CN103314132B - The surface treatment of metal object - Google Patents
The surface treatment of metal object Download PDFInfo
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- CN103314132B CN103314132B CN201180064637.1A CN201180064637A CN103314132B CN 103314132 B CN103314132 B CN 103314132B CN 201180064637 A CN201180064637 A CN 201180064637A CN 103314132 B CN103314132 B CN 103314132B
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- metal
- treatment stove
- activation
- diffusion
- metal base
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Crucibles And Fluidized-Bed Furnaces (AREA)
Abstract
The invention discloses a kind of method of the diffusion surface layer extended internally for the formation of the outside surface from pending metal base or component, described method comprises: in activation stage first, activation treatment stove is provided, it contains inert particle refractory materials and for the formation of described diffusion surface layer, comprise the metal_based material of metal and metal halide, described activation treatment stove and accessory has the inert gas flow and the hydrogen halide stream that are directed in inert particle refractory materials in described activation treatment stove and metal_based material and continue first time period, at least to activate the exterior surface area of described metal_based material, form the metal_based material of activation, and in diffusion phase subsequently, DIFFUSION TREATMENT stove is provided and described metal base is imported in described DIFFUSION TREATMENT stove, described metal base is pretreated to form the spreading area extended internally from the outside surface of metal base, in described metal base, nitrogen has been diffused to form internal divergence district with at least partly by nitrided iron, the external compounds layer of iron carbide or carbon nitrided iron compound formation or white layer, the described outside surface of metal base do not have oxide skin, and under the metal_based material of described activation exists, by seal to prevent ambient air from entering DIFFUSION TREATMENT stove in, under inert gas atmosphere, when there is not hydrogen halide by metal base process at least the second time period, to form described diffusion surface layer on described metal base.
Description
The present invention relates to for the treatment of metal base to obtain the method and apparatus of diffusion surface layer on the substrate.
Traditionally, metal finishing is included on base material and forms nitrided surface, then physical vapor deposition such as titanium, chromium nitride coating or using carbon carbonitriding on said surface as adhering coating.Carry out a few thing, in working described in it, while nitrogen diffuses to the surface, surfacing material has been diffused in the surface region of base material, manufacture chromium or titanium nitride or carbon nitride layer on said surface.European patent number 0471276,0252480,0303191 and international publication number WO/47794 delivered patent specification discloses such treatment process.Such method can provide performance better surface treatment, this is not only because described upper layer is diffusion layer the coating being attached to base material, but, for obtaining the working control of this results needed to required material and parameter, be proved to be very difficult.The use of the halide gas such as HCl mixed with reactant gas or inflammable gas such as hydrogen and/or ammonia, causes difficulty in the structure of mixed gas group.In addition, HCl is relatively costly with other halide gas, and a large amount of uses of such gas can bring the relatively costly processing of required product.In addition, halide gas can form solid ammonium chloride with ammonia instantaneous reaction at low temperatures, and it in barrier gas pipeline the magnetic valve even draining back to gas transportation facilities and rate of flow meter, may cause blocking and the latent lesion of equipment.
International patent application no PCT/AU2006/001031 discloses the treatment process and treatment unit that can form required diffusion layer on metal base product, described method discloses supplies halide gas within whole very long processing period, although and the satisfactory operation of method, but due to use halide gas needed for volume, tooling cost is very expensive.
Therefore, the object of this invention is to provide and form diffusion surface layer on metal base in the mode more more economical than art methods, still retain the method for the reliable of described metal base and processed safely simultaneously.
Therefore, first aspect, the invention provides the method forming the diffusion surface layer extended internally from the outside surface of metal base, described method comprises:
(i) in activation stage, activation treatment stove containing inert particle refractory materials and the metal_based material for the formation of described diffusion surface layer is provided, described activation treatment stove and accessory has the inert gas flow being directed in inert particle refractory materials in described activation treatment stove and metal_based material and continuing first time period, to process the exterior surface area of described metal_based material under hydrogen halide existence, form the metal_based material with the activation of the surf zone of activation; And
(ii) in diffusion phase, DIFFUSION TREATMENT stove is provided and described metal base is imported in described DIFFUSION TREATMENT stove, described metal base is pretreated to form the spreading area extended internally from the outside surface of metal base, in described metal base, nitrogen has been diffused to form internal divergence district with at least partly by nitrided iron, the external compounds layer of iron carbide or carbon nitrided iron compound formation or white layer, the described outside surface of metal base do not have oxide skin, and under the metal_based material of described activation exists, by seal to prevent ambient air from entering DIFFUSION TREATMENT stove in, under inert gas atmosphere, when there is not hydrogen halide by metal base process at least the second time period, to form described diffusion surface layer on described metal base.
Easily, aforesaid method can also comprise:
(i) in pretreatment stage, form the described spreading area extended internally from the surface of metal base, in described metal base, nitrogen has been diffused the external compounds floor or the white layer that form internal divergence district and nitrided iron, iron carbide or carbon nitrided iron compound; And
(ii) before the described metal diffusing stage, the metal base formed in described pretreatment stage is processed, to prevent from forming oxide on surface on said surface, or remove any described oxide on surface formed on said surface.
In preferable configuration, aforesaid method can carry out in single process stove, and wherein DIFFUSION TREATMENT stove is also used as activation treatment stove.But described method can be carried out in the different stoves being used as activation treatment stove and DIFFUSION TREATMENT stove.
In activation stage, inert gas flow is preferably nitrogen and/or argon gas.In the situation of being applicable to, the inert particle refractory materials used in one or more process stove can be aluminum oxide or silicon carbide.
In the situation of being applicable to, when DIFFUSION TREATMENT stove contains inert particle refractory materials, it carries out fluidisation by inert gas flow in the metal diffusing stage.Or such inert particle refractory materials can by mode of vibration fluidisation or at least part of fluidisation.In the metal diffusing stage, preferably not to DIFFUSION TREATMENT stove supply ammonia.
In particularly preferred embodiments, described second time period is longer than described first time period.In this way, obtain required diffusion layer on metal base and use the time period much shorter of relatively costly hydrogen halide.In described diffusion phase, hydrogen halide may do not used completely, but if needed, a small amount of hydrogen halide can be used the short period of time to reactivate metal_based material.If needed, in diffusion phase, usually pulse can supply hydrogen halide, last and do not provide the time period of hydrogen halide and at least one to provide the time period of hydrogen halide in burner hearth.
Be applicable in situation, inert gas flow can be provided to DIFFUSION TREATMENT stove in described second time period, described inert gas flow can zero flow velocity to be equal to or higher than described DIFFUSION TREATMENT stove incipient fluidization speed flow velocity between change.
In the situation of being applicable to, in activation stage and diffusion phase, the operating temperature of the first and second time periods of one or more process stove is between 500 to 750 DEG C.
In one embodiment, in described first time period, preferably can to activation treatment stove hydrogen halide stream without interruption.In possible choosing in mode, in described first time period, hydrogen halide can to comprise the pulse mode supply of supply time section and not supply time section.In the situation of being applicable to, the hydrogen halide used can be selected from hydrogen chloride gas, bromize hydrogen gas, hydrogen fluoride gas or hydrogen iodide gas.Supplying seasonable to activation treatment stove or DIFFUSION TREATMENT stove, hydrogen halide preferably mixes with inert carrier gas (such as nitrogen and/or argon gas) in one or more process stove outside.In the situation of being applicable to, supplying at once, hydrogen halide and inert carrier gas enter wherein at the lower region place of one or more process stove.
In another embodiment, can by supply ammonium chloride (NH
4cl) in one or more process stove, hydrogen is produced.Ammonium chloride can be managed or pipeline supply by delivering with solid or pellets, and therefore it is heated to be dissociated into nitrogen and hydrogenchloride (HCl) gas in delivery pipeline or pipe.Rare gas element such as nitrogen or argon gas also can, by described delivery pipe supply, make HCl gas mix with rare gas element at least partly when entering stove.Such delivery system can be used in activation stage, if or needed in diffusion phase.If use this delivery system, the operating temperature of stove can close to 700 DEG C or even higher temperature.
Metal_based material for the formation of diffusion surface layer can be selected from following at least one:
(i) solid metal or metal alloy;
(ii) be coated in the metal or metal alloy in substrate carrier;
(iii) particle or powder metal or metal alloy;
(iv) be coated in the metal or metal alloy on inert particle refractory materials;
(v) metallic halide particles or powder (anhydrous or hydration); And
(vi) be coated in the metal halide material (anhydrous or hydration) in inertia refractory particulate material or substrate carrier.
Metal_based material can be selected from chromium, titanium, vanadium, niobium, tantalum, tungsten, molybdenum, manganese and alloy thereof, comprises ferrous alloy, or the metal halide be made up of with the halogen root being selected from chlorine root, bromine root, iodine root and fluorine root the metallic element of above-mentioned metal.
In the situation of being applicable to, metal base is ferrous metals or ferrous metals alloy.
In the situation of being applicable to, in described second time period, the nitrogen as rare gas element is imported in DIFFUSION TREATMENT stove.
Term " metal base " intend refer to be made up of ferrous metals or ferrous metals alloy be suitable for heat treated any metal parts.
According to method of the present invention, using hydrogenchloride as halide gas and using chromium metallics in the situation forming diffusion surface layer, it is believed that in activation stage, hydrogenchloride produces active chromium chloride on the chromium metallics of aluminum oxide (non-reactive fluidizing medium) on the surface and in fluid bed furnace.In the metal diffusing stage of method, between the chromium chloride and the iron surface being rich in nitrogen of metal base of activation, there is solid state interaction, form diffusion surface layer on the substrate.This at process stove, be generally fluid bed furnace and substantially do not occurred by during inert gas flow fluidisation, and also to occur when described bed is fluidized.As known in the art, the fluidisation of bed by applicable gas stream or can be undertaken by some vibration means.Described method has sizable economical advantage, because hydrogen halide, to be generally hydrogenchloride be expensive, be down to by its consumption and minimumly provide much economic method.
Generally wish that the external portion (white layer) of spreading area is substantially free of hole.Described white layer is nitrided iron, iron carbide and/or carbon nitrided iron normally, is generally ε and/or γ form.
Be described referring now to the preferred implementation of accompanying drawing to the inventive method, in the drawing:
Fig. 1 is the cross sectional representation of the fluid bed furnace that can use in enforcement of the present invention;
Fig. 2 and 3 is the detailed cross sectional view of the seal arrangement that can use together with the fluid bed furnace shown in Fig. 1;
Fig. 4 shows in the metal sample of the process of producing according to the present invention of embodiment 1, and % by weight concentration of nitrogen (N), chromium (Cr) and iron (Fe) is with the variation diagram of the degree of depth;
Fig. 5 shows in the copper carrier substrate of the chromiumcoating of the activation in embodiment 1, and nitrogen (N), chromium (Cr), iron (Fe) and copper (Cu) are with the variation diagram of the degree of depth;
Fig. 6 shows in the metal sample of the process of producing not in accordance with the present invention of embodiment 1, and % by weight concentration of nitrogen (N), chromium (Cr) and iron (Fe) is with the variation diagram of the degree of depth;
Fig. 7 shows in the copper carrier substrate of the non-activated chromiumcoating of embodiment 1, and % by weight concentration of nitrogen (N), chromium (Cr), iron (Fe) and copper (Cu) is with the variation diagram of the degree of depth;
Fig. 8 shows in the metal sample of the process of producing according to the present invention of embodiment 2, and % by weight concentration of chromium (Cr), iron (Fe) and nitrogen (N) is with the variation diagram of the degree of depth;
Fig. 9 shows in the activation chromium sample of process obtained by performing method of the present invention used in example 2, and % by weight concentration of chromium (Cr), iron (Fe) and nitrogen (N) is with the variation diagram of the degree of depth;
Figure 10 shows in the in example 2 described metal sample not by preactivated chromium sample preparation, and % by weight concentration of iron (Fe), nitrogen (N) and chromium (Cr) is with the variation diagram of the degree of depth;
Figure 11 is quantitative depth distribution plan, it illustrates in the metal sample of in embodiment 3 described use activation chromium powder end according to process of the present invention, and % by weight concentration of iron (Fe), chromium (Cr), nitrogen (N), carbon (C) and oxygen (O) is with the change of the degree of depth;
Figure 12 shows the microstructure of the metal sample (embodiment 3) of process represented in Figure 11;
Figure 13 is X-ray diffraction analysis, demonstrates the diffusion layer mainly CrN in the metal sample (embodiment 3) processed;
Figure 14 and 15 is quantitative depth distribution plans, and it illustrates in the corresponding metal sample processed described in example 4, chromium (Cr), iron (Fe), nitrogen (N), carbon (C) and oxygen (O) are with the change of the degree of depth; And
Figure 16 shows the microstructure of the metal sample of the process described in embodiment 4.
Referring now to accompanying drawing, described accompanying drawing schematically illustrates the associated components of the fluidized bed processor of preferred form of the present invention, can recognize from foregoing disclosure, the at least pretreatment stage of heat treating method need not complete in fluid bed heat treatment facility, can use any other known equipment for Heating Processing in this stage.In addition, although ideally activation stage and diffusion phase are carried out in same Fluidised Bed Heat Treatment Furnace, activation and diffusion phase can use Fluidised Bed Heat Treatment Furnace separately equally.
As shown in fig. 1, device comprises the fluid bed furnace 10 with inner burner hearth 11, and described inner burner hearth contains particulate inert refractory materials 12 such as aluminum oxide (Al
2o
3), but also can use other such inert refractories.Stove comprises outer insulative layer 13 and heating zone 14, and described heating zone can be passed through combustion fuel gas in any usual manner, be heated by resistive heating or by any other means be applicable to.In the drawings, heating zone 14 is heated by the burner 16 being supplied with fuel gas.Primary inert gas supply line 17 is provided, for making refractory materials 12 fluidisation when needed bottom burner hearth 11.Gas feedthroughs 17 leads to gas distributing system, and it comprises main allocated equipment 18 and secondary dispenser 19, and secondary dispenser is generally porous material structure, is intended to prevent gas stream from flowing in burner hearth and even therefore fluidisation and thermal treatment.Halide gas and inert carrier gas provide another gas and deliver pipeline 20, so that can import burner hearth bottom by another divider 21 separated with divider 18/19.Inert carrier gas (such as nitrogen and/or argon gas) can be supplied by pipeline 70, and hydrogen halide is supplied by pipeline 71, and mixes in valve 72 before being delivered by pipeline 20.Can measure, to know the gas volume being shipped to stove 10 amount of the amount of the rare gas element delivered by pipeline 70 and 17 and the hydrogen halide delivered by pipeline 71.Divider 21 can be arranged in the gross refractory district 80 of burner hearth 11 lower region.Optionally, deliver pipeline 20 can be entered by burner hearth bottom or other positions as shown in dotted line outline, as long as make divider 21 be arranged in lower furnace portion region.In this arrangement mode, deliver pipeline 20 upwards can pass through shown in 20 ', and before halogenide and inert carrier gas being turned back to the divider 21 in burner hearth 11 lower region, comprises one or more heating coil 81.Be applicable in situation, heating coil 81 to be just positioned at above gross refractory district 80 or just therein.Halide gas and inert carrier gas preferably fully mix outside burner hearth 11, and mixed gas was preferably heated before entering burner hearth.In the situation of being applicable to, by there is heat exchange to heat with the region of fluidized bed processing stove.With in the arrangement mode shown in solid line, when pipeline 20 passes downwardly through refractory materials heated in burner hearth, there is the heating of the gas to external mix.Other arrangement modes are equally also possible.Such as, in the pipeline 20 in burner hearth, one or more delivery pipeline coil pipe can be provided.Or delivering pipeline 20 can pass through heating zone 14, and it is with one or more coil pipe being arranged in district 14.In the arrangement mode that another kind is possible, the inert carrier gas of premix and hydrogen halide without preheating, can be discharged by divider 21 and directly entering in stove.Use metering and mixing equipment (not being shown specifically) to guarantee to use the halide gas of appropriate ratio and inert carrier/fluidizing gas in the activation stage for the treatment of process.
Exhaust steam passage 22 is derived from the upper area of burner hearth 11, enables waste gas overflow in a controlled manner thus, and carries out process (not shown) for security object in downstream.Some refractory materials may be overflowed along this path, and such material is collected in gravel collection box or container 23 aptly.Sometimes, some reaction product may be solidified in this passage 22, and it finally may cause passage to become blocking.Removing device 24 can be provided to strike off such material, preferably return it in collection box 23.Additive method instead of illustrated physics scaler can be used.Such as, can frequently use the impulsive burst of rare gas element to break up or material in mobile exhaust steam passage 22, make it get back in burner hearth 11.Suitable granular metal or metal alloy (when using in treatment process) also can be imported by exhaust steam passage 22.Storage area 25 for such granular metal is provided with metering valve etc. 26, the metal-powder of aequum or the particulate material of metallic coating to be shipped in passage 22.Then when needed, can use removing device 24, if you are using, or this metal pushes in burner hearth 11 by some puopulsion units.This preferably carries out when bed slump (slumped) (namely not running), and making does not have in an outward direction along passage 22 or only have little gas stream.
As shown in fig. 1, around the top access hole 28 leading to burner hearth 11 inner area, the first tightness system 27 be connected with covering member 29 is provided.First tightness system 27 can seal burner hearth 11 in case ambient air enters in treating processes.The feature of the first tightness system 27 can be seen better in Fig. 2 or 3, they is depicted as in the drawings and operates together with the covering member 29 being used for top access hole 28.First tightness system 27 comprises the first outer seal portion 30, its by the outer peripheral flange 31 on covering member 29 be fixed to burner hearth 11 and engaging around the sealing material 32 of two on the component 35 of access hole 28 in periphery and between the flange 33 and 34 that separates of radial direction and formed.First tightness system 27 also comprises the second seal inside part 36 formed by outer peripheral flange 37, described outer peripheral flange 37 is carried on component 35, and engages with the sealing material 38 between the more inner outer peripheral flange 39 of the external flanges 31 on covering member 29 and the position entrained by covering member 29.Sealing material 32 or 38 can be any compressible seal material that can operate under the relevant operating temperature of stove, but can comprise ceramic fiber or VITON(registered trademark) elastomeric material.When operability engages the first tightness system 27 as shown in Figure 2 a, between flange 31 and 37, set up seal area 40.Gas distributor pipe 41 is arranged in this district 40, and be shown as the pipeline of 42 from outside charging by signal, nitrogen, argon gas or some other rare gas elementes are delivered to district 40 with certain pressure, therefore if possible leak, such gas will leak to burner hearth opening 29, thus stop ambient oxygen to enter burner hearth 11.Tightness system 27 also comprises the 3rd hermetic unit 43, and it is formed by interior periphery flange 39, and described flange 39 is bonded in the district 44 of the inertia refractory particulate material 45 containing the usual identical type with comprising in burner hearth 11.Particulate material 45 can by the rare gas element supply fluidisation delivered to divider 47 by pipeline 46, thus when covering member 29 moves to illustrated off-position, at least help flange 39 to enter in particulate material 45.In order to burner hearth 11 can be entered, covering member 29 is removed.This occurs when such as introducing to burner hearth or therefrom withdrawing from process component (such as metal base).
In sealing arrangement mode shown in Figure 3, provide two annular flanges 82,83 erected from periphery furnace sections or component 35, limit seal area 84 betwixt.Flange 82,83 soldered or be fixed on furnace sections 35 by other means, and there is different heights to obtain seal area 84.The upper limb 85,86 of flange 82,83 to be pressed in the sealing material 87 be applicable in the ring groove 88 in covering member or lid 29 and with its sealing.The edge of the upper limb 85 of flange 82 is preferably low than the upper limb 86 of flange 83, if make the leakage of gas from seal area 84 occurs, it is by the preferred inside towards burner hearth 11 instead of its External leakage.Sealing material 87 can be with above to the material of the identical type that the sealing material 32,38 of Fig. 2 a is discussed.Provide rare gas element and deliver pipe 42, rare gas element (such as nitrogen) to be shipped to the divider ring 41 in seal area 84, make when stove 10 in use and covering member 29 is closed time, seal area 84 is with higher than normal atmosphere and pressurize than the pressure rare gas element of burner hearth Nei Genggao.Occur from the both direction that flange upper limb 85,86 is being crossed in gas leakage " possibility " of seal area 84, but if really leaked, it occurs preferentially crossing edge to burner hearth for 85 times.Therefore maintain in burner hearth and have required atmosphere, do not allow undesired oxygen to enter burner hearth from outside atmosphere.From seal area 84 toward in, provide another annular flange 89, have thermal insulation material 87 in-between, it can be the material identical with sealing material 87 discussed above.As shown in Figure 3, refractory particulate material 91 may accumulate, but when certain is a bit about 60 ° when the pitch angle of this material and horizontal plane, crossing any under the inert gas assist of internal leakage of flange periphery 85, more such material will fall back to due to gravity in burner hearth 11.Therefore refractory materials is prevented from or remains on low-down level from the effusion of burner hearth.In suitable situation, the volume of seal area 84 minimally, to minimize rare gas element consumption.Lid or covering member 29 are with process basket (treatment basket) (or similar) bracing or strutting arrangement 92, and in suitable situation, covering member 29 is at least insulated in case calorific loss.In some applications, particularly when batch treatment, may also need to comprise spiral coil cooling tube or pipeline in lid or covering member 29, when needed stove 10 is cooled down at the end of process operation.Lid or covering member 29 can also be optional with stopper 93, with the space above minimization bed.
To be described method of the present invention according to a large amount of preferable case now.In pretreatment stage, pending metal parts (or base material) is commonly called to the surface treatment of nitriding or carbonitriding.This can be realized by various different device, comprises salt bath, gas heat treatment apparatus, vacuum plasma equipment and fluid bed furnace.But ideally, the so-called white layer set up by this first stage there is no obvious porosity.Factor needed for other also relates to the concentration of white layer, the degree of depth and microstructure, comprises and wherein lacks porosity.
When producing the structure of nitrogenize or carbonitriding, produce Liang Ge district.First inner area is spreading area, wherein nitrogen to be diffused in base material by spreading area from substrate surface and to improve the hardness of base material, second outside area is white layer, and it can be made up of such as ε and/or the γ layer as shown in international patent application no PCT/AU2006/001031.
When carrying out the pretreatment stage of the inventive method in Fluidised Bed Heat Treatment Furnace, it controls to need to bed supply ammonia/nitrogen (for nitriding) and the gas (such as Sweet natural gas and/or carbonic acid gas) containing carbon for carbonitriding.During carbonitriding, importantly comprise some oxygen during the course, it can be contributed by hydrocarbon gas, carbonic acid gas and/or oxygen.Once after completing this pretreatment stage satisfactorily, need to process pending parts or base material, to guarantee the surface of diffuse metal wherein will not exist oxide on surface.Surface smoothness that (or maintenance) is applicable in order to obtain, can in accordance with one of option below:
(i) parts or substrate surface such as can carry out mechanical treatment by polishing again, and keep before entering subordinate phase under an inert atmosphere subsequently;
Pretreatment stage and between activation stage and metal diffusing stage until and comprise activation stage and metal diffusing stage, parts or substrate surface can be maintained under an inert atmosphere completely or in vacuum;
(iii), in activation stage, the combination of halide gas and hydrogen can be used to remove any oxide on surface formed on parts or substrate surface; Or
(iv) wet-milling processing be can carry out to parts surface, sand grains and air and hydraulic pressure wherein can be changed to clear up surface.This process choosing removes any tectum and retains required white layer simultaneously.
In the activation stage of method, the metal or metal_based material that need to carry out surface diffusion can be placed in or remain on lower than 750 DEG C, the fluid bed furnace that runs preferably more than 700 DEG C of temperature.In suitable situation, temperature within the scope of 700 DEG C, is about 575 DEG C at 500 DEG C usually.Bed itself can comprise inertia refractory particulate material such as Al
2o
3, wherein in bed, take particle or powder type to diffuse to the metal target in surface, or wrap alternatively by inertia refractory particle.Such metal preferably accounts for 5 to 30 % by weight of a material, and namely all the other are inert refractory.Then when there is no pending metal base, by halide gas (such as hydrogenchloride) and inert gas flow by bed fluidisation first time period.Rare gas element can be argon gas and/or nitrogen, there is the halide gas (such as HCl) separately imported be mixed in advance in inert carrier gas flow (such as nitrogen and/or argon gas) simultaneously.
The metal-powder imported in bed preferably should have high purity and should not contain oxide on surface.Therefore, time before powder enters bed and in they are retained in bed itself, need to take measures to contact with air-prevention.The gas used also needs to be highly purified.The conventional rare gas element that can be used in described process is high pure nitrogen (oxygen level is lower than 10ppm), high-purity argon gas (oxygen level is lower than 5ppm), and for the first pretreatment stage processing technical grade ammonia, it contains the water vapor being no more than 500ppm, and before use by it is carried out further drying by siccative.The hydrogen halide used can be technical grade HCl usually, although also can use other hydrogen halides.
Hydrogen halide accounts for 0.2 to 3% of the total gas stream entering fluidisation thermal treatment pool furnace usually.Hydrogen halide stream needs regulation and control closely, and fully mixes with inert carrier gas before entering bed.This is important for the ununiformity avoided in bed.Before hydrogen halide enters bed, preheating can be carried out to it, to guarantee to be in its most reactive stage when it enters bed.The preheating of halide gas and inert carrier gas has the benefit that can reduce the amount of required hydrogen halide further.First time period usually can between 45 to 120 minutes, preferably between 60 to 90 minutes, to produce active layer in the diffuse metal in bed He on non-reactive fluidizing medium (aluminum oxide).When using chromium and hydrogen halide is hydrogenchloride, active layer will be chromium chloride.
At the end of this initial activation stage, pretreated metal base (carrying out pre-treatment as mentioned above) is imported immediately siege or the siege containing activated metal sill, then stop halide gas stream.In this metal diffusing stage subsequently, then will need the metal base forming diffusion layer thereon in preactivated bed, kept under inert gas atmosphere for the second time period (be generally 1 to 8 hour, be preferably 4 to 8 hours).In suitable situation, bed is remained on lower than 750 DEG C, aptly at 500 DEG C within the scope of 700 DEG C, under being generally the temperature of about 575 DEG C.In the metal diffusing stage, fluidized-bed can have minimum inert gas flow until high inert gas flow, and minimum inert gas flow makes its remarkable slump, and high inert gas flow makes its high degree of fluidization.Rare gas element can be nitrogen.In some cases, if think that bed needs some to reactivate, the halide gas stream comprising pulse in subordinate phase may be needed.
In treatment process, in bed, namely, maintain relatively uniform temperature between the various height of bed, be generally desirable.This can change by comprising device for detecting temperature and making response to the temperature detected the inert gas flow leading to bed, realizes.
For providing metal or the metal_based material of the metal in the diffusion surface layer being diffused into pending metal base, can be selected from following at least one: solid metal or metal alloy, it takes particle form or as one or more solid block components; Be coated in the metal or metal alloy in substrate carrier, wherein said substrate carrier takes particle form or as one or more solid block components, and wherein said substrate carrier is not reacted with metallizing or metal alloy or pending metal base under processing conditions; Metallic halide particles or powder (anhydrous or hydration); And the metal halide material (anhydrous or hydration) be coated in substrate carrier, wherein said substrate carrier takes particle form or as one or more solid block components, and wherein said substrate carrier is not reacted with coating material or pending metal base under processing conditions.In suitable situation, for providing the metal of the metal_based material treating diffuse metal, chromium, titanium, vanadium, niobium, tantalum, tungsten, molybdenum, manganese and alloy thereof can be selected from, comprise ferrous alloy.In suitable situation, the metal halide of censuring above can comprise selected metal above-mentioned and be selected from the halogen root of chlorine root, bromine root, iodine root or fluorine root.Such as, CrCl
2and CrCl
3to form slurry in water soluble and ethanol, it can be coated on applicable carrier substrate thus, or carrier substrate can be immersed in suspension to form applicable coating.
Several examples of the preferred implementation of method of the present invention will be described below.
Embodiment 1
Be 38mm by diameter, thickness is hardened and tempered (1020 DEG C of austenitizings (autenitised) the air cooling of 5mm, 575 DEG C of dual tempering) sample of AISI H13 Hot Work Tool Steel, in 35% ammonia, 5% carbonic acid gas, 60% nitrogen atmosphere, carbonitriding 3.5 hours at 575 DEG C.Before carbonitriding, 1200 grades of SiC abrasive materials are used to be prepared this sample surfaces, to guarantee good surface smoothness.This generates by direct 1 micron of oxygen enrichment upper layer on 10 microns of compound layers be made up of ε-carbon nitrided iron, and be finally the surface tissue that the internal divergence district of 70-90 micron is formed.Then vapour blasting is carried out to remove oxide skin to the surface of this carbonitriding sample, retain compound layer and spreading area simultaneously.In compound layer, the composition of chromium is about 4 % by weight after measured.
The fine copper block of diameter 38mm, thickness 5mm is polished to 1200 grades of SiC smooth finish, then plating comes from the hard chrome of commercialization supplier.Produce the pure layers of chrome of 2 microns by this method.Select copper to be because Cr and Cu is substantially insoluble as substrate carrier, therefore during heating layers of chrome can not be decomposed by being diffused in copper sample.Then this chromium plating sample is immersed in diameter 90mm, degree of depth 250mm and containing 3kg median size be 125 microns, purity is in the fluid bed heat treatment reactor of the alumina powder of 99.99%.This fluidized-bed is heated to 575 DEG C under a nitrogen, and to add hydrogen chloride gas to concentration be 1% of total gas stream to input gas stream at such a temperature.Should " activation " phase lasts 1 hours.After this activation stage, plating chrome on copper layer sample is cooled to room temperature in nitrogen gas stream.
To take out from fluidized-bed reactor and after entering in ambient air conditions, the plating chrome on copper layer sample immediately hydrogenchloride activated and carbonitriding sample physical bond, and applying clamping pressure.Then this conjunction is placed in fluid bed furnace, and is heated to 575 DEG C under nitrogen flowing, keep 4 hours at such a temperature, be then cooled to room temperature under nitrogen flowing.This experiment is repeated to the conjunction be made up of the plating chrome on copper layer and carbonitriding sample that do not carry out hydrochlorination as mentioned above.After untiing combination, glow discharge luminescent spectrum art (GDOES) is used to analyze the chemical constitution of two surface in contacts.
Find, by using surface, this surface and the carbonitriding example reaction of hydrogen chloride gas activation plating chrome on copper layer sample.Chromium transfers to carbonitriding sample (Fig. 4) from the chromium plating sample of activation, consumes the chromium (Fig. 5) on plating chrome on copper layer sample.Make response to the enrichment of chromium on carbonitriding surface, nitrogen diffuses to the surface, to produce the peak (Fig. 4) consistent with chromium peak.Iron shifts (Fig. 5) from carbonitriding sample to chromium plating sample.Correspondingly, the concentration of iron on carbonitriding sample is consumed (Fig. 4).On the contrary, do not react between non-activated plating chrome on copper layer and carbonitriding surface.Do not observe the consumption (Fig. 7) from plating chrome on copper layer sample of chromium enrichment (Fig. 6) on carbonitriding surface or chromium.This embodiment shows the hydrogenchloride surface active of chromium to chromium metal from chromium source to the importance of transfer of surface region being rich in nitrogen.
Embodiment 2
Be 38mm by diameter, thickness is hardened and tempered (1020 DEG C of austenitizings the air cooling of 5mm, 575 DEG C of dual tempering) sample of AISI H13 Hot Work Tool Steel, in 35% ammonia, 5% carbonic acid gas, 60% nitrogen atmosphere, carbonitriding 3.5 hours at 575 DEG C.Before carbonitriding, 1200 grades of SiC abrasive materials are used to be prepared this sample surfaces, to guarantee good surface smoothness.This generates by direct 1 micron of oxygen enrichment upper layer on 10 microns of compound layers be made up of ε-carbon nitrided iron, and be finally the surface tissue that the internal divergence district of 70-90 micron is formed.Then vapour blasting is carried out to remove oxide skin to the surface of this carbonitriding sample, retain compound layer and spreading area simultaneously.In compound layer, the composition of chromium is about 4 % by weight after measured.
The chromium block being 99.99% by the purity of diameter 38mm, thickness 5mm is polished to 1200 grades of SiC, be then immersed in diameter 90mm, degree of depth 250mm and containing 3kg median size be 125 microns, purity is in the fluidized-bed reactor of the alumina powder of 99.99%.This fluidized-bed is heated to 575 DEG C under a nitrogen, and to add hydrogen chloride gas to concentration be 1% of gas stream to input gas stream at such a temperature.Should " activation " phase lasts 1 hours.After this activation stage, chromium sample is cooled to room temperature in nitrogen gas stream.
To take out from fluidized-bed reactor and after entering in ambient air conditions, the chromium sample immediately hydrogenchloride activated and carbonitriding sample physical bond, and applying clamping pressure.Then this conjunction is placed in fluid bed furnace, and is heated to 575 DEG C under nitrogen flowing, keep 4 hours at such a temperature, be then cooled to room temperature under nitrogen flowing.This experiment is repeated to the conjunction be made up of the chromium and carbonitriding sample that do not carry out hydrochlorination.After untiing combination, glow discharge luminescent spectrum art (GDOES) is used to analyze the chemical constitution of two surface in contacts.
Identical with embodiment 1, by using surface, this surface and the carbonitriding example reaction of hydrogen chloride gas activation chromium.Chromium transfers to carbonitriding sample and nitrogen is diffused into described surface, to produce the peak (Fig. 8) consistent with chromium peak from the chromium sample of activation.Iron shifts (Fig. 9) from carbonitriding sample to chromium plating sample.Correspondingly, the concentration of iron on carbonitriding sample is consumed (Fig. 8).On the contrary, do not react between the chromium and carbonitriding surface of not activation in advance.Do not observe the chromium enrichment (Figure 10) on carbonitriding surface.
Embodiment 3
Be 38mm by diameter, thickness is two of 5mm hardened and tempered (1020 DEG C of austenitizings air coolings, 575 DEG C of dual tempering) AISI H13 hot forged mould steel sample, in 35% ammonia, 5% carbonic acid gas, 60% nitrogen atmosphere, carbonitriding 3.5 hours at 575 DEG C.Before carbonitriding, 1200 grades of SiC abrasive material surfaces to each sample are used to be prepared, to guarantee good surface smoothness.This generates by direct 1 micron of oxygen enrichment upper layer on 10 microns of compound layers be made up of ε-carbon nitrided iron, and be finally the surface tissue that the internal divergence district of 70-90 micron is formed.Then vapour blasting is carried out to remove oxide skin to the surface of carbonitriding sample, retain compound layer and spreading area simultaneously.In compound layer, the composition of chromium is about 4 % by weight after measured.
Diameter be 90mm, the degree of depth is in the fluidized-bed reactor of 250mm, 380g median size is 80 microns and the chromium powder end that purity is 99.99% is 125 microns with 3.4kg median size and the alumina powder that purity is 99.99% mixes.Be heated to 575 DEG C under being enough to this fluidized-bed at flow to carry out the high-purity nitrogen of fluidisation, and at such a temperature, the carbonitriding AISH13 sample as above prepared be immersed in the time period of in the fluidized powder of heating 4 hours.By sample under nitrogen flowing, in fluidized-bed, be cooled to 350 DEG C, and to cool in atmosphere.As the result of this process, carbonitriding surface does not experience chromium enrichment.
Diameter be 90mm, the degree of depth is in the fluidized-bed reactor of 250mm, 380g median size is 80 microns and the chromium powder end that purity is 99.99% is 125 microns with 3.4kg median size and the alumina powder that purity is 99.99% mixes.Be heated to 575 DEG C under being enough to this fluidized-bed at flow to carry out the high-purity nitrogen of fluidisation, and to add hydrogen chloride gas to concentration to input gas stream be at such a temperature 1% of gas stream.Should " activation " phase lasts 1 hours.After this activation, be immersed in the fluidized powder of heating by the carbonitriding AISH13 sample as above prepared, stop hydrogen chloride gas stream, the time period of 4 hours is carried out in thermal treatment at 575 DEG C simultaneously.Then by sample under nitrogen flowing, in fluidized-bed, be cooled to 350 DEG C, and to cool in atmosphere.In this experiment, the carbonitriding surface significant chromium enrichment of experience (about 70 % by weight, the quantitative depth distribution plan see Figure 12), forms layer (Figure 12) that is unique, all even continuous print 2.5 micron thickness.X-ray diffraction analysis shows that this layer is mainly CrN(Figure 13).
Embodiment 4
In order to assess the possibility brought up to by process temperature higher than 575 DEG C, have selected the steel of two kinds of ranks with the tempering resistance higher than AISI H13 Hot Work Tool Steel.Be 38mm by diameter, thickness is hardened and tempered (1050 DEG C of austenitizings with oil annealing, 575 DEG C of dual tempering) powder metallurgy die steel Crucible CPM of 5mm
with conventional mold metallurgy steel Bohler-Uddeholm
the sample of 90, in 35% ammonia, 5% carbonic acid gas, 60% nitrogen atmosphere, carbonitriding 3.5 hours at 575 DEG C.Before carbonitriding, 1200 grades of SiC abrasive materials are used to be prepared each sample surfaces, to guarantee good surface smoothness.This generates by direct 1 micron of oxygen enrichment upper layer on 10 microns of compound layers be made up of ε-carbon nitrided iron, and be finally the surface tissue that the internal divergence district of 70-90 micron is formed.Then vapour blasting is carried out to remove oxide skin to the surface of carbonitriding sample, retain compound layer and spreading area simultaneously.In compound layer, the composition of chromium is about 4 % by weight after measured.
Diameter be 90mm, the degree of depth is in the fluidized-bed reactor of 250mm, 380g median size is 80 microns and the chromium powder end that purity is 99.99% is 125 microns with 3.4kg median size and the alumina powder that purity is 99.99% mixes.Be heated to 625 DEG C under being enough to this fluidized-bed at flow to carry out the high-purity nitrogen of fluidisation, and to add hydrogen chloride gas to concentration to input gas stream be at such a temperature 1% of gas stream.Should " activation " phase lasts 1 hours.After activation, by the carbonitriding sample of often kind of grade as above prepared in the fluidized powder of heating, the submergence time period of 4 hours under high-purity nitrogen.By sample under nitrogen flowing, in fluidized-bed, be cooled to 350 DEG C, then from fluidized-bed reactor take out and cool in atmosphere.In this experiment, the carbonitriding surface significant chromium enrichment of experience (about 70 % by weight, the quantitative depth distribution plan see Figure 14 and 15), has corresponding nitrogen peak.Compared with the processing at 575 DEG C, at 625 DEG C, carry out the chromium deposition stage causes layer thickness to be increased to about 4-6 micron (Figure 15).Below CrN layer, substantially remain spreading area and core hardness.
Claims (25)
1. form the method for the diffusion surface layer extended internally from the outside surface of metal base, described method comprises:
I () is in activation stage, activation treatment stove containing inert particle refractory materials and the metal_based material for the formation of described diffusion surface layer is provided, described activation treatment stove and accessory has the inert gas flow being directed in inert particle refractory materials in described activation treatment stove and metal_based material and continuing first time period, to process the exterior surface area of described metal_based material under hydrogen halide existence, form the metal_based material with the activation of the surf zone of activation; And
(ii) in diffusion phase, DIFFUSION TREATMENT stove is provided and described metal base is imported in described DIFFUSION TREATMENT stove, described metal base is pretreated to form the spreading area extended internally from the outside surface of metal base, in described metal base, nitrogen has been diffused to form internal divergence district with at least partly by nitrided iron, the external compounds layer of iron carbide or carbon nitrided iron compound formation or white layer, the described outside surface of metal base do not have oxide skin, and under the metal_based material of described activation exists, by seal to prevent ambient air from entering DIFFUSION TREATMENT stove in, under inert gas atmosphere, when there is not hydrogen halide by metal base process at least the second time period, to form described diffusion surface layer on described metal base.
2. the process of claim 1 wherein that described activation treatment stove is identical with described DIFFUSION TREATMENT stove.
3. the process of claim 1 wherein that described DIFFUSION TREATMENT stove is different from described activation treatment stove.
4. the method for any one of claims 1 to 3, it also comprises:
I () is in pretreatment stage, form the described spreading area extended internally from the surface of metal base, in described metal base, nitrogen has been diffused the described external compounds floor or the white layer that form described internal divergence district and nitrided iron, iron carbide or carbon nitrided iron compound; And
(ii) before the described metal diffusing stage, the metal base formed in described pretreatment stage is processed, to prevent from forming oxide on surface on said surface, or remove any described oxide on surface formed on said surface.
5. the process of claim 1 wherein that the inert gas flow in described activation stage is nitrogen and/or argon gas.
6. the process of claim 1 wherein that described inert particle refractory materials is aluminum oxide or silicon carbide.
7. the process of claim 1 wherein that described DIFFUSION TREATMENT stove contains the inert particle refractory materials by inert gas flow fluidisation in the described metal diffusing stage.
8. the process of claim 1 wherein that described DIFFUSION TREATMENT stove contains the inert particle refractory materials by least part of fluidisation of mode of vibration in the described metal diffusing stage.
9. the process of claim 1 wherein in the described metal diffusing stage not to DIFFUSION TREATMENT stove supply ammonia.
10. the process of claim 1 wherein that described second time period is longer than described first time period.
11. the process of claim 1 wherein in described second time period, to described DIFFUSION TREATMENT stove pulse supply hydrogen halide stream, last the time period of time period and at least one the hydrogen halide stream not having hydrogen halide stream.
The method of 12. claims 1, wherein said DIFFUSION TREATMENT stove contains inert particle refractory materials, and in described second time period, provide inert gas flow to described DIFFUSION TREATMENT stove, described inert gas flow can zero flow velocity and be equal to or higher than described DIFFUSION TREATMENT stove incipient fluidization speed flow velocity between change.
13. the process of claim 1 wherein that the temperature in described activation treatment stove between maintenance 500 DEG C to 750 DEG C lasts described first time period.
14. the process of claim 1 wherein that the temperature in described DIFFUSION TREATMENT stove between maintenance 500 DEG C to 750 DEG C lasts described second time period.
15. the process of claim 1 wherein in described first time period, to described activation treatment stove described hydrogen halide without interruption.
16. the process of claim 1 wherein in described first time period, are supplied described hydrogen halide with supply time section by the pulse mode that supply time section does not separate to described activation treatment stove.
17. the process of claim 1 wherein that described hydrogen halide is selected from hydrogen chloride gas, bromize hydrogen gas, hydrogen fluoride gas and hydrogen iodide gas.
18. the process of claim 1 wherein that described hydrogen halide mixed with described rare gas element before entering activation treatment stove.
19. the process of claim 1 wherein that described hydrogen halide mixed with described rare gas element before entering DIFFUSION TREATMENT stove.
20. the process of claim 1 wherein that described ammonium chloride is heated to resolve into nitrogen and hydrogen chloride gas when being imported into, for the activation of described metal_based material to described activation treatment stove supply ammonium chloride in described activation stage.
The method of 21. claims 18, wherein the mixture of hydrogen halide and rare gas element enters described activation treatment stove or DIFFUSION TREATMENT stove at the lower region place of activation treatment stove or DIFFUSION TREATMENT stove.
22. the process of claim 1 wherein that the metal_based material for the formation of diffusion surface layer is selected from following at least one:
(i) solid metal or metal alloy;
(ii) metal or metal alloy in substrate carrier is coated in;
(iii) particle or powder metal or metal alloy;
(iv) metal or metal alloy on inert particle refractory materials is coated in;
(v) metallic halide particles or powder (anhydrous or hydration); And
(vi) metal halide material (anhydrous or hydration) in inertia refractory particulate material or substrate carrier is coated in.
The method of 23. claims 1, metal_based material wherein for the formation of diffusion surface layer is selected from chromium, titanium, vanadium, niobium, tantalum, tungsten, molybdenum, manganese and alloy thereof, comprise ferrous alloy, or the metal halide be made up of with the halogen root being selected from chlorine root, bromine root, iodine root and fluorine root the metallic element of above-mentioned metal.
24. claim 1 methods, wherein said metal base is ferrous metals or ferrous metals alloy.
25. the process of claim 1 wherein in described second time period, and the described rare gas element be imported in described DIFFUSION TREATMENT stove is nitrogen.
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| AU2010905095 | 2010-11-17 | ||
| AU2010905095A AU2010905095A0 (en) | 2010-11-17 | Surface Treatment of Metal Objects | |
| PCT/AU2011/001479 WO2012065220A1 (en) | 2010-11-17 | 2011-11-17 | Surface treatment of metal objects |
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| EP (1) | EP2640867A1 (en) |
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| DK2804965T3 (en) | 2012-01-20 | 2020-12-14 | Swagelok Co | Simultaneous flow of activating gas at low temperature carburization |
| EP4086366A1 (en) * | 2014-07-31 | 2022-11-09 | Case Western Reserve University | Enhanced activation of self-passivating metals |
| CN107201496A (en) * | 2017-06-12 | 2017-09-26 | 武汉铭高新材料有限公司 | A kind of method for preparing chromium based ceramic metal hardened layer in stainless steel surfaces |
| CN107377968A (en) * | 2017-09-08 | 2017-11-24 | 安徽工业大学 | A kind of preparation facilities and preparation method of the Heterogeneous Composite powder based on injection fluidisation |
| US11060186B2 (en) * | 2018-04-13 | 2021-07-13 | Massachusetts Institute Of Technology | In situ generation of gaseous precursors for chemical vapor deposition of a chalcogenide |
| US11193197B2 (en) | 2018-06-11 | 2021-12-07 | Swagelok Company | Chemical activation of self-passivating metals |
| JP2023523333A (en) | 2020-04-29 | 2023-06-02 | スウェージロック カンパニー | Activation of self-passivating metals using reagent coatings for low-temperature nitrocarburizing |
| CN115505867B (en) * | 2022-10-25 | 2024-04-05 | 北京酷捷科技有限公司 | Preparation method and application of hydrogen-reduced stainless steel chrome copper alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4765847A (en) * | 1985-06-17 | 1988-08-23 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of treating the surface of iron alloy materials |
| CN101519763A (en) * | 2008-02-27 | 2009-09-02 | 通用电气公司 | Diffusion coating systems with binders that enhance coating gas |
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| DK0471276T3 (en) * | 1990-08-10 | 1996-03-18 | Toyoda Chuo Kenkyusho Kk | Process for preparing a nitride or carbon nitride layer |
| EP0919642B1 (en) * | 1997-11-28 | 2007-10-17 | Maizuru Corporation | Method for treating surface of ferrous material and salt bath furnace used therefor |
| JP4063709B2 (en) * | 2003-05-15 | 2008-03-19 | エア・ウォーター株式会社 | Method for surface modification of austenitic metal, refractory metal product and turbo part obtained thereby |
| CN101268209B (en) * | 2005-07-21 | 2012-07-18 | 哈德技术有限公司 | Duplex surface treatment of metal objects |
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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4765847A (en) * | 1985-06-17 | 1988-08-23 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of treating the surface of iron alloy materials |
| CN101519763A (en) * | 2008-02-27 | 2009-09-02 | 通用电气公司 | Diffusion coating systems with binders that enhance coating gas |
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| AU2011331909B2 (en) | 2016-06-23 |
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| AU2011331909A1 (en) | 2013-06-20 |
| JP5951623B2 (en) | 2016-07-13 |
| US20130299047A1 (en) | 2013-11-14 |
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| WO2012065220A1 (en) | 2012-05-24 |
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