure, it is regional that reaction solution is preferably neutral region～alkalescence, pH is preferably more than 7, more preferably more than 8, further be preferably more than 9, be preferably more than 10 especially.When reaction solution is an acidic region, the calcium phosphate layer outside the precipitation of phosphorus lime stone sometimes then, the said aqueous solution and the aqueous solution that becomes source of phosphoric acid that becomes the calcium source preferably is adjusted into pH more than 7 through alkali such as ammoniacal liquor in advance.
As reaction temperature, at room temperature also it doesn't matter, but in order to add fast response, be preferably more than 50 ℃, more preferably more than 70 ℃, is preferably especially more than 90 ℃.When solvent is under the situation of water, is the reflux temperature of reactant liquor as its ceiling temperature, promptly near 100 ℃.
As the reaction time, and different, concentration is high more according to the said concentration that becomes the aqueous solution in calcium source and the aqueous solution that becomes source of phosphoric acid, and the reaction time can be short more, and concentration is low, then preferably extends the reaction time.In preparation method of the present invention, the said aqueous solution that becomes the calcium source and as the concentration of the aqueous solution of source of phosphoric acid preferably is respectively the scope of 0.003～0.5M, as the reaction time at this moment, is preferably 1～10 hour.
(adhering to of SiO 2 powder)
Secondly, on the metal powder that is covered by apatite that obtains through said method, adhere to above-mentioned silicon dioxide granule.Can enumerate following method as this method, the dispersion liquid of above-mentioned silicon dioxide granule is joined in the metal powder that is covered by apatite, vibrate, stirring method.Under the situation of using commercially available organic silicon sol, use after also can being diluted to suitable concentration.In addition, such as stated, to the surface of silicon dioxide granule in the commercially available organic silicon sol, organic groups such as use silane compound have carried out under the situation of surface modification the reactant liquor that uses in the time of also can directly using surface modification.Need to prove that employed silicon dioxide granule can be attached on the apatite layer here, also can the metal powder surface of being exposed attached to the inadequate defect part of covering of apatite layer on.
Solvent as silicon dioxide granule is disperseed has no particular limits, and specifically, for example can enumerate, and is the alcohols solvent of representative with the isopropyl alcohol, is the ketones solvent of representative with the MEK, is the aromatic series kind solvent of representative with toluene.Aromatic solvent especially preferably, said aromatic solvent make in the organic silicon sol silicon dioxide granule keep colloidal solution shape easily.
(precuring)
Such as stated, with the metal powder that is covered by apatite that has adhered to silicon dioxide granule from the teeth outwards, precuring under the temperature below 350 ℃.Solidify apatite layer through such method, can form firm hear resistance overlay film.Do not implement precuring, when these material powder compression moldings were prepared dust core, the silicon dioxide granule on surface was embedded in the apatite layer, can't obtain sufficient insulating properties.As the temperature of above-mentioned precuring, preferably 100～300 ℃.
Need to prove that the addition of silicon dioxide granule of the present invention is with respect to employed 100 mass parts metal powders, to be preferably 0.05～1.0 mass parts.When addition is 0.05 weight portion when above, silicon dioxide granule can cover metal powder equably, obtains the effect that insulating properties is improved.On the other hand, when addition is 1.0 mass parts when following, when being prepared into dust core, can prevent the reduction of formed body density, and can prevent the reduction of the bending strength of dust core.
(manufacturing of dust core)
The powder that is used for dust core of the present invention, the mixed-powder compression molding with having mixed lubricant as required can form the compression magnetic core.Lubricant is that its dispersion liquid is coated on the metal die wall, can after drying, use.As lubricant, can use long chain hydrocarbons such as metallic soaps such as zinc stearate, calcium stearate, lithium stearate, wax, silicone oil etc.Forming pressure is preferably 500～1500MPa.And then, in order to reduce magnetic hystersis loss, can implement annealing to the dust core that manufacturing obtains.At this moment annealing temperature is preferably selected in 500～800 ℃ scope.This annealing is preferably carried out in non-active gas such as nitrogen or argon gas.
Through the dust core that above-mentioned method manufacturing obtains, demonstrate high formed body density and insulating properties.Need to prove that though can not get across for the mechanism that shows this specific character, inventor of the present invention is judged as following mechanism.That is, cover metal powder with apatite layer, through the distinctive high absorption affinity of apatite, silicon dioxide granule is more easily attached on the metal powder.And then, the silicon dioxide granule that adheres to like this, the crack site of the apatite layer that when being shaped, takes place is filled silicon dioxide granule effectively, so formed body density (7.0g/cm for example 3More than) height, so be considered to, can keep high-fire resistance and insulating properties.As above-mentioned, as silicon dioxide granule, why the particle of the following particle diameter of sub-micron is preferred, and this is because the silicon dioxide granule of small particle diameter moves easily, silicon dioxide granule more effectively is filled on the crack site of apatite layer.
The formed body density of the dust core of making by powder of the present invention, preferably 7.0g/cm 3More than, be more preferably 7.4g/cm 3More than.When density is 7.4g/cm 3When above, has the tendency that magnetic density improves.
In addition, the resistance value on said dust core surface is preferably more than the 30 μ Ω m, more preferably more than the 50 μ Ω m, further is preferably more than the 90 μ Ω m.When resistance is 30 μ Ω m when above, has the tendency of the effect of the eddy-current loss that can reduce said dust core.
Embodiment
Below, more specify the present invention through embodiment, but the present invention is not limited to these embodiment.
Embodiment 1
In the four-hole boiling flask of 300ml, add and by 25% ammoniacal liquor pH is adjusted into calcium nitrate aqueous solution 75ml 11 or more (1.79mmol is 0.024M) with iron powder 30g (the straight iron powder 300NH of Kobe Steel, Ltd society manufacturing).In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.Content in the four-hole boiling flask when room temperature (25 ℃) stirs down, was splashed into the ammonium dihydrogen phosphate aqueous solution in the dropping funel through 10 minutes.
Then, in 90 ℃ oil bath, reaction is 2 hours in the time of stirring with four-hole boiling flask.Slurries to obtaining are implemented suction filtration, and dry cake obtains grey powder (yield is 96 quality %) in 110 ℃ baking box.Through x-ray photoelectron power spectrum (XPS); The result that the atom distributive law of the near surface of resulting powder is analyzed; Atom distributive law Fe:4.58%, Ca:15.7%, Ca/P are 1.64 than (mol ratio), can confirm the fact that iron powder is covered by hydroxyapatite.
And then; The iron powder 20g that is covered by apatite that mixing has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, and 200 ℃ of following precuring 30 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m, removes huge association particle, has prepared the iron powder that is covered by apatite that adheres to nano silicon.
The section SEM picture of the iron powder that is covered by apatite for preparing as stated is shown on Fig. 1,2, and the section SEM picture that has adhered to the iron powder that is covered by apatite of nano silicon is shown on Fig. 3,4.On the surface of these particles, can confirm to be formed with the fact of hydroxyapatite layer, nanometer titanium dioxide silicon layer.
The apatite overlay film iron powder 5.92g that the nano silicon that obtains is adhered to is filled in the metal die that internal diameter is 14mm, and with the forming pressure of 1000MPa, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 296 μ Ω m.In addition, density is 7.48g/cm 3This tablet in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 91 μ Ω m.In addition, density is 7.47g/cm 3
Comparative example 1
That kind that is described below covers iron powder according to having prepared hydroxyapatite with embodiment 1 identical method.That is, in the four-hole boiling flask of 300ml, add and by 25% ammoniacal liquor pH is adjusted into calcium nitrate aqueous solution 75ml 11 or more (1.79mmol is 0.024M) with iron powder 30g (the straight iron powder 300NH of Kobe Steel, Ltd society manufacturing).In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.Content in the four-hole boiling flask when room temperature (25 ℃) stirs down, was splashed into the ammonium dihydrogen phosphate aqueous solution in the dropping funel through 10 minutes.
Then, four-hole boiling flask was reacted in 90 ℃ oil bath 2 hours while stirring.Slurries to obtaining are implemented suction filtration, and dry cake obtains grey powder (yield is 96 quality %) in 110 ℃ baking box.To the powder for preparing, utilize the sieve screening of 250 μ m, prepared the iron powder that is covered by apatite.The apatite overlay film iron powder 5.95g that obtains is filled in the metal die that internal diameter is 14mm, and with the forming pressure of 1000MPa, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 144 μ Ω m.In addition, density is 7.54g/cm 3Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 0.54 μ Ω m.In addition, density is 7.53g/cm 3
Comparative example 2
Apatite layer is not set,, on iron powder, has adhered to nano silicon according to the method for adhering to nano silicon among the embodiment 1.Promptly; Toluene solution (solid component concentration the is 3.0 quality %) 2g that mixes iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 20g and nano silicon; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml, then 200 ℃ of following precuring 30 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m, removes huge association particle, has prepared the iron powder that is covered by apatite that nano silicon adheres to.With the iron powder 5.99g that obtains, with the forming pressure of 1000MPa, be shaped diameter 1.4cm, thickness are the cylindric tablet of 5.145mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 79 μ Ω m.In addition, density is 7.57g/cm 3The tablet that ground in nitrogen atmosphere, being burnt till 1 hour with 600 ℃ of annealing, follow lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 20 μ Ω m.In addition, density is 7.57g/cm 3
Shown in the table 1 to the density of resulting dust core, than the mensuration result of resistance.
Table 1
Formed body Cover hydroxyapatite Adhere to silicon dioxide granule Density (g/cm 2) after 600 ℃ of annealing Than resistance (μ Ω m) After 600 ℃ of annealing of resistance (μ Ω m)
Embodiment 1 Have Have 7.47 296 91
Comparative example 1 Have Do not have 7.53 144 0.54
Comparative example 2 Do not have Have 7.57 79 20
Reference table 1, in order to obtain high ratio resistance, adhering to of the covering of hydroxyapatite and silicon dioxide granule all is absolutely necessary.In addition, the formed body density of embodiment 1 does, and in embodiment 1, whether covers hydroxyapatite and whether adhered to silicon dioxide granule irrelevant, compares with the formed body density of comparative example 1 and comparative example 2, almost not reduction.This is because when compression molding, be destroyed, thereby imbedded silicon dioxide granule in the pore of the crackle of the apatite layer that produces.
Then; In order to estimate the absorption affinity intensity between apatite layer and the silicon dioxide granule; Cover on the iron powder at the different straight iron powder of surface state and apatite respectively and adhered to silicon dioxide granule,, compared from the teeth outwards residual how many silicon dioxide granules through quantitative analysis.Method is following: the HPPS that uses the Mlvern manufactured; Average grain diameter based on dynamic light scattering determination is the silicon dioxide granule of 20nm; Organic silicon sol liquid (the solvent: (solid component concentration 3.0 quality %) 5.0g toluene) that contains above-mentioned particle; Adding heap(ed) capacity is the glass helix tube of 10ml, to wherein adding various powder 3.0g.Is in the mixing circulator of 105rpm with helix tube at speed setting, stirs 3 hours.With the liquid after stirring, use quantitative analysis to carry out suction filtration with No.5B (JIS P3801) filter paper, use toluene to clean filtrate, obtained various powder after the vacuum drying.
Use the ICP-OES method that the powder that obtains is carried out elementary analysis, with the silicon atom amount quantitative attached to the silicon dioxide granule on the powder.The result is shown in Table 2.
Table 2
No. Powder Si adsorbance (quality ppm)
1 Straight iron powder (300NH) 160
2 By the iron powder of apatite covering 360
From the result of table 2, be that it is many that the silicon atom amount during with straight iron powder is in a ratio of twice from the quantitative silicon atom amount of iron powder that is covered by apatite.Silicon atom singly is not from silica, and therefore, the adhesion amount of silica is many, compares with the straight iron powder superficial layer, and apatite layer is stronger to the absorption affinity of silicon dioxide granule.
Embodiment 2
In embodiment 1, increased following steps, in calcium nitrate aqueous solution, add iron powder, in 30 ℃ oil bath, stir 15 minutes step then.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder 30g (the straight iron powder 300NH that Kobe Steel, Ltd society makes), in 30 ℃ oil bath, stirred 15 minutes then.In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, and dry cake obtains the grey powder in 110 ℃ baking box.Through the x-ray photoelectron power spectrum; The result that the atom of the near surface of resulting powder is analyzed; Atom distributive law Fe:3.31%, Ca:17.1%, Ca/P are 1.63 than (mol ratio), can confirm the fact that iron powder is covered by hydroxyapatite.
And then; The powder 20g that is covered by apatite that mixing has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The powder of 6g after the sieve screening is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 236 μ Ω m.In addition, formed body density is 7.50g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 75 μ Ω m.In addition, density is 7.50g/cm 2
Embodiment 3
In embodiment 2, increased following steps, in the four-hole boiling flask content, splash into ammonium dihydrogen phosphate aqueous solution after, in 30 ℃ oil bath, stirred 1.5 hours.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, and dry cake obtains the grey powder in 110 ℃ baking box.Through the x-ray photoelectron power spectrum; The result that the atom of the near surface of resulting powder is analyzed; Atom distributive law Fe:5.56%, Ca:14.85%, Ca/P are 1.63 than (mol ratio), can confirm the fact that powder is covered by hydroxyapatite.
And then; The powder 20g that is covered by apatite that mixing has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The iron powder that after precuring, obtains is utilized the sieve screening of 250 μ m.
The iron powder that is covered by apatite that the nano silicon that 6g has prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 111 μ Ω m.In addition, formed body density is 7.51g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 55 μ Ω m.In addition, formed body density is 7.51g/cm 2
Embodiment 4
In embodiment 3, the reaction time under 90 ℃ changed to 10 minutes from 2 hours.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.Afterwards, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 10 minutes down.Slurries to obtaining are implemented suction filtration, and dry cake obtains the grey powder in 110 ℃ baking box.Through the x-ray photoelectron power spectrum, to the result that the atom of the near surface of resulting powder is analyzed, atom distributive law Fe:6.79%, Ca:12.77%, Ca/P are 1.44 than (mol ratio).
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The iron powder that after precuring, obtains is utilized the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 214 μ Ω m.In addition, formed body density is 7.50g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 53 μ Ω m.In addition, formed body density is 7.49g/cm 2
Embodiment 5
In embodiment 3, the reaction time under 90 ℃ changed to 5 hours from 2 hours.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 5 hours down.Slurries to obtaining are implemented suction filtration, and dry cake obtains the grey iron powder in 110 ℃ baking box.Through the x-ray photoelectron power spectrum; The result that the atom of the near surface of resulting powder is analyzed; Atom distributive law Fe:6.07%, Ca:13.98%, Ca/P are 1.67 than (mol ratio), can confirm the fact that powder is covered by hydroxyapatite.
And then; With the powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The iron powder that after precuring, obtains is utilized the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 218 μ Ω m.In addition, formed body density is 7.47g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 93 μ Ω m.In addition, formed body density is 7.47g/cm 2
Embodiment 6
In embodiment 3, reaction temperature is changed to 30 ℃ from 90 ℃.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.Then, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 3.5 hours through 10 minutes.
Then, the slurries that obtain are implemented suction filtration, dry cake obtains the grey iron powder in 110 ℃ baking box.Through the x-ray photoelectron power spectrum; The result that the atom of the near surface of resulting powder is analyzed; Atom distributive law Fe:7.84%, Ca:11.67%, Ca/P are 1.65 than (mol ratio), can confirm the fact that iron powder is covered by hydroxyapatite.
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 119 μ Ω m.In addition, formed body density is 7.53g/cm 2
Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 31 μ Ω m.In addition, density is 7.53g/cm 2
Embodiment 7
In embodiment 3, reaction temperature is changed to 50 ℃ from 90 ℃.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 50 ℃ from 30 ℃ through 5 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, and dry cake obtains the grey iron powder in 110 ℃ baking box.Through the x-ray photoelectron power spectrum; The result that the atom of the near surface of resulting powder is analyzed; Atom distributive law Fe:7.08%, Ca:13.24%, Ca/P are 1.77 than (mol ratio), can confirm the fact that iron powder is covered by hydroxyapatite.
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.
The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 176 μ Ω m.In addition, formed body density is 7.46g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 53 μ Ω m.In addition, density is 7.47g/cm 2
Embodiment 8
In embodiment 3, reaction temperature is changed to 30 ℃ from 90 ℃, implemented 110 ℃ burn till.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 3.5 hours through 10 minutes.
Then, the slurries that obtain are implemented suction filtration, in stainless steel tray, take out filter cake, drying is 5 minutes under the pressure below the 1MPa, obtains the iron powder of grey.Through the x-ray photoelectron power spectrum, to the result that the atom of the near surface of resulting powder is analyzed, atom distributive law Fe:5.53%, Ca:13.63%, Ca/P are 1.52 than (mol ratio).
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.
The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 168 μ Ω m.In addition, formed body density is 7.50g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 56 μ Ω m.In addition, formed body density is 7.49g/cm 2
Embodiment 9
In embodiment 3, reaction temperature is changed to 50 ℃ from 90 ℃, implemented 110 ℃ burn till.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 50 ℃ from 30 ℃ through 5 minutes, when stirring the four-hole boiling flask content 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, in stainless steel tray, take out filter cake, and drying is 5 minutes under the pressure below the 1MPa, obtain the iron powder of grey.Through the x-ray photoelectron power spectrum; The result that the atom of the near surface of resulting powder is analyzed; Atom distributive law Fe:4.89%, Ca:15.54%, Ca/P are 1.77 than (mol ratio), can confirm the fact that powder is covered by hydroxyapatite.
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 137 μ Ω m.In addition, formed body density is 7.50g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 44 μ Ω m.In addition, formed body density is 7.50g/cm 2
Embodiment 10
In embodiment 3, implemented 110 ℃ burn till.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (1.79mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.Then, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.07mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, and are dry at the vacuum under pressure of 0MPa, obtain the iron powder of grey.Through the x-ray photoelectron power spectrum, to the result that the atom of the near surface of resulting powder is analyzed, atom distributive law Fe:3.85%, Ca:16.63%, Ca/P are 1.56 than (mol ratio).
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the lMPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 137 μ Ω m.In addition, formed body density is 7.50g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 30 μ Ω m.In addition, formed body density is 7.50g/cm 2
Embodiment 11
In embodiment 3, the addition of calcium nitrate is changed to 0.60mmol from 1.79mmol, the addition of ammonium dihydrogen phosphate (ADP) changes to 0.36mmol from 1.07mmol.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (0.60mmol more than 11 with pH; 0.008M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.Then, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (0.36mmol 0.005M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, the dry iron powder that obtains grey in 110 ℃ baking box.Through the x-ray photoelectron power spectrum, to the result that the atom of the near surface of resulting powder is analyzed, atom distributive law Fe:7.29%, Ca:13.14%, Ca/P are 1.52 than (mol ratio).
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 122 μ Ω m.In addition, formed body density is 7.56g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 30 μ Ω m.In addition, formed body density is 7.56g/cm 2
Embodiment 12
In embodiment 3, the addition of calcium nitrate is changed to 2.98mmol from 1.78mmol, the addition of ammonium dihydrogen phosphate (ADP) changes to 1.78mmol from 1.07mmol.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (2.98mmol more than 11 with pH; 0.040M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.Then, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (1.78mmol 0.024M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, the dry iron powder that obtains grey in 110 ℃ baking box.Through the x-ray photoelectron power spectrum, to the result that the atom of the near surface of resulting powder is analyzed, atom distributive law Fe:2.76%, Ca:17.59%, Ca/P are 1.67 than (mol ratio).
And then; With the iron powder 20g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 2g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 213 μ Ω m.In addition, formed body density is 7.44g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 88 μ Ω m.In addition, formed body density is 7.44g/cm 2
Embodiment 13
According to the method identical with embodiment 11, the iron powder that is covered by hydroxyapatite that preparation is made up of the individual layer hydroxyapatite layer, and then repeat identical processing, the preparation hydroxyapatite layer is the double-deck iron powder that is covered by hydroxyapatite.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (0.60mmol more than 11 with pH; 0.008M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.After this, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (0.36mmol 0.005M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, when stirring the four-hole boiling flask content 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, the dry iron powder (yield is 96 quality %) that obtains grey in 110 ℃ baking box.
Then, in the four-hole boiling flask of 300ml, add resulting apatite individual layer overlay film powder 28.8g and by 25% ammoniacal liquor pH is adjusted into calcium nitrate aqueous solution 72ml more than 11 (0.57mmol 0.008M), stirred 15 minutes then in 30 ℃ oil bath.Then, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 72ml more than 11 (0.34mmol 0.005M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, the dry iron powder that obtains grey in 110 ℃ baking box.Through the x-ray photoelectron power spectrum, to the result that the atom of the near surface of resulting powder is analyzed, atom distributive law Fe:7.05%, Ca:13.84%, Ca/P are 1.59 than (mol ratio).
And then; With double-deck toluene solution (solid component concentration the is 3.0 quality %) 2g that covers powder 20g and organic silicon sol of the apatite that has prepared; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 131 μ Ω m.In addition, formed body density is 7.53g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 59 μ Ω m.In addition, formed body density is 7.53g/cm 2
Embodiment 14
According to the method identical with embodiment 13, preparation covers iron powder by the hydroxyapatite that double-deck hydroxyapatite layer constitutes, and then repeats identical processing, and the preparation hydroxyapatite layer is that the hydroxyapatite of three-decker covers iron powder.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 300ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 75ml (0.60mmol more than 11 with pH; 0.008M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 30g, in 30 ℃ oil bath, stirred 15 minutes then.After this, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 75ml more than 11 (0.36mmol 0.005M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, the dry iron powder that obtains grey in 110 ℃ baking box.
Then, in the four-hole boiling flask of 300ml, add resulting apatite individual layer overlay film iron powder 29.5g and by 25% ammoniacal liquor pH is adjusted into calcium nitrate aqueous solution 74ml more than 11 (0.59mmol 0.008M), stirred 15 minutes then in 30 ℃ oil bath.Then, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 74ml more than 11 (0.35mmol 0.005M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, the dry iron powder that obtains grey in 110 ℃ baking box.
Then, in the four-hole boiling flask of 300ml, add the double-deck overlay film iron powder 29.5g of resulting apatite and by 25% ammoniacal liquor pH is adjusted into calcium nitrate aqueous solution 74ml more than 11 (0.59mmol 0.008M), stirred 15 minutes then in 30 ℃ oil bath.In addition, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 74ml more than 11 (0.35mmol 0.005M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 1.5 hours through 10 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, the dry iron powder that obtains grey in 110 ℃ baking box.Through the x-ray photoelectron power spectrum, to the result that the atom of the near surface of resulting powder is analyzed, atom distributive law Fe:10.33%, Ca:10.95%, Ca/P are 1.69 than (mol ratio).
And then; Three layers of toluene solution (solid component concentration is 3.0 quality %) 2g that covers iron powder 20g and organic silicon sol of the apatite that has prepared; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 95 μ Ω m.In addition, formed body density is 7.494g/cm 2Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 31 μ Ω m.In addition, formed body density is 7.50g/cm 2
Embodiment 15
In embodiment 3; With more 33 times of the iron powder quantitative changes that is added; Simultaneously reaction vessel volume, quantity of solvent etc. are also changed to 33 times, in the four-hole boiling flask content, splash into ammonium dihydrogen phosphate aqueous solution after, the time of in 30 ℃ oil bath, stirring changed to 2 hours from 1.5 hours.
Promptly; The ammoniacal liquor that in the four-hole boiling flask of 1000ml, adds by 25% is adjusted into the calcium nitrate aqueous solution 250ml (5.95mmol more than 11 with pH; 0.024M) and iron powder (the straight iron powder 300NH that Kobe Steel, Ltd society makes) 100g, in 30 ℃ oil bath, stirred 15 minutes then.Then, in having the dropping funel of side pipe, add and by 25% ammoniacal liquor pH is adjusted into ammonium dihydrogen phosphate aqueous solution 250ml more than 11 (3.57mmol 0.014M), is fixed on the four-hole boiling flask then.When four-hole boiling flask stirred in 30 ℃ oil bath, the ammonium dihydrogen phosphate aqueous solution in the dropping funel is splashed into, then the temperature of oil bath is remained 30 ℃ and stirred 2 hours through 30 minutes.
Then, the temperature of oil bath is warming up to 90 ℃ from 30 ℃ through 10 minutes, in the time of stirring 90 ℃ of reactions 2 hours down.Slurries to obtaining are implemented suction filtration, and dry cake obtains the grey powder in 110 ℃ baking box.Through the x-ray photoelectron power spectrum; The result that the atom of the near surface of resulting powder is analyzed; Atom distributive law Fe:3.85%, Ca:15.30%, Ca P are 1.76 than (mol ratio), can confirm that iron powder is by the covered fact of hydroxyapatite.
And then; With the iron powder 60g that is covered by apatite that has prepared and toluene solution (solid component concentration the is 3.0 quality %) 6g of organic silicon sol; In the greatest content amount is vibration 10 minutes in the polypropylene system bottle of 50ml; Then content is taken out in stainless steel tray, with the pressure drying below the 1MPa 5 minutes, with the powder that takes out 200 ℃ of following precuring 25 minutes.The powder that after precuring, obtains utilizes the sieve screening of 250 μ m.The iron powder that is covered by apatite that the nano silicon that 6g has been prepared adheres to is filled in the metal die that internal diameter is 14mm, with 1000MPa/cm 2Forming pressure, columned tablet has been shaped.The thickness of the tablet for preparing at this moment, is about 5mm.Tablet surface to being shaped is ground, and uses four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 193 μ Ω m.In addition, formed body density is 7.51g/cm 3Tablet after this grinding in nitrogen atmosphere, with 600 ℃ of annealing 1 hour, being followed lapped face once more, use four point probe determination of resistivity appearance to measure the result of specific volume resistance (than resistance), is 41 μ Ω m.In addition, formed body density is 7.51g/cm 2
In table 3～5, having concluded the hydroxyapatite that in embodiment 1～15, obtains covers the hydroxyapatite that iron powder and nano silicon adhere to and covers the relevant evaluation result of iron powder.
Table 3
Figure GPA00001151438200291
Table 4
Figure GPA00001151438200301
Table 5
Figure GPA00001151438200311
Reference table 4 even if clear and definite synthetic method is different, also can form the hydroxyapatite layer of the coverage rate of same degree on metal powder.In addition, reference table 3 and table 5, the hydroxyapatite that the clear and definite nano silicon that in manufacturing process, is included in the step of 100～300 ℃ of following precuring adheres to covers the dust core of iron powder, shows the high ratio resistance and the thing of formed body density.

Claims (8)

1. powder, it comprises metal powder, covers the apatite layer of said metal powder, attached to the silicon dioxide granule on the said apatite layer.
2. the described powder of claim 1, said apatite layer contains the perhaps compound shown in (I-b) of formula (I-a),
Ca 10(PO 4) 6X 2 (I-a)
Ca (10-(m×n)/2)M n(PO 4) 6X 2 (I-b)
In the formula, M representes to give cationic atom, and m representes the cationic valence mumber that M gives, and n is above 0 and is below 5 that X representes to give the anionic atom or the former subgroup of monovalence.
3. claim 1 or 2 described powder, said silicon dioxide granule is the silicon dioxide granule through the organic group surface modification.
4. the described powder of claim 3, said silicon dioxide granule through the organic group surface modification for use formula (II) perhaps compound shown in (III) carry out the silicon dioxide granule of surface modification,
R 1 nSi(OR 2) 4-n (II)
R 1 nSiX 4-n (III)
In the formula, n is 1～3 integer, R 1And R 2Expression any monovalent organic radical group, X representes halogen.
5. claim 1 or 2 described powder, said metal powder is the powder of soft magnetic material.
6. claim 1 or 2 described powder are the powder that are used for dust core.
7. the preparation method of a powder, this method may further comprise the steps:
First step covers metal powder and obtains apatite covering metal powder with apatite;
Second step, the apatite that in said first step, obtains cover the metal powder surface of metal powder and perhaps adhere to SiO 2 powder on the apatite layer surface;
Third step; For the powder that in said second step, obtains; Implementing precuring below 350 ℃, obtaining comprising said metal powder, cover the apatite layer of said metal powder, attached to the powder of the silicon dioxide granule on said metal powder or the apatite layer.
8. the preparation method of the described powder of claim 7 wherein, as the said metal powder that supplies in said first step, uses the metal powder of handling through phosphoric acid.
CN2008801199246A 2007-12-10 2008-11-19 Powder and method for producing the same Expired - Fee Related CN101896300B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2007318251 2007-12-10
JP2007-318251 2007-12-10
PCT/JP2008/071031 WO2009075173A1 (en) 2007-12-10 2008-11-19 Powder and method for producing the same

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201210225600.9A Division CN102717069B (en) 2007-12-10 2008-11-19 Powder and method for producing the same

Publications (2)

Publication Number Publication Date
CN101896300A CN101896300A (en) 2010-11-24
CN101896300B true CN101896300B (en) 2012-08-22

Family

ID=40755416

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201210225600.9A Expired - Fee Related CN102717069B (en) 2007-12-10 2008-11-19 Powder and method for producing the same
CN2008801199246A Expired - Fee Related CN101896300B (en) 2007-12-10 2008-11-19 Powder and method for producing the same

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201210225600.9A Expired - Fee Related CN102717069B (en) 2007-12-10 2008-11-19 Powder and method for producing the same

Country Status (6)

Country Link
EP (1) EP2226142A4 (en)
JP (1) JP5321469B2 (en)
CN (2) CN102717069B (en)
CA (1) CA2708830C (en)
TW (1) TWI433741B (en)
WO (1) WO2009075173A1 (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011127201A (en) * 2009-12-18 2011-06-30 Hitachi Chem Co Ltd Coated metal powder, powder magnetic core and their production methods
US9646756B2 (en) * 2010-03-26 2017-05-09 Hitachi Powdered Metals Co., Ltd. Powder magnetic core and method for producing the same
JP5382947B2 (en) * 2010-04-08 2014-01-08 株式会社アルバック DIFFERENTIAL TRANSFORMER CORE FOR PROTECT TYPE STEP METER AND ITS MANUFACTURING METHOD
JP5565595B2 (en) * 2010-04-09 2014-08-06 日立化成株式会社 Coated metal powder, dust core and method for producing them
JP4927983B2 (en) * 2010-04-09 2012-05-09 日立化成工業株式会社 Powder magnetic core and manufacturing method thereof
JP5555945B2 (en) * 2010-04-09 2014-07-23 日立化成株式会社 Powder magnetic core and manufacturing method thereof
JP2012088507A (en) * 2010-10-19 2012-05-10 Nitto Denko Corp Depolarizing film, liquid crystal panel, and liquid crystal display device
JP2012104573A (en) * 2010-11-08 2012-05-31 Hitachi Chem Co Ltd Powder for core, manufacturing method of the same, dust core using the same, and electromagnetic device
JP5027945B1 (en) * 2011-03-04 2012-09-19 住友電気工業株式会社 Dust compact, manufacturing method of compact compact, reactor, converter, and power converter
JP5997424B2 (en) * 2011-07-22 2016-09-28 住友電気工業株式会社 Manufacturing method of dust core
CN104335300A (en) * 2012-05-25 2015-02-04 Ntn株式会社 Powder core, powder core manufacturing method, and method for estimating eddy current loss in powder core
KR20150002172A (en) * 2013-06-28 2015-01-07 삼성전기주식회사 Composite and method for forming the composite, and inductor manufactured using the composite
KR20150011168A (en) * 2013-07-22 2015-01-30 삼성전기주식회사 Magnetic material, the manufacturing method of the same and electric part comprising the same
US9754710B2 (en) 2013-09-27 2017-09-05 Hitachi Chemical Company, Ltd. Powder magnetic core, method of manufacturing powder compact for magnetic core, die and die assembly for manufacturing powder magnetic core, and die lubricating composition for manufacturing powder magnetic core
US11915847B2 (en) * 2017-03-09 2024-02-27 Tdk Corporation Dust core
CN111842874A (en) * 2019-04-24 2020-10-30 昆山磁通新材料科技有限公司 Method for improving insulation impedance characteristic of metal powder core and metal powder core thereof
CN110358941B (en) * 2019-08-12 2021-04-16 河南科技大学 Tungsten-based alloy material and preparation method thereof
EP4058225A1 (en) * 2019-11-11 2022-09-21 Carpenter Technology Corporation Soft magnetic composite materials and methods and powders for producing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5039559A (en) * 1988-05-24 1991-08-13 Sang Jean V Method of making magnetically attractable particles
JP2687683B2 (en) * 1989-06-09 1997-12-08 松下電器産業株式会社 Composite material and method for producing the same
US6210625B1 (en) * 1996-02-20 2001-04-03 Mikuni Corporation Method for producing granulated material

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3062969B2 (en) * 1991-10-14 2000-07-12 科学技術振興事業団 Bioactive layer coating method
JPH09180924A (en) * 1995-12-27 1997-07-11 Kobe Steel Ltd Dust core and manufacture thereof
JP3959564B2 (en) * 1997-12-24 2007-08-15 村樫石灰工業株式会社 Method for producing a solid substance converted into porous apatite from the surface layer to the core
JP4060101B2 (en) * 2002-03-20 2008-03-12 株式会社豊田中央研究所 Insulating film, magnetic core powder and powder magnetic core, and methods for producing them
JP4328170B2 (en) * 2003-10-03 2009-09-09 トライアル株式会社 Method for producing coated resin particles
JP2006348335A (en) * 2005-06-14 2006-12-28 Jfe Steel Kk Iron-based mixed powder for powder metallurgy
JP2007027480A (en) * 2005-07-19 2007-02-01 Sumitomo Metal Mining Co Ltd Resin bonding magnet composition, its manufacturing method, and resin bonding magnet using the composition
JP2007194273A (en) 2006-01-17 2007-08-02 Jfe Steel Kk Dust core and soft magnetic metal powder therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5039559A (en) * 1988-05-24 1991-08-13 Sang Jean V Method of making magnetically attractable particles
JP2687683B2 (en) * 1989-06-09 1997-12-08 松下電器産業株式会社 Composite material and method for producing the same
US6210625B1 (en) * 1996-02-20 2001-04-03 Mikuni Corporation Method for producing granulated material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JP特开平4-332562A 1992.11.19
JP第2687683号B2 1997.08.22

Also Published As

Publication number Publication date
CN102717069B (en) 2014-12-17
CN101896300A (en) 2010-11-24
TWI433741B (en) 2014-04-11
EP2226142A4 (en) 2017-04-12
CN102717069A (en) 2012-10-10
CA2708830C (en) 2013-01-22
WO2009075173A1 (en) 2009-06-18
JP5321469B2 (en) 2013-10-23
JPWO2009075173A1 (en) 2011-04-28
CA2708830A1 (en) 2009-06-18
EP2226142A1 (en) 2010-09-08
TW200932404A (en) 2009-08-01

Similar Documents

Publication Publication Date Title
CN101896300B (en) Powder and method for producing the same
JP5565595B2 (en) Coated metal powder, dust core and method for producing them
CN105612014B (en) Metal powder slurry and its manufacture method
CN101479062A (en) Iron-based soft magnetic powder for dust core, method for producing the same and dust core
CN102598163B (en) Ferromagnetic powder composition and method for its production
TWI659928B (en) Temperature-stable soft-magnetic powder
CN102834208A (en) Powder magnetic core and process for production thereof
JP2013243268A (en) Dust core, coated metal powder for dust core, and methods for producing them
JP6265210B2 (en) Reactor dust core
JP2014072367A (en) Coated metal powder and dust core
CN101855681A (en) Iron powder for dust core
CN103415899A (en) Iron base soft magnetic powder for powder magnetic core, fabrication method for same, and powder magnetic core
CN105828982A (en) Soft magnetic composite powder and component
JP2005113258A (en) Metal powder for powder magnetic core, and powder magnetic core using it
JP2007042883A (en) Soft magnetic material, its manufacturing method, and dust core containing same
JP2012104573A (en) Powder for core, manufacturing method of the same, dust core using the same, and electromagnetic device
JP4790224B2 (en) SOFT MAGNETIC MATERIAL, ITS MANUFACTURING METHOD, AND DUST MAGNETIC CORE CONTAINING THE SOFT MAGNETIC MATERIAL
JP2011127201A (en) Coated metal powder, powder magnetic core and their production methods
JP4436172B2 (en) Powder for powder magnetic core, powder magnetic core using the same, and method for producing powder magnetic core
JP7014231B2 (en) A coating liquid for forming an insulating film for grain-oriented electrical steel sheets, and a method for manufacturing grain-oriented electrical steel sheets.
JP6267836B1 (en) Method for producing metallic silver fine particles
JP6790584B2 (en) Soft magnetic metal powder and powder magnetic core
KR101542191B1 (en) Complex of core-shell, Ceramic pigment containing that and Ceramic phosphor containing that
JP5657280B2 (en) Coated magnetite particles and method for producing the same
JPH09241583A (en) Inorganic binder composition and production thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120822

Termination date: 20161119