CN101307399A - Methods of making superfine alloys - Google Patents
Methods of making superfine alloys Download PDFInfo
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- CN101307399A CN101307399A CNA2008100984202A CN200810098420A CN101307399A CN 101307399 A CN101307399 A CN 101307399A CN A2008100984202 A CNA2008100984202 A CN A2008100984202A CN 200810098420 A CN200810098420 A CN 200810098420A CN 101307399 A CN101307399 A CN 101307399A
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- growth inhibitor
- grain growth
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- ultra tiny
- alloy
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Abstract
A method of making a superfine alloy comprises: incorporating a grain growth inhibitor polymeric precursor into a composition for synthesis of a superfine material; synthesizing the superfine material from the composition comprising the incorporated precursor; incorporating an alloy additive into the composition for synthesis of the superfine material before synthesizing the superfine material, or alternatively, into the as-synthesized superfine material to produce a superfine alloy-grain growth inhibitor polymeric precursor composite; and treating the superfine alloy-grain growth inhibitor polymeric precursor composite to convert the grain growth inhibitor polymeric precursor to a grain growth inhibitor.
Description
The cross reference of related application
The application is the Application No. of submitting on April 2nd, 2,003 10/405,450 divide an application, described number of patent application 10/405, the 450th, the U.S. Patent number 6 that submit to May 1 calendar year 2001,576, the division of 036 B2, the described patent No. 6,576,036 B2 is the U.S. Patent number of submitting on August 21st, 1,998 6, the division of 277,774 B1, the described patent No. 6,277,774 B1 require the right of priority of the U.S. Provisional Patent Application submitted on August 22nd, 1997 number 60/057,339, and all above-mentioned patent applications are incorporated its full content into this paper by reference.
Technical field
The present invention can relate to the method for synthetic ultra tiny material usually, and described ultra tiny material contains greater than 100nm and is less than or equals the particle or the crystal grain of about 10 microns sizes.Particularly, thus the present invention relates to grain growth inhibitor and/or alloy addition be added to makes material have the controlled microtexture and the chemical process of form in the ultra tiny material.The material that obtains demonstrates good character, comprise improved fracture toughness property, hardness and resistance to wear, anticorrosive and anti-erosion.
Background technology
In decades, the material that has realized that the microtexture with fine sizes demonstrates uncommon and the character of technology magnetism is arranged.At present, other interest of following material type is increased: be less than or equal to the crystal grain of 100 nanometers (nm) range size or the material of granulometric composition by very fine having, be called the material of " nanostructure "; By having greater than 100nm and being less than or equaling the crystal grain of about 10 micrometer range sizes or the material of granulometric composition, be called
Material; And a class material with size between about 1 micron and about 10 microns.As hereinafter used,
Material system refers to have greater than 100nm and is less than or equals the particle of about 10 microns sizes or the material of crystal grain.The feature of ultra tiny material is that the atom that relatively is positioned at crystal grain or granular boundary with bigger material has high refraction (fraction).Therefore, with the large size respective material comparison with same composition of routine, nanostructure can have different basically frequent excellent in chemical and physical properties with ultra tiny material.Therefore, the natural increase of appreciable advantage along with the macrostructure material of nanostructure and ultra tiny material substitution routine in using widely, for example good intensity, in martensitic steel (martensitic steels) improved fracture toughness property and hardness, minimizing be used for fixed sintering temperature and in the superplastic incidence of pottery.Especially, wish that nanostructure and ultramicrofine metal alloy and metallic carbide have good character, comprise improved fracture toughness property, hardness and resistance to wear, anticorrosive, anti-erosion.Synthetic and the core texture of optimization nanostructure and ultra tiny material and the ability of tap density are the strong tool that obtains the new classification of these materials under atomic level.These new classifications are with specified multi-functional dressing, and the raising of material character and performance in engineering is used is widely had unprecedented advantage.
Inframat company has obtained significant progress in nanostructure and ultramicrofine material field: comprise the metal-powder by organic solution reaction (OSR) method, reactant aqueous solution (ASR) method synthesis of nano structure; Advanced chemical process with the oxide compound and the hydroxide materials of store battery that is used for structure and fuel cell.Prepare the Ni/Cr alloy that examples of material comprises nanostructure, the NiCr/Cr of nanostructure according to these methods
3C
2The ZrO of the stabilized with yttrium oxide of mixture, nanostructure
2, nanofiber MnO
2And Ni (OH)
2Inframat company further develops the technology of a large amount of preparation nanostructures and ultra tiny material, described in " Nanostructured Oxide andHydroxide Materials and Methods of Synthesis Therefor " (oxide compound of nanostructure and hydroxide materials and its synthetic method)-this is the theme (U.S.S.N.08/971 that comprises submission on November 17th, 1997 of the United States and abroad application of pendency, 811, present U.S. Patent number 6,162,530), and comprise the nanostructure of nanostructure WC-Co mixture and the hot-spraying techniques of ultra-fine feed, as " Nanostructured Feeds for ThermalSpray Systems; Method of Manufacture; and Coating Formed Therefrom " (the nanostructure feed that is used for thermal spray system, the method of its preparation and the dressing of its formation) described-this also is the theme (U.S.S.N.09/019 that comprises submission on February 5th, 1998 of the United States and abroad patent application of pendency, 061, present U.S. Patent number 6,025,034), these two pieces of U.S. Patent application full contents are incorporated this paper by reference into.Use the metal of OSR and ASR method chemosynthesis nanostructure, pottery and mixture be existing description in following document at first also: the existing resigned U.S.S.N.08/989 that Xiao and Strutt submitted on December 5th, 1996,000 " Nanostructured Metals; Metal Alloys; Metal Carbides and Metal AlloyCarbides and Chemical Synthesis Thereof (nanostructured metal; metal alloy; metallic carbide and metal alloy carbide and its chemical synthesis) "-it incorporates this paper by reference into, and " Synthesis and Processing of Nanostructured Ni/Cr and Ni-Cr
3C
2Viaan Organic Solution Method is (by the Ni/Cr and the Ni-Cr of organic solution method nanostructure
3C
2Synthetic and method) " Nanostructured Mater.Vol.7 (1996) pp.857-871 and " Synthesis of Si (C, N) Nanostructured Powders From anOrganometallic Aerosol Using a Hot-Wax Reactor (uses hot wax reactor from the synthetic Si (C of organo-metallic aerosol, N) nanostructured powders) " J.Mater.Sci.Vol.28 (1993), pp.1334-1340.
Described OSR and ASR method are used the method for substep, and it generally includes: (OSR) organic solution of (1) preparation mixed metal halide or (ASR) aqueous solution; (2) reactant generates the nanostructure precipitation by the reaction of atomised jet technology; (3) wash and filter this throw out.This throw out often carries out heat treated, and/or carries out gas carburization under the following conditions to form the nitride of nanostructure: controlled carbon/oxygen activity condition (carbide that forms expectation in the matrix phase of metal spreads mutually) or controlled nitrogen/hydrogen activity condition.Use this program with synthetic different nanostructure composition, comprised the nanostructure NiCr/Cr of the thermospray that is used for anticorrosive hard coatings
3C
2Powder.Advanced chemical process method combines ASR and OSR method with atomised jet and ultrasonic agitation.
The method of another kind of synthesis of nano structured material is inert-gas condensation (IGC) method.As " Materials with Ultrafine Microstructures:Retrospective and Perspectives (material with ultra tiny microstructure: look back and prospect) " Nanostructured MaterialsVol.1, pp.1-19 is described, and Gleiter makes at first and prepares nanostructured metal and ceramic cluster (cluster) in this way.Later this method is made widely by Siegel and is used for preparing nanostructure TiO
2And other system, as " Creating Nanophase Materials (creation nano-phase material) " Scientific American Vol.275 (1996), pp.74-79 is described.This method is to use the method in common of the nanostructured metal and the ceramic powder of synthetic test amount now.Described IGC method is used evaporation of metals source (evaporative sources), described metal convection current subsequently (convectively) transhipment and concentrated on the refrigerative substrate.Ceramic particle must be by this source metal of initial vaporization, obtain by oxidising process slowly then.The feature of this method is the ability that produces the nanostructured powders of loose reunion, but described nanostructured powders sintering at low temperatures.
The method of another synthesis of nano structured material is chemical evapn condensation (CVC) method.People such as Kear the molecule of MSR symposial specified ultra tiny/" Chemical Vapor Synthesis of Nanostructured Ceramics (chemical evapn of nanostructure pottery is synthetic) " Proc.Vol.351 (1994) in the material of nanostructure, pp.363-368 has described CVC.In CVC, reaction vessel is similar to use IGC method, uses evaporation source but replace, thereby and uses the hot wall tubular reactor to form the nano particle cluster stream that successive withdraws from reactor tube with the precursor/carrier of degrading.These clusters diffuse to the major reactor chamber apace then, and concentrate on the substrate of cooled with liquid nitrogen.This CVC method is used for precursor or commercially available precursor at first.Kear has described the nanostructure SiC of hexamethyldisilazane (hexametnyldisilazane)
xN
yPreparation with oxide compound.
Finally, Kear is at " Synthesis and Processing of Nanophase WC-CoComposite (nanostructure WC-Co mixture synthetic and processing) " Mater.Sci.Techn.Vol.6 (1990), discloses the method that the thermochemistry of preparation nanostructure WC-Co transforms in p.953.In this method, the water-soluble solution that contains tungsten and cobalt precursors is spray-dried to form the intermediate precursor under the temperature of about 150-300EC.Described intermediate precursor is with the amorphous oxidation tungsten of the form of the spherical hollow shell with about 50 micron diameters and about 10 microns wall thickness and the mixture of cobalt.Obtain nanostructure WC-Co by the carbonization of described precursor powder under 800-900EC and in carbon monoxide/carbon dioxide mixture then.Use this technology synthesis of nano structure WC-Co existing description in following several pieces of patents: Multiphase Composite Particle (multi-phase composites particle) U.S. Patent number 4 that comprises people such as McCandlish, 851,041 and Carbothermic Reaction Process for Making Nanophase (preparation nanophase WC-Co carbon thermal reaction method) U.S. Patent number 5,230,729.Synthesis of nano structure and ultramicrofine WC/Co are particularly conducive to industry, can select to be used for parting tool, drill bit and lost material at present as it.
Should expect: a large amount of technology of developing nano structural material especially also can be used for the synthetic of ultra tiny material by the operation of control grain size under synthetic level or by using grain growth inhibitor.Yet the main drawback of the technology of above-mentioned technology and other synthetic ultra tiny materials known in the art is: the material of preparation is at sintering or particularly at high temperature bear the trend of uncontrolled grain growing during using this groups of nanostructures to divide.For example, just the tungsten carbide crystal grain diameter of synthetic nanostructure WC-Co is about 30nm.During liquid phase sintering, tungsten carbide crystal grain diameter (for example several minutes) in the short relatively time is grown up fast to several microns or bigger.After detailed research and engineering judgment, can reach a conclusion: VC and/or Cr
3C
2It is the most effective carbide phase of the material of the broad range estimated for many years.
For example, (Brunswick NJ) makes and is used for preventing this disadvantageous grain growing, as passing through described in the trade mark Nanocarb7 product sold specification sheets of Nanodyne the vanadium carbide by Nanodyne company.In this method, by the mixing of machinery, the vanadium carbide powder of micron size can be mixed to the WC/Co powdered compound, and shape forms (shape-formation) and sinters to a large amount of components then.Using the vanadium carbide can prevent to a certain degree grain growing effectively, is in sub-micrometer range as the final grain size of fixed a large amount of parts (piece), as the 0.2-0.8 micron.The main drawback of this grain growing technology is the heterogeneous mixing of VC and WC/Co composite materials and the difficulty of sintering kinetics, and this causes the heterogeneous of lot of materials character, or the increase of cost in the sintering process.
For addressing the above problem, Nanodyne uses the chemical precipitation technology at present, introduces vanadic salts in the material synthetic initial stage with chemical process in the described chemical precipitation technology.Although the use of this technology has overcome heterogeneous blended problem, it has produced vanadium oxide rather than vanadium carbide.Well-known is that any oxide material that is present in the WC/Co system is deleterious to this material.Being introduced into the WC/Co system and can not only producing the sintering difficulty of this vanadium oxide, and in the WC/Co powder, need to be used under extreme high-temperature (as 1450EC), vanadium oxide being changed into the extra carbon source of vanadium carbide.Under many circumstances, described extra carbon source can make fixed material embrittlement.
The material that originally boron compound is bonded to fine-grain by Xiao and Strutt at " Synthesisof AlN/BN Composite Materials (AlN/BN composite materials synthetic) " J.Am.Ceram.Soc., Vol.76, p.987 describe in (1993), the document discloses the synthetic of the mixture precursor that comprises aluminium, boron and nitrogen.By frothing ammonia is fed in the aqueous solution of boric acid and urea, form described boron nitride polymkeric substance.
People such as Scoville are at " Molecularly Designed Ultrafine/NanostructuredMaterials " K.E.Gonsalves, D.M.Chow, T.D.Xiao and R.Cammarato, MRS Symp.Vol.351, p.431 (1994) have been described the BN nano-structured particles have been bonded to sige lattice with the electrical method of remarkable minimizing thermal conductance.In this method, the BN of micron size is in the same place with the Si/Ge powder mixes, and uses the plasma torch evaporation to form mixture, and the condensation subsequently of described mixture enters the mixture of BN/Si/Ge.Heat treated causes the big crystal of Si/Ge (＞1 micron), and wherein Li San 2-10nm BN crystal grain is hunted down in bigger crystal.
Boron nitride also has been bonded to the titanium dioxide system that conventional (greater than the grain size of 100nm) contains the WC/Co additive, and is as the U.S.P.N.5 people such as Mehrotra, open in 632,941.BN adds with powder type.U.S.P.N.4,713,123 further disclose BN as the grain growth inhibitor in (greater than the grain size of 100nm) silicon steel of routine.Yet, when the amount of BN is too big, grows and have 110}＜001 the secondary recrystallization crystal grain of direction will be very difficult, to such an extent as to described amount is limited in the scope of 0.0003%-0.02%.The form of boron with ferro-boron is added in the silicon steel, nitrogenize by described steel is to provide nitrogen then, cause the formation of trace B or BN like this, wherein boron or BN can suppress the migration of crystal grain boundary, as Grenoble at IEEE Trans.Mag., May 13th, p.1427 (1977) and Fiedler IEEE Trans.Mag.May 13th p.1433 (1977) described.These quote all openly, and the BN polymkeric substance can be used as the grain growth inhibitor precursor.
Therefore, during the processing of firm synthetic nanostructure and ultramicrofine material and nanostructure and ultramicrofine material intermediate, need to suppress and/or control the method for grain growing in the art, particularly can be used for method for compositions widely.
Summary of the invention
Above-mentioned shortcoming and the defective with other of background technology overcomes by method of the present invention or alleviates, and described method of the present invention comprises the intermediate that the grain growth inhibitor polymer precursor is bonded to ultra tiny material or is used to prepare ultra tiny material.For more effectively spreading this precursor, be lower than under the grain growing temperature of this material randomly this precursor/nanostructure of heat treated (or ultra tiny) material composite.Therefore this mixture of heat treated under to this precursor efficient temperature of degrading forms and contains the material of equally distributed grain growth inhibitor therein, preferably on crystal grain boundary then.Synthetic preferred inorganic polymer solution comprises and forms inorganic polymer from the solution of metal-salt, filter and dry this polymkeric substance.
In first embodiment of the present invention, this inorganic polymer precursor is introduced in the described ultra tiny material in described powdered preparation step, promptly synthetic this material maybe can form this product material intermediate during, be converted into grain growing by heat treated then and suppress kind, therefore make the grain growing kind and in the material of molecular level, mix equably.This heat treated also can be used for the ultra tiny material of intermediate is converted into ultramicrofine material product.
In second embodiment, this polymer precursor is bonded to ultra tiny material of synthetic or intermediate.In a method, this polymer precursor is dissolved in the solution that contains synthetic particulate dispersion, and with slurry (slurry) oven drying that generates or spraying drying in the crystal grain boundary of ultra-fine particles, to form the dried powder that contains equally distributed grain growth inhibitor.Perhaps, the synthetic particle also randomly is being lower than heat treated under this grain growing temperature with the polymer precursor dressing, after this by any matrix precursor is dissolved and diffuses to the interface of crystal grain.Then with oven drying, spray-dired or coated granules/precursor composite heat treated (if necessary), so that this polymer precursor is converted into grain growth inhibitor, and randomly further handles (for example by nitrogenize or carbonization) and contain product material at the equally distributed grain growth inhibitor of crystal grain boundary with preparation.This method can coat each particle with the grain growth inhibitor barrier basically, maybe can obtain to mix with the homogeneous phase of nano particle at the nanometer level grain growth inhibitor.
In another embodiment of the invention, alloy addition and/or grain growth inhibitor are bonded in this material.Described alloy addition and/or grain growth inhibitor precursor can be bonded to as the described reaction mixture that is used for synthetic this material of top first embodiment, or described alloy addition precursor can be in conjunction with the material as top second embodiment described just synthetic (as-synthesized).Just the synthetic material can comprise grain growth inhibitor or the precursor that is combined in this synthesis phase.Perhaps, described alloy addition and polymkeric substance grain growth inhibitor combination of precursors, and be bonded to subsequently in the synthetic particle.Mix the homogeneous mixture that for example prepares this particle and described alloy addition and grain growth inhibitor precursor, then by spraying drying or the oven drying and as the described course of processing of top second embodiment by ball milling.
Particularly advantageous characteristics of the present invention is that it can be used for material system widely, comprises metal, metal alloy, carbide, nitride, intermediate, pottery and its composition.Preferably, this grain growth inhibitor itself is high performance material, and demonstrates the character of outstanding mechanics and other physics and chemistry.The interpolation of alloy addition further improves the character of this product material, and described character comprises hardness, toughness, density, anticorrosive and anti-erosion.The present invention can make economically in a large number has the ultra tiny material of high-performance of target set of applications compound widely.
Description of drawings
Fig. 1 illustrates the influence of the amount (weight %) of increase BN to the hardness of WC-Co nanostructured composites material.
Fig. 2 shows the hardness data of the Vicker of sample in the thermospray test.
Fig. 3 illustrates the funtcional relationship between the alloy addition that contains the 1wt.%BN grain growth inhibitor and the toughness influence.
Embodiment
Method of the present invention is particularly useful in grain growth inhibitor and/or alloy addition is bonded to ultra tiny material (contain greater than 100nm and be less than or equal the material of about 10 microns grain size).Therefore, the present invention is directly about suppressing the method for grain growing during powdered material processing, and described method comprises and the grain growth inhibitor polymer precursor is bonded to ultra tiny material or is used for block and the intermediate of the ultra tiny material preparation that dressing is used.(preferably in the firm synthetic intermediate stage) is bonded to ultra tiny material or intermediate with described polymer precursor and/or alloy addition when this material is synthetic or after synthetic.Preferably when this material is synthetic described polymer precursor and optional alloy addition are combined, when the reduced number of procedure of processing, the cost of this method is lower, and this grain growth inhibitor more likely distributes equably.Therefore, the invention provides the method that preparation has the ultra tiny material of controlled morphologies, microstructure and chemical composition.This material that obtains can be as the charging and the advanced high performance extensive application of ultra tiny dressing.
Be not subject to theory, suppose that obtaining wonderful good result by the present invention causes the effective distribution of this grain growth inhibitor at crystal grain boundary, the evolving path that strides across this crystal grain boundary owing to atom is difficult, and this distribution is reduced to grain growing minimum.About special BN grain growth inhibitor in the WC/Co system, by high density/nonmetal in conjunction with the molten mass of rich cobalt in the presence of right in cluster stability may be important factor because the liquid phase that its suppresses tungsten and carbon is transported to next adjacent crystal grain from a WC grain.By BN is added to Co, melt B N can be by the solution in liquid Co; Under these environment, melt has had competent tungsten and carbon under the situation of nano-phase material, and molten mass becomes and further be rich in boron and nitrogen, to such an extent as to the stable potentiality of cluster are improved.Along with the adding of alloy addition such as Cr, Si etc., the plyability of molten mass increases, thereby has improved so-called
Principle, described principle can detect the liquid molten body to decrystallized susceptibility.Boron is the molten mass of well-known inhibition transition element, and the application of the signal METGLASS technology of associating is added to iron, nickel and cobalt with boron.In the embodiment of this paper, boron also can be used as the molten mass inhibitor, makes that material is more responsive to thickening at low temperatures closely, and promotes decrystallized in cooling period subsequently.The possibility of selecting be nitrogen with the WC surface reaction with formation W
2The passive film of N or tungsten carbonitride.Under any circumstance, because under the existence of passive film, this effect will suppress alligatoring.
Be applicable to that ultra tiny material of the present invention comprises metal, metal alloy, sintering metal (particularly metallic carbide and metal nitride), intermetallic compound (intermetallics), pottery or ceramic to ceramic mixture.More particularly, preferred ultra tiny material is selected from Cu, FeCu, FeCo, NiAl, MoC, MoSi, NiCr, TiC, Mo
2Si, NiCr/Cr
3C
2, Fe/TiC, Ni/TiC, Mo/TiC and WC/Co, above-mentioned metal and one or more alloyings that contain Ti, Cr, Mo, Ni, Zr, Ce, Fe, Al, Si, V, TiC, Mn, Y, W, and above-mentioned metal, metal alloy, intermetallic compound and ceramic-metallic mixture.Get rid of the metallic sulfide system in the above-mentioned tabulation.
Being applicable to that grain growth inhibitor of the present invention is preferred chemically inertly is easy to uniform distribution on the crystal grain boundary of ultra tiny material, and preferably add or the described ultra tiny material that do not detract at least basically in the character of chemistry, physics and the mechanics expected.Importantly, this inhibitor also can be used for being applicable to the precursor forms that is bonded to ultra tiny material.Particularly important of the present invention and favourable feature is that this grain growth inhibitor is bonded to described ultra tiny material with deliquescent (preferably water miscible) polymer precursor or with the form of the polymer precursor of eutectic (low-melting).Use deliquescent precursor to make this precursor (thereby and grain growth inhibitor) by ultra tiny material uniform distribution more.Use the polymer precursor of eutectic, promptly be lower than the precursor that fuses under the grain growing temperature of this ultra tiny material, also make this precursor by ultra tiny material uniform distribution more.Certainly, this precursor must be converted into described grain growth inhibitor by processing subsequent, preferably passes through heat treated.
The suitable grain growth inhibitor that contains above-mentioned feature includes but not limited to grain growth inhibitor known in the art, and it comprises metal, metal alloy, carbide, nitride, intermetallic compound and pottery.Special grain growth inhibitor comprises metal (as B, Si, Al, Cr, Ni, Mo, Hf, Ta, Fe, W, Zr), and rare earth metal (as Ce, La and Sm); Metal alloy (as, above-mentioned metal with as Cr, Ti and Mo alloying); Carbide (as based on the carbide of silicon with based on the carbide of titanium); Nitride (as based on the nitride of aluminium, based on the nitride and the BN of titanium); Intermetallic compound (comprising metal silicide such as AlSi and TiSi and metal aluminide such as TiAl); With other boron compounds (as TiB2).The preferred boron compound of this paper, preferred especially boron nitride is because the character of its easy synthetic operability, its favourable distribution characteristics, its unreactiveness and its excellent in chemical, physics and mechanics.
The synthetic polymer precursor that can generate grain growth inhibitor generally includes and form inorganic polymer from metal salt solution, filters this polymkeric substance and dry this polymkeric substance to obtain the dry polymer precursor.Under the situation of boron nitride, the boric acid and the urea of suitable chemical dose ratio are dissolved in the solvent, preferably water.Nitride gas such as ammonia froth (bubbled) by this solution then, make it become strong basicity, have been converted into the inorganic polymer precursor up to this metal precursor salts, and it will generate boron nitride by heat treated.Dry this product is to obtain the precursor polymer gel, and this precursor polymer gel can be stored by dried forms.
First embodiment of the present invention comprises: when synthetic this ultra tiny material or intermediate, this polymer precursor in-situ junction is bonded to this ultra tiny product or ultra tiny intermediate (being generally powder).Suitable synthetic technology includes but not limited to those technology known in the art, as the technology of OSR, ASR, IGC, CVC, mechanical alloying technology or other physics and chemistry.Preferred OSR of this paper and ASR technology.In this embodiment, this polymer precursor is dissolved to (preferably water) in the solvent, its comprise this ultra tiny material precursor under controlled temperature to select the suitable ratio of desired product.When this salt of dissolving, the pH value that should control solution takes place too early with the reaction that prevents this salt.
Then with the solution spray drying or the oven drying (this depends on the application of material) of gained, to form solid exsiccant ultramicro powder product or intermediate.The normally preferred process of this spraying drying.Control this spray-dired parameter and form different powder morphologies, comprise the spherical hollow shell and the solid ball of different porosities and structure.During drying process, the drop of this solution reaches a high temperature, and becomes more concentrated when solvent evaporation.During spraying drying or oven drying, partly or entirely polymer precursor can be converted into grain growth inhibitor.
If necessary, these dried powders obtain handling then, and preferred heat treated is randomly in reduction and carbonization or nitrogenize and can prepare under the condition of desired ultra tiny product.This grain growth inhibitor precursor can partly or entirely be converted into this grain growth inhibitor under this step.The condition of selecting suitable carbonization or nitrogenize is within those skilled in the art's ability, and in order to reach the particle size dispersion of expectation, need select suitable temperature and gas ratio with the activity of controlled C, O or N, for example use ammonia/hydrogen (as 600-800EC) reduced oxide at high temperature.
In second embodiment of the present invention, this polymer precursor is bonded to ultra tiny material of synthetic or ultra tiny intermediary material.This embodiment comprises with this polymer precursor dressing ultra-fine particles (as the submicron particle of ultra tiny WC/Co) with at the crystal grain that is being lower than this material and generates this coating material of heat treated (if necessary) under the temperature, therefore any matrix by this material and cause the diffusion of this polymer precursor on this crystal grain boundary.Then in controlled gas condition at high temperature in order to degrade this polymer precursor and in order further this grain growth inhibitor to be diffused to this crystal grain boundary, handle described combination of polymers precursor-nano structural material or intermediate mixture, preferred heat treated.
Particularly, this polymer precursor fuses or directly is dissolved in this ultra tiny material or the intermediate, preferably with form of powder.This polymer precursor is preferably dissolved in the solvent, and is added to the slurry of this ultra tiny material or this material.When to such an extent as to the enough little or enough porous of this particle make this polymer precursor obtain fully fine distribution by this material, then the precursor solution with proper concn is used for the described powder of humidification, and the powder that forms dry air or oven drying simply on described powder.Perhaps, the ultra-fine particles of this dressing is being lower than heat treated for some time under the grain growing temperature of this ultra tiny material, this polymer precursor is diffused to effectively this ultra tiny material or intermediate.
When this ultra tiny material was big or small less than the final powder of expectation, the spraying drying of the slurry of this polymer precursor and ultra tiny material can strengthen diffusion, and caused having the hollow or solid spherical gathering of scope for the diameter of about 1-200 micron.The spraying drying of this slurry causes the formation of dried powder, and wherein this grain growth inhibitor is evenly distributed in the crystal grain boundary of this ultra-fine particles basically.This exsiccant powder is the form with solid ball, and described solid ball has the diameter of scope for about 1-200 micron, and each bag contains the set of individual ultra-fine particles.
If necessary, the material (whether spraying drying, oven drying or dry air) of handling this dressing then is with this inhibitor precursor of degrading, preferably in controllable gas atmosphere under high temperature heat treated, and by any matrix (if exist) so that this inhibitor atom further is diffused on the crystal grain boundary of this ultra-fine particles.Carbonization or nitrogenize also can take place under this step.The dressing that subsequently this mixture ultramicro powder course of processing will form lot of materials or have advantageous property in controlled environment.
In another embodiment of the invention, at least a alloy addition is bonded in this ultra tiny material, no matter be with or without the combination of grain growth inhibitor.This alloy addition can be a powder any metal or pottery, described powder can by following or additive method effectively with this ultra tiny material alloys, and this can be to the remarkable bad influence of effect generation of this grain growth inhibitor (if existence).Suitable alloy addition includes but not limited to Ti, Cr, Mo, Ni, Zr, Ce, Fe, Al, Si, V, TiC, Mn, Y, W, above-mentioned alloy, above-mentioned nitride and above-mentioned intermetallic compound.
This alloy addition can be introduced by any substantial point in the method for the invention.Therefore, alloy addition can be introduced into this reaction mixture (being used for synthetic this ultra tiny material or ultra tiny intermediary material), and before synthetic this ultra tiny material or ultra tiny intermediary material (the first above-mentioned embodiment) or (the second above-mentioned embodiment) afterwards, subsequently in conjunction with grain growth inhibitor precursor (if existence).This alloy addition also can be bonded to this ultra tiny material of synthetic or ultra tiny intermediary material, and described in superincumbent first embodiment, it is synthetic also in conjunction with grain growth inhibitor precursor (if existence).Preferred this alloy addition and grain growth inhibitor precursor are bonded to ultra tiny material of firm synthetic or ultra tiny intermediary material simultaneously.
A method that is suitable for this preferred combining method is to obtain more uniform powdered mixture by at least one described alloy addition of ball milling, then this alloy addition is diffused to and contain this inorganic polymer grain growth inhibitor, thereby form colloidal solution.Then should ultra tiny material or ultra tiny intermediary material mix mutually with this colloidal solution, and with the solution spray drying or the oven drying that form.As second embodiment relevant as described in, by this alloy addition of ball milling and this ultra tiny material together, pass through in conjunction with this polymkeric substance grain growth inhibitor then, this alloy addition also can be introduced into this synthetic material or intermediary material.
Be suitable for synthetic or with the instrument that precursor is introduced into ultra tiny material comprise solution reaction container, ball mill device or ultrasonic machining system, spray-dryer, be equipped with common and necessary annex (as pH meter, temperature and gas flow control), vacuum system and high temperature cabonization unit's (fixed bed, moving-bed or flowing bed reactor).
This carbonization or nitrogenize device can be fixed-bed reactor, fluid bed reactor and/or moving-burden bed reactor.In this carbonization, can use reactant gases such as H
2, CO/CO
2, NH
3, acetylene, N
2, Ar.In moving-burden bed reactor, this solid particulate suspends by this flowing gas (it can increase total volume and separate this particle), to such an extent as to they are in the uniform motion and can contact with each other continuously.Therefore, this particle often contacts this reactant gases, causes very fast and effective carbonization process, and can reduce this spray-dired agglomeration of particles.Use the considerable advantage of this reactor to be that it prepares the powder of commercial usefulness in enormous quantities.Yet from the viewpoint of preparation, this moving-burden bed reactor is preferred reactor, because this moving-bed is applicable to the successive production line, and can be more effective in energy expenditure and gas consumption.
The present invention illustrates further by following non-restrictive example.
Embodiment
Embodiment 1: synthetic grain growth inhibitor polymer precursor
Arrival uses boric acid, H
3BO
3And urea (NH
2)
2CO (Aldrich chemical company, Milwaukee, WI).Originally, 61.831g (1mol) boric acid and 63.784g (1.062 moles) urea are dissolved to 1 liter de-oxygenised water.After mixing, this aqueous solution is heated to 90EC lentamente.Vigorous stirring froths ammonia to solution on one side on one side, becomes strong basicity until this solution.After reacting 4 hours, remove water by distillation, obtain residue, i.e. this polymer precursor is with the form of amorphous solid about 80g that weighs.Suppose in the presence of ammonia, thereby boric acid and urea reaction form the polyureas boron compound.This boron nitride precursor is tremelloid white resin, and is solvable at the water camber, and is easy to be milled to powder.In the presence of ammonia, be heated to higher temperature, originally this gel will fuse about 200EC, form the glass material of foam sample, be heated to about 500-650EC continuously, be transformed into the BN with the form of white powder.
Embodiment 2: the material that will be bonded to nanostructure
At first being dissolved in the distillatory deionized water to obtain of known quantity near saturated solution as synthetic BN polymer precursor as described in the embodiment 1.This then solution and hollow shell nanostructure WC-Co (Nanodyne company, New Brunswick, New Jersey; Arrival uses) combination, and ball milling makes slurry.The slurry that should grind is dry to remove moisture under the 100EC in baking oven then.Prepare a large amount of samples, wherein the molar percentage of boron in BN is 0.1%, 0.25%, 0.5%, 1%, 2%, 5% and 10%.Be converted into weight percent (wt.%), these values correspondingly are: promptly boron wt.% is respectively 0.006wt.%, 0.015wt.%, 0.03wt.%, 0.06wt.%, 0.119wt.%, 0.293wt.% and 0.569wt.% among the BN.
Embodiment 3: the material intermediate of sintering precursor/nanostructure
The sample that ground among the embodiment 2 is pressed into the 1.5cm dish by each sample that at first will about 10g, then 1400EC (using the heating rate of 10EC/min) and under the mobile argon gas each sample of heat treated, continue 0.5h.After the heat treated, the pelletizing of gained is contracted to half of about original size, and has been thickened in various degree, about 99% density of as many as.
The hardness value of the Vicker of these samples (VHN 300g) as shown in Figure 1.Average hardness with this sample of 0.0wt.% boron is about 2135, and maximum can reach 2228.All these samples are considerably tough and tensile.For example, when measuring conventional WC-Co (its VHN value is 1200-1600), the crack always occurs on the angle of each diamond shaped indent.The visible crack does not all appear in the sample of any one detection indenture place in nanostructure WC-Co material.
Embodiment 4: precursor solid diffuses to crystal grain boundary (argon gas processing)
The sample that ground among the embodiment 2 (in BN, containing 1 mole of % and 10 moles of %B) 600EC heat treated 5 hours under argon gas.Right reprocessed powder compression becomes the 1.5cm pelletizing, and 1400EC (use 10EC/min heating rate) and under the mobile argon gas heat treated, continue 0.5h.After the heat treated, the pelletizing of gained is contracted to half of about original size, and has been thickened in various degree, about 99% density of as many as.
Embodiment 5: precursor solid diffuses to crystal grain boundary (hydrogen treat)
The sample that ground among the embodiment 2 (in BN, containing 1 mole of % and 10 moles of %B) 600EC heat treated 5 hours under hydrogen.Right reprocessed powder compression becomes the 1.5cm pelletizing, and 1400EC (use 10EC/min heating rate) and under the mobile argon gas heat treated, continue 0.5h.After the heat treated, the pelletizing of gained is contracted to half of about original size, and has been thickened in various degree, about 99% density of as many as.
Embodiment 6: precursor solid diffuses to crystal grain boundary (ammonia processing)
The sample that ground among the embodiment 2 (in BN, containing 1 mole of % and 10 moles of %B) 600EC heat treated 5 hours under ammonia.Right reprocessed powder compression becomes the 1.5cm pelletizing, and 1400EC (use 10EC/min heating rate) and under the mobile argon gas heat treated, continue 0.5h.After the heat treated, the pelletizing of gained is contracted to half of about original size, and has been thickened in various degree, about 99% density of as many as.
Embodiment 7: the thermospray test
(about 1 pound) preparation is used for the sample (boron that contains 0.06wt.%) that the embodiment 2 of thermospray test ground in a large number.Carry out this thermospray test with Metco 9MB arc blood plasma spray gun.This spraying condition is summarized as follows:
| Test number | Spray is apart from (foot) | Voltage | Arc electric current (amps) | Play first air (scfm) | Relative temperature (A/scfm) | Relative time (inch/scfm) |
| 1 | 4 | 65 | 450 | 150 | 3.0 | 0.027 |
| 2 | 4 | 65 | 400 | 150 | 2.7 | 0.027 |
| 3 | 4 | 65 | 400 | 150 | 2.7 | 0.027 |
| 9 | 4 | 65 | 400 | 150 | 2.7 | 0.027 |
| 10 | 4 | 65 | 450 | 200 | 2.3 | 0.020 |
| 11 | 2.5 | 65 | 450 | 200 | 2.3 | 0.013 |
| 12 | 4 | 65 | 450 | 250 | 1.8 | 0.016 |
| 13 | 4 | 65 | 450 | 150 | 3.0 | 0.027 |
| 14 | 4 | 65 | 450 | 200 | 2.3 | 0.020 |
| 15 | 4 | 65 | 400 | 200 | 2.0 | 0.020 |
| 16 | 4 | 65 | 600 | 250 | 2.4 | 0.016 |
The physical properties of the material of thermospray is summarized as follows:
| Test number | Resistance to wear relatively | Satisfactory degree * | HV300 | HV300 | HV300 | HV300 | HV300 (on average) |
| 1 | 3 | 0.53 | 786 | 1051 | 855 | 898 | |
| 2 | 2 | ||||||
| 3 | 9 | 1.00 | 1042 | 829 | 1377 | 1083 | |
| 9 | 8 | 0.79 | 446 | 1215 | 622 | 761 | |
| 10 | 1 | 0.24 | 618 | 836 | 406 | 369 | 557 |
| 11 | 5 | 0.43 | 348 | 427 | 295 | 357 | |
| 12 | 0.05 | 0.04 | 385 | 275 | 267 | 309 |
| 13 | 6 | 0.61 | 550 | 459 | 715 | 675 | 600 |
| 14 | 5 | 0.48 | 389 | 484 | 496 | 456 | |
| 15 | 8 | 0.65 | 639 | 402 | 499 | 513 | |
| 16 | 1.5 |
* satisfactory degree=[max architecture of the structure/reservation of reservation) * (mean thickness/maximum mean thickness)]
0.05
SEM detects the material that shows test number 3 preparations and has best combination and microstructure.Measure these samples in the cross section of this dressing and the hardness value of the Vicker in the vertical surface, and these results are summarised among Fig. 2.Data presentation among Fig. 2 is the contact of dressing character under the different plasma condition in the thermospray test.This dressing character comprise relative resistance to wear, hardness and satisfactory degree.
Embodiment 8: the synthetic powder that contains the nanostructure of grain growth inhibitor of original position
By (NH with 22.64g (7.70mmol)
4)
6W
39O
12H
2Co (the NO2 of O, 9.88g (34m mol)
3)
2H
2O (Xiao Suangu) and 13.80g (77mol) glucose are dissolved in the 20mL water and prepare the aqueous solution.The certain volumetrical aqueous solution that comprises the BN of 12mg (0.5mmol) is added in the above-mentioned aqueous solution.This reaction mixture of spraying drying is to make W-C-Co-BN pre-composite powder then.Be transferred to this precursor powder in the High Temperature Furnaces Heating Apparatus then and at H
2(use the heating rate of 10EC/min) under/CO gaseous mixture and carry out carbonization, and lasting 30min, therefore preparation contains the nanostructure WC/Co of BN grain growth inhibitor.
Embodiment 9: the synthetic powder that contains the alloy nano structure of grain growth inhibitor of original position
By (NH with 22.64g (7.70mmol)
4)
6W
39O
12H
2The Xiao Suangu of O, 9.88g (34m mol) and 13.80g (77mol) glucose are dissolved in the 20mL water and prepare the aqueous solution.The certain volumetrical aqueous solution that comprises the BN of 12mg (0.5mmol) is added in the above-mentioned aqueous solution.The mixture that will comprise the Mo of the Cr of TiC, 0.0002g of 0.2g (3.3mmol) and 0.02g (0.2mmol) then adds the reaction mixture that contains 0.06wt%BN, 0.1wt.%Mo, 0.01wt.%Cr and 1wt.%TiC (with respect to WC) with preparation.This reaction mixture of spraying drying is to make the W-C-Co-BN pre-composite powder that contains alloy addition then.Be transferred to this precursor powder in the High Temperature Furnaces Heating Apparatus then and at H
2(use the heating rate of 10EC/min) under/CO gaseous mixture and carry out carbonization, and lasting 30min, therefore preparation contains the nanostructure WC/Co alloy of Ti, Cr and Mo and BN grain growth inhibitor.
Embodiment 10: alloy addition and BN grain growth inhibitor are to nanostructure WC/Co
Use 6g (0.1mol) TiC, 0.06g (1.2mmol) Cr, 0.6g (6.3mmol) Mo to prepare a series of compositions, and 1 mole of BN precursor solution of 29mL is added to 600g contains different amount Co (Nanodyne company; Arrival uses) nanostructure WC/Co contain the composition of 1wt.%TiC, 0.01wt.%Cr, 0.1%Mo and 0.06wt.%BN (with respect to WC/Co) with formation, wherein Co changes from 6wt.% to 15wt.%.These powder fully mix to form intermediate powder composition, subsequent spray drying or oven drying by ball milling then.
A part of spraying drying of this intermediate powder composition contains spherical WC/Co composition and this alloy addition of BN grain growth inhibitor with formation.These compositions can be used as the thermospray feed material or are used for fixed in a large number.
Another part of this intermediate powder composition attaches to the 1cm dish by hydropress, and at 1400EC (using the heating rate of 10EC/min) and at mobile H
2Heat treated under the gas continues 0.5h.After the heat treated, the pelletizing of gained is contracted to half of about original size, and has been thickened in various degree, at most near theoretical value or 100% density.When the wt.% of Co changes from 15% to 6%, these durometer levels of WC/Co agglomerated pellet that contain BN and Cr and Ti from 1900 to 2400VHN.The hardness that contains the nanostructure WC/Co of this grain growth inhibitor and alloy addition is drawn to Co content, with without any the result of the nanostructure WC/Co of alloy addition and/or grain growth inhibitor more as shown in Figure 3.
The toughness that contains the nanostructure WC/Co of this grain growth inhibitor and alloy addition also has increase with respect to the WC/Co that does not have grain growth inhibitor or alloy addition.For example, do not have grain growth inhibitor or alloy addition, typical WC-10Co has 10-12 (MPa) (meter
1/2) toughness, the toughness that wherein contains the nanostructure WC/Co of alloy addition and this grain growth inhibitor is 15-30 (MPa) (meter
1/2).
Embodiment 11: alloy addition and BN grain growth inhibitor are to sub-micron WC/Co
Sub-micron (0.2 micron) WC and micron size (1-5 micron) are bought from the Dow chemical company.1 mole of BN precursor solution of 6g (0.1mol) TiC, 0.06g (1.2mmol) Cr, 0.6g (6.3mmol) Mo and 29mL is added to 600g submicron WC/Co, contain the composition of 1wt.%TiC, 0.01wt.%Cr, 0.1%Mo and 0.06wt.%BN (with respect to WC/Co) with formation, wherein Co changes from 6wt.% to 15wt.%.These powder fully mix to form intermediate powder composition, sprayable drying of described composition or oven drying by ball milling then.
A part of spraying drying of this intermediate powder composition contains spherical WC/Co composition and this alloy addition of BN grain growth inhibitor with formation.These compositions can be used as the thermospray feed material or are used for fixed in a large number.
Another part of this intermediate powder composition attaches to the 1cm dish by hydropress, and at 1400EC (using the heating rate of 10EC/min) and at mobile H
2Heat treated under the gas continues 0.5h.After the heat treated, the pelletizing of gained is contracted to half of about original size, and has been thickened in various degree, at most near theoretical value or 100% density.When the wt.% of Co changes from 15% to 6%, the durometer level that makes pelletizing that comprises the WC/Co that contains alloy and grain growth inhibitor from 1600 to 1900VHN.
Conventional alloy technology comprises usually: with micron size powder mixes to form mixture, then by at high-temperature digestion to obtain this alloy material.On the contrary, particularly advantageous characteristics of the present invention is to use the grain growth inhibitor precursor of soluble and eutectic and/or alloy addition to obtain and this ultra tiny material uniform mixing.Use these technology that the grain growth inhibitor of controlled amount is bonded to nano structural material thereby grows to ultra-fine particles with making nano-structured particles control, this also is possible.
When showing and describing embodiment preferred, do not departing under the spirit and scope of the present invention, then can carry out different modifications and substitute.In addition, should understand: the mode by explanation rather than qualification is described the present invention.
Claims (26)
1. the method for preparing superfine alloys, described method comprises:
The grain growth inhibitor polymer precursor is bonded to the composition of synthetic ultra tiny material;
From containing the synthetic described ultra tiny material of described composition in conjunction with precursor;
Before synthetic described ultra tiny material, alloy addition is bonded to the composition of synthetic described ultra tiny material, perhaps, is bonded to the ultra tiny material of firm synthetic with preparation superfine alloys-grain growth inhibitor polymer precursor mixture; With
Described superfine alloys-grain growth inhibitor polymer precursor mixture processing is become grain growth inhibitor to transform this grain growth inhibitor polymer precursor.
2. the process of claim 1 wherein that described synthesis step comprises that reactant aqueous solution, inorganic solution reaction, inert-gas condensation, chemical vapour deposition, mechanical alloying or thermochemistry transform.
3. the process of claim 1 wherein that described ultra tiny material comprises nanostructure crystal grain, ultra tiny crystal grain or comprises the combination of at least a above-mentioned crystal grain.
4. the process of claim 1 wherein that described grain growth inhibitor comprises metal, metal alloy, metallic carbide, intermetallic compound, pottery or comprises the combination of at least a above-mentioned materials.
5. the process of claim 1 wherein that described grain growth inhibitor polymer precursor comprises water-soluble polymers precursor or low-melting polymer precursor.
6. the method for claim 1, wherein said grain growth inhibitor is TiC, BN or the combination that comprises at least a above-mentioned grain growth inhibitor, wherein said ultra tiny material is WC/Co, and described alloy addition is Cr, TiC, Mo or the combination that comprises at least a above-mentioned alloy addition.
7. the process of claim 1 wherein that described ultra tiny material comprises metal, metal alloy, sintering metal, intermetallic compound, pottery, ceramic to ceramic mixture or comprises the combination of at least a above-mentioned materials.
8. the process of claim 1 wherein that described ultra tiny material is selected from Cu, FeCu, FeCo, NiAl, MoC, MoSi, NiCr, TiC, Mo
2Si, NiCr/Cr
3C
2, Fe/TiC, Ni/TiC, Mo/TiC and WC/Co, the alloy of one or more among above-mentioned metal and Ti, Cr, Mo, Ni, Zr, Ce, Fe, Al, Si, V, TiC, Mn, Y, the W and comprise the combination of at least a above-mentioned materials.
9. the process of claim 1 wherein that described alloy addition comprises metal-powder, ceramic powder or comprises the combination of at least a above-mentioned powder.
10. the process of claim 1 wherein that described alloy addition comprises the nitride of the alloy of Ti, Cr, Mo, Ni, Zr, Ce, Fe, Al, Si, V, TiC, Mn, Y, W, aforementioned additive, aforementioned additive or the intermetallic compound of aforementioned additive.
11. the process of claim 1 wherein that described treatment step is included in the described mixture of heat treated under described this grain growth inhibitor polymer precursor efficient temperature of degrading.
12. prepare the method for superfine alloys, described method comprises:
The synthetic ultra tiny material that contains ultra-fine particles;
With the grain growth inhibitor polymer precursor with described ultra-fine particles dressing;
Before synthetic, alloy addition is bonded to the composition that synthesizes described ultra tiny material, perhaps, to such an extent as to be bonded to the result of the ultra tiny material preparation of described firm synthetic superfine alloys-grain growth inhibitor polymer precursor compound as described dressing; With
Described superfine alloys-grain growth inhibitor polymer precursor compound is handled so that described grain growth inhibitor polymer precursor to small part is converted into grain growth inhibitor.
13. the method for claim 12 wherein by grain growth inhibitor polymer precursor and described alloy addition is combined with the solution of the dressing that is used for described ultra-fine particles, is bonded to the ultra tiny material of described firm synthetic with described alloy addition.
14. the method for claim 12, wherein by before dressing with described alloy addition with described ultra-fine particles ball milling, described alloy addition is bonded to the ultra tiny material of described firm synthetic.
15. the method for claim 12, wherein said synthesis step comprise that reactant aqueous solution, inorganic solution reaction, inert-gas condensation, chemical vapour deposition, mechanical alloying or thermochemistry transform.
16. the method for claim 12, wherein said ultra tiny material comprise nanostructure crystal grain, ultra tiny crystal grain or comprise the combination of at least a above-mentioned materials.
17. the method for claim 12, wherein said grain growth inhibitor comprise metal, metal alloy, metallic carbide, intermetallic compound, pottery or comprise the combination of at least a above-mentioned materials.
18. the method for claim 12, wherein said grain growth inhibitor polymer precursor comprises water-soluble polymers precursor or low-melting polymer precursor.
19. the method for claim 12, wherein said grain growth inhibitor is TiC, BN or the combination that comprises at least a above-mentioned grain growth inhibitor, wherein said ultra tiny material is WC/Co, and described alloy addition is Cr, TiC, Mo or the combination that comprises at least a above-mentioned alloy addition.
20. the method for claim 12, wherein said ultra tiny material comprise metal, metal alloy, sintering metal, intermetallic compound, pottery, ceramic to ceramic mixture or comprise the combination of at least a above-mentioned materials.
21. the method for claim 12, wherein said ultra tiny material is selected from Cu, FeCu, FeCo, NiAl, MoC, MoSi, NiCr, TiC, Mo
2Si, NiCr/Cr
3C
2, Fe/TiC, Ni/TiC, Mo/TiC and WC/Co, the alloy of one or more among above-mentioned metal and Ti, Cr, Mo, Ni, Zr, Ce, Fe, Al, Si, V, TiC, Mn, Y, the W, and the combination that comprises at least a above-mentioned materials.
22. the method for claim 12, wherein said ultra tiny material comprise metal, metal alloy, sintering metal, intermetallic compound, pottery, ceramic to ceramic mixture or comprise the combination of at least a above-mentioned materials.
23. the method for claim 12, wherein said ultra tiny material is selected from Cu, FeCu, FeCo, NiAl, MoC, MoSi, NiCr, TiC, Mo
2Si, NiCr/Cr
3C
2, Fe/TiC, Ni/TiC, Mo/TiC and WC/Co, the alloy of one or more among above-mentioned metal and Ti, Cr, Mo, Ni, Zr, Ce, Fe, Al, Si, V, TiC, Mn, Y, the W and comprise the combination of at least a above-mentioned materials.
24. the method for claim 12, wherein said alloy addition comprise metal-powder, ceramic powder or comprise the combination of at least a above-mentioned powder.
25. the method for claim 12, wherein said alloy addition comprise the alloy of Ti, Cr, Mo, Ni, Zr, Ce, Fe, Al, Si, V, TiC, Mn, Y, W, aforementioned additive, the nitride of aforementioned additive or the intermetallic compound of aforementioned additive.
26. the method for claim 12, wherein said treatment step are included in the described mixture of heat treated under described this grain growth inhibitor polymer precursor efficient temperature of degrading.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/801,206 US7537636B2 (en) | 1997-08-22 | 2007-05-08 | Methods of making superfine alloys |
| US11/801,206 | 2007-05-08 |
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| CN102441673A (en) * | 2011-12-08 | 2012-05-09 | 九江学院 | Mechanical alloying preparation of TiB2Method for ceramic phase reinforced Co-based alloy composite powder |
| CN109019692A (en) * | 2018-10-19 | 2018-12-18 | 长沙小如信息科技有限公司 | The preparation method of tungsten carbide |
| CN112080661A (en) * | 2020-09-02 | 2020-12-15 | 四川大学 | A kind of preparation method of ultrafine cemented carbide |
| CN119264971A (en) * | 2024-10-09 | 2025-01-07 | 江阴豪景纺织有限公司 | A low-viscosity lubricating oil and preparation method thereof |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102441673A (en) * | 2011-12-08 | 2012-05-09 | 九江学院 | Mechanical alloying preparation of TiB2Method for ceramic phase reinforced Co-based alloy composite powder |
| CN109019692A (en) * | 2018-10-19 | 2018-12-18 | 长沙小如信息科技有限公司 | The preparation method of tungsten carbide |
| CN109019692B (en) * | 2018-10-19 | 2021-06-22 | 湖南金雕能源科技有限公司 | Preparation method of tungsten carbide |
| CN112080661A (en) * | 2020-09-02 | 2020-12-15 | 四川大学 | A kind of preparation method of ultrafine cemented carbide |
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