CN103526077A - Micro-nano oxide particle enhanced nickel base alloy powder as well as preparation method thereof - Google Patents

Micro-nano oxide particle enhanced nickel base alloy powder as well as preparation method thereof Download PDF

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CN103526077A
CN103526077A CN201310502656.9A CN201310502656A CN103526077A CN 103526077 A CN103526077 A CN 103526077A CN 201310502656 A CN201310502656 A CN 201310502656A CN 103526077 A CN103526077 A CN 103526077A
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micro
powder
nano
alloy powder
oxide particle
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丁刚
丁家伟
耿德英
张莹
符寒光
谢宗翰
王爱华
郭洪才
印杰
孙健
张宁
强颖怀
郭长庆
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JIANGSU SHENGWEI MOLD MATERIALS CO LTD
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JIANGSU SHENGWEI MOLD MATERIALS CO LTD
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Abstract

The invention relates to micro-nano oxide particle enhanced nickel base alloy powder as well as a preparation method thereof. The micro-nano oxide particle enhanced nickel base alloy powder is characterized in that the micro-nano oxide particle enhanced nickel base alloy powder contains matrix alloy powder and micro-nano oxide hard particles as well as a binder. The micro-nano oxide particle enhanced nickel base alloy powder is prepared from the following components in percent by weight: 50-98% of the matrix alloy powder, 1-45% of combined mixture powder of one or more than two out of micro-nano Al2O3 or micro-nano Cr3C2 and micro-nano ZrO2, and 1-5% of the binder which are prepared as combined powder. The preparation process comprises the following steps: preparation of the matrix alloy powder; addition of the micro-nano particle particles; addition of the binder; stirring and ball-milling; combination of powder; drying; crushing; sieving. The micro-nano oxide particle enhanced alloy powder provided by the invention not only has higher hardness and tenacity, but also has excellent wear resistance and corrosion resistance, so that the powder is particularly applicable to laser-cladding parts in high impact and high-wear-resisting working conditions. The powder can effectively prevent segregation in the storage, transportation and using processes due to wide difference of the components in proportion.

Description

Micro-nano oxide particle strengthens Co-based alloy powder and preparation method thereof
Technical field
The invention belongs to nickel-base alloy technical field, relate to a kind of powdered alloy and preparation method thereof, particularly a kind of particularly a kind of micro-nano oxide particle strengthens Co-based alloy powder and preparation method thereof, and this micro-nano oxide particle strengthens Co-based alloy powder and is applicable to laser melting coating HI high impact, high abrasion operating mode component.
Background technology
In modern daily life and industrial production, the attrition and attack of metallic substance there will be in every field, one of two large major ways that destroy component of machine, engineering component, corrosion will cause a large amount of consumption of mechanical component, and wearing and tearing are to cause one of major reason of mechanical component inefficacy.They,, in a large amount of metallic substance of loss, have also wasted ample resources, occupy very large proportion in financial loss.
The inefficacy of the engineering component that high temperature, burn into friction and wear cause occurs in surface mostly, and this phenomenon is impelled the very big concern of Materials science worker to material surface, and impels the fast development of material surface modifying technology.People wish when material monolithic keeps enough toughness and intensity, make material surface obtain higher, specific use properties, as wear-resisting, anti-corrosion and anti-oxidant etc.
It is reported, at present, in , whole world industrialized country, the energy consuming in wearing and tearing accounts for 1/2nd of total energy, approximately has 60%~80% component of machine because wearing and tearing were lost efficacy.A highly developed industrialized country, the financial loss causing because of wearing and tearing every year almost accounts for 1%~2% of total value of production in national economy.For example, the financial loss that the U.S. causes due to wearing and tearing is every year on average up to 20,000,000,000 dollars; The financial loss that Britain is caused by wearing and tearing is every year on average over 51,500 ten thousand pounds.In China, the financial loss being caused by wearing and tearing is equally also quite serious.Only according to department's rough Statistics such as oil, chemical industry, coal, electric power, agricultural machinery, just there is steel consumption up to millions of tons in China every year in wearing and tearing, and financial loss reaches 200~30,000,000,000 yuan more than.Thus, the effect of attrition of metallic substance performance quality and the work-ing life of mechanical component, and then affects the competitive capacity of these mechanical component on market.
Meanwhile, metallic corrosion problem also spreads all over national economy every field, from the industrial and agricultural production that is applied to of top science technology, and the manufacture that is applied to national defense industry from daily life, the place of every use metallic substance, all exists etching problem in varying degrees.According to relevant expert's statistics, each minute half in the whole world just has one ton of steel to be etched into iron rust.For example, the financial loss that the 1975 Nian, U.S. are caused by corrosion every year, up to 82,000,000,000 dollars, accounts for 4.9% of total value of production in national economy; Nineteen ninety-five, the financial loss straight line that the U.S. causes due to corrosion rises to 3,000 hundred million dollars.Statistics shows, in a country that industry is flourishing, because corroding the financial loss causing, accounts for 2%~4% of total value of production in national economy, the summation of the loss causing over all natural disasteies such as floods, fire, earthquake and ancient measure of length, equal to 8 cun wind.Although China Jin Weiyige developing country, because the loss that corrosion brings is also considerable, annual about 5,000 hundred million yuans, accounts for 6% left and right of Chinese national economy total output value.The financial loss only being caused by corrosion every year in oil and gas field is with regard to approximately 10,000,000,000 yuan, and the fund waste that coal-mining industry is caused by corrosion is every year about 55.6 hundred million yuan, nearly 1,700,000,000 yuan of the annual corrosion loss of power system.
Therefore, from limited resources and the energy, modern demand of industrial production component of machine has enough wear and corrosion behaviors, can extremely under rugged environment, work long hours at high temperature, high loading etc., and the attrition and attack problem that therefore solves metal is extremely urgent.
Laser melting coating ceramic technology can combine the high obdurability of metal, good manufacturability and wear-resisting, anti-corrosion, the high temperature resistant and anti-oxidation characteristics of stupalith excellence, for the surface strengthening technology of most worthy and competitive power, it is also one of focus of laser melting and coating technique development.
Laser melting coating is the technology of emerging a, fast development, it is under high-energy-density laser beam irradiation, matrix surface skim melts with the alloy adding as required simultaneously, forming thickness is 10~1000 μ m surface melting layers, the processing method that rapid solidification requires to meet a certain property, be a new technology of the multidisciplinary intersection such as material interaction and rapid solidification moulding in set laser heat fused, molten bath, this technology obtains more careful research aspect surface treatment.
Because local surfaces is subject to heat density large, spot diameter is little, and heated time is short, therefore melting area is very little on workpiece surface, passes to inside workpiece less calories, has very large thermograde in melting area, and speed of cooling can reach 10 4~10 9℃/s.Just because of rapid solidification, give the feature that alloy is different from normal freezing.As the laser melting coating of one of surface modification means, be suitable for top layer modification and the reparation of each metalloid.Cladding laser surfaces can keep former coating alloy composition (thinning ratio 5~8%), only at the intersection of reflow zone and matrix, exists very limited ,Er Ci spreading area, phase diffusion zone to realize just the metallurgical binding of coat and matrix necessary.It is upper that it can be coated in common material (workpiece) high performance powdered alloy, thereby obtain the top coat (as good coatings such as heat-resisting, anti-corrosion, wear-resisting, shock resistances) of excellent specific property.
Compare with traditional surface modification (thermospray, plasma spraying etc.) technology, it mainly contains following advantage: interface is metallurgical binding; Organize superfine; Cladding layer composition is even and extent of dilution is low; Coating thickness is controlled; Heat distortion is little; Easily realize constituency cladding and technological process and easily realize automatization.In process for modifying surface, laser melting coating has become more active research field.
Laser surface coating technology is one of the advanced subject in the material surface engineering field that grows up of middle nineteen seventies, both at home and abroad just flourish.Along with the development and perfection of superpower laser and supporting technology, it progressively moves towards industrial application from laboratory study, in following material surface modifying field, will have powerful vitality.Laser melting coating both can be used for the surface modification of traditional material, promoted the performance of material, can be used for again the reparation of surface failure part, therefore available body material is very extensive, as carbon steel, steel alloy, cast iron and aluminium alloy, copper alloy, nickel base superalloy etc.In addition, material scientific research personnel has also developed non-crystalline state and quasi crystal coating etc.At present, more at the study on the modification on traditional material surface to laser technology both at home and abroad, the research of high quality steel, high-temperature alloy surface modification also has report, yet application laser melting coating is repaired the practical engineering application of some components of machine and is but awaited further popularization, major cause is in laser cladding process, often to have the problems such as crackle, coating be inhomogeneous, awaits the further research of scientific worker.
That the state of laser melting coating layer material generally has is Powdered, thread, paste etc.In addition also can be using sheet metal, sintered metal product, steel band and welding rod etc. as cladding material, wherein powdered alloy is most widely used in laser melting and coating technique.
Practical service environment condition depending on workpiece is different, also different to the performance requriements of surface coating.Cladding alloy system mainly contains ferrous alloy, nickel-base alloy, cobalt-base alloy and complex alloy powder etc.It is local wear-resisting and hold yielding part that iron(-)base powder is suitable for requirement; Nickel-base alloy is suitable for that requirement part is wear-resisting, the member of heat and corrosion resistant and thermal fatigue resistance, and required laser power density is slightly higher than cladding ferrous alloy; Cobalt-base alloy coating is suitable for the part of wear-resisting, the anti-corrosion and thermal fatigue resistance of requirement; Ceramic coating at high temperature has higher intensity, and Heat stability is good, and chemical stability is high, is applicable to the part of wear-resisting, anti-corrosion, high temperature resistant and oxidation-resistance.
Wear-resistant coating is in laser melting coating ceramic coating, to study to such an extent that be also maximum a kind the earliest.Although Ni base, Co base, Fe base self-fluxing alloy itself just have good wear-resisting, anti-corrosion, resistance toheat, utilize their laser cladding layer carry out material surface strengthening research report oneself through a lot.But under the serious condition of slip, gouging abrasion and abrasive wear, simple Ni base, Co base, the not competent service requirements of Fe base self-melting alloy.
Nano material and nanotechnology are novel material and the new and high technologies that 20 th century later occur.Metal-base nanometer composite material be by nano level metal or nonmetal particle equably disperse in metal and alloy substrate, form, show the mechanics, calorifics, electricity, magnetics and the optical property that are different from general macrocomposite, there is property and function that stock blend does not possess, than traditional metallic substance, its specific tenacity, specific modulus, wear resistance, conduction, heat conductivility etc. all have significantly and significantly improve.
Yet because the surface of nanoparticle can be large, surfactivity is high, so single nanoparticle is extremely unstable, there is strong absorption particle and reach stable trend around, thereby cause the generation of agglomeration between particle.And the coacervate that forms of nanoparticle hard agglomeration often, thereby the specific surface of material is reduced, and the excellent specific property of nanoparticle is almost completely lost, and practical application effect is very poor.And the preparation cost of nano particle and height.
But, with respect to nanoparticle, micron particle be no matter surface can, surfactivity, or intergranular magnetism is all less, a little less than.Therefore, compare with the situation that is easy to form hard aggregation between nanoparticle, the reunion degree of micron particle is just less, and formed coacervate is soft-agglomerated form mostly, this soft-agglomerated be can be scattered by common mechanicals efforts or other less strength.Micron-nano composites is except the small-size effect, surface and interface effect, quantum size effect and the macro quanta tunnel effect that have single nano material and have, also there is compound collaborative several functions: can change single particle surface properties, increase the contact area of two or more components; Can prevent particle agglomeration, the physicochemical property such as the dispersiveness of raising nanoparticle, free-running property, catalytic effect.Possess the more not available excellent properties of common matrix material.
Nano/micron compounding technology is a new technique of field of nanometer material technology.Utilize this technology can obtain nanoparticle without reuniting, nano functional characteristic is not fully exerted, nanoparticle disperses good nano composite material in system.And for nano composite material, greatly reduce the preparation cost of matrix material.
Adopt micron particle to replace pure nano particle to strengthen and modification metallic substance, because had cost is low, granule preparing process is simple, and the excellent property of prepared reinforced composite, is the new development trend of metal-base composites preparing technical field.
Matrix material is a kind of novel surface strengthening engineering materials, metal and metal, metal and pottery, pottery and pottery etc., and the range of choice of the collocation between powdered alloy and between powdered alloy and pottery is very extensive.Recent domestic has been carried out various dystectic carbide, nitride, boride and the ceramic oxide particle that adds certain content in the powdered alloy system of above-mentioned laser melting coating for this reason, make the even pure ceramic coating of cermet composite coating, to improve the wear resistance of cladding layer.
Although adopt matrix material to carry out laser melting coating, can prepare high performance composite coating, but at present domestic most still research in laboratory, and its preparation technology adopts nickel-based self-fluxing alloy to mix with the WC powder of certain content in laboratory, then add saturated turps or homemade organic binder bond, furnishing slip or paste, precoating is overlying on workpiece, then carries out laser melting coating or sintering.Its hard particles adding is large, density is different from matrix metal, and the distribution of particle in cladding layer is often inhomogeneous, conventionally presents Gradient distribution; The wettability of added particulate material and matrix, stability, the coefficient of expansion and chemical reactivity etc. all cause the ununiformity of the microstructure and property of cladding layer.And prepared combination powder is because each constituent element proportion differs greatly, thereby in storage, transportation and use procedure and easily produce segregation.Cannot carry out commercialization supply, on market, there is not yet at present micro-nano granules and strengthen the merchandise sales of laser melting coating special powder.For above-mentioned reasons, there is not yet so far laser melting coating special combination powder, thereby restricted the application of laser melting coating on high abrasion operating mode field.
Summary of the invention
The object of the invention is to avoid above-mentioned deficiency of the prior art, develop and a kind ofly can meet required a kind of micro-nano oxide particle under the serious abrasive wear working condition of engineering machinery and strengthen Co-based alloy powder and preparation method thereof.
For achieving the above object, the design that the present invention can be by following basic chemical composition and add that micro-nano oxide particle strengthens Co-based alloy powder and accordingly technology of preparing scheme realize:
A kind of micro-nano oxide particle provided by the present invention strengthens Co-based alloy powder and is comprised of matrix alloy powder and micro-nano oxide compound enhanced granule and binding agent, and its proportioning is: 50~98% matrix alloy powder, 1~45% micro-nano Al 2o 3or micro-nano Cr 3c 2, micro-nano ZrO 2the micro-nano mixture powder of combination that one of them or two kinds are above, 1~5% binding agent is prepared into combination powder; Wherein the nano-particle content in micro-nano granules is 20~30%; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.4~0.8%C, 2~3%Si, 1~3%B, 12~18%Cr, 6~8%Cu, 0.5~1%Sn, 10~15%Fe, 0.1~1.2%MgO, 0.2~2%CaF 2, CeO 2, Y 3o 2, La 2o 3above combination≤0.9% of one of them or two kinds, Ni surplus and inevitably impurity elements;
Micro-nano oxide particle provided by the present invention strengthens Co-based alloy powder and preparation method thereof, and its step of preparation process is:
Micro-nano oxide particle → interpolation binding agent → stirring ball-milling → combination the powder of matrix alloy powder preparation → add → dry → broken → screening; Concrete technology step is as follows:
(1) matrix alloy preparation
The technical process of matrix alloy powder preparation is: batching → melting → atomization → dry → screening;
Batching: raw material is pure nickel, Graphite Powder 99, FeCr, FeB, FeSi, Cu, Sn, re-si-mg alloy, Rare-Earth Ce;
Melting: the above-mentioned raw material preparing is carried out to melting in vacuum induction furnace or medium-frequency induction furnace, and temperature of fusion is about 1250 ℃-1350 ℃, controls carbon content and reaches requirement, after stokehold adjusting component is qualified, and 1200~1280 ℃ of tapping temperatures;
Atomization: adopt indifferent gas or hydraulic atomized, atomization aperture 5~10mm, atomizing pressure, 10~14MPa;
Dry: equipment used is coated infrared drier, and bake out temperature is 220 ℃~280 ℃;
Screening: sift out size range for+150 orders~-350 object powder is as finished powder by powder shifter;
(2) add micro-nano oxide particle
Choose size range for the commercially available micro-nano Al of+150 orders~-350 object 2o 3or micro-nano Cr 3c 2, micro-nano ZrO 2one of them or two kinds of above micro-nano mixture powder of combination are as strengthening hard particles; Wherein the nano-particle content in micro-nano granules is 20~30%;
(3) add binding agent
Adopt resol, epoxy resin or the water glass of heat curing-type to make binding agent, add pimelinketone or methanol solvate, make it be dissolved into resin solution;
(4) stirring ball-milling
By the matrix alloy powder preparing and micro-nano Al 2o 3or micro-nano Cr 3c 2, micro-nano ZrO 2after the micro-nano mixture powder of combination that one of them or two kinds are above and binding agent are configured according to required ratio, pour in agitating ball mill, in pimelinketone or methanol solvate, make it be dissolved into resin solution the resin dissolves of required dosage; After stirring, pour in the powder mix of required processing in ball mill, after being prepared according to 2:1~3:1 ratio of grinding media to material, the abrading-ball of sphere diameter 10~20mm joins in agitating ball mill, starting agitating ball mill, abundant stirring ball-milling through 5~60 hours, each component of powder mix and resin liquid are all evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into micro-nano combination powder;
(5) dry
The combination powder that ball milling is good is poured out from ball mill, then dry through 150 ℃~200 ℃;
(6) broken and screening
Dried combination powder is carried out to fragmentation, by powder shifter, sift out size range for+150 orders~-350 object powder is respectively as finished powder, obtain required composition, desired particle size grade and don't the combination powder of solute segregation can occur.
Beneficial effect
Compared with prior art, tool of the present invention has the following advantages:
1) micro-nano oxide particle of the present invention strengthens by the existing higher toughness of powdered alloy, and high hardness, has again excellent wear resistance and solidity to corrosion, and its abrasive wear resistance can be 10 times of rich chromium cast iron, and its solidity to corrosion and 1Cr18Ni9Ti are suitable.Be applicable to laser melting coating HI high impact, high abrasion operating mode component.
2) the micro-nano oxide particle enhancing of the present invention base alloy powder has excellent laser melting and coating process performance, and the laser cladding layer after processing has the advantages such as flawless, pore-free, inclusion-free, dense structure, grain refining.
3) the micro-nano oxide particle of preparing through technique of the present invention strengthens Co-based alloy powder and each constituent element powder particle can be wrapped up, and is bonded together; There is enough cohesive strengths, can effectively prevent that composition powder from producing segregation because each constituent element proportion differs greatly in storage, transportation and use procedure.
4) the micro-nano oxide particle of the present invention strengthens Co-based alloy powder, be specially adapted to the laser melting coating reparation of the alloy workpiece of high surfaces hardness, toughness and high-wearing feature, gained cladding alloy powder technology performance is good, under the condition without preheating and subsequent heat treatment, can obtain the flawless Laser Clad Alloy Coatings of the large thickness of big area, cladding layer intensity, hardness and wear resistance are high, plasticity and toughness are good, and significantly reduce with powdered alloy cost than existing most of used for hot spraying self-fluxing alloy powders and existing most of laser melting coating.Can reduce the consumption of strategic rare elements, significantly reduce laser melting coating cost.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment mono-
A kind of micro-nano oxide particle strengthens Co-based alloy powder and preparation method thereof, this micro-nano oxide particle strengthens Co-based alloy powder and is comprised of matrix alloy powder and micro-nano oxide particle and binding agent, its proportioning is: 60% matrix alloy powder, 37% micro-nano Al 2o 3, 3% phenolic resin adhesive is prepared into combination powder; Wherein the nano-particle content in micro-nano granules is 20~30%; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.5%C, 2%Si, 1.5%B, 14%Cr, 6%Cu, 0.5%Sn, 13%Fe, 0.1%MgO, 0.5%CaF 2, 0.2%CeO 2, 0.2%Y 3o 2, 0.2%La 2o 3, Ni surplus.
Its manufacturing technology steps:
Micro-nano oxide particle → interpolation binding agent → stirring ball-milling → combination the powder of matrix alloy powder preparation → add → dry → broken → screening; Concrete technology step is as follows:
(1) matrix alloy preparation
The technical process of matrix alloy powder preparation is: batching → melting → atomization → dry → screening;
Batching: raw material is pure nickel, Graphite Powder 99, FeCr, FeB, FeSi, Cu, Sn, re-si-mg alloy, Rare-Earth Ce; By above-mentioned weight percent proportioning, be ready to make the starting material of matrix metal powder.
Melting: start vacuum induction intermediate frequency furnace, by the requirement of melting technology, put into metal and start melting, the metal of general easy oxidation was put in the later stage of fusing.Temperature of fusion is approximately controlled at 1250-1300 ℃; After the metal of this stove all melts in stove, carry out slag making, remove the impurity in molten metal, then enter refining period and carry out refining, before cast, add reductor to carry out deoxidation, control carbon content and reach requirement, after stokehold adjusting component is qualified, tapping temperature is controlled at 1200~1250 ℃.
Atomization: the qualified alloy liquid of melting is poured in cone bottom pour ladle, start to carry out the atomization of metal-powder, open high-pressure inert gas, using the high pressure gas from gas cylinder as air knife, after the constraint of leting slip a remark that is 5~10mm by aperture to fusing, become the molten metal bath stream of a thread to cut atomization, atomizing pressure 10~14MPa, by the small molten drop of metal atomization poling, final set becomes powdered alloy.Metal-powder after solidifying, still quite easily oxidation when high temperature, so must allow its cool to room temperature under the environment of anaerobic or hypoxemia, could reduce the oxygen level of powder.Normal nebulisation time is about 5~20 minutes.
Dry: equipment used is coated infrared drier, approximately 250 ℃ of bake out temperatures, dried metal-powder, the chemical examination of Chemical Composition is carried out in first sampling, proceeds to next procedure after qualified.
Screening: sift out size range for+150 orders~-350 object powder is as finished powder by powder shifter.
(2) add micro-nano oxide particle
Choose size range for the commercially available micro-nano Al of-250 object 2o 3powder is as enhanced granule; Wherein the nano-particle content in micro-nano granules is 20~30%;
(3) add binding agent
Adopt the resol of heat curing-type to make binding agent, add cyclohexanone solvent, make it be dissolved into resin solution;
(4) stirring ball-milling
By the matrix alloy powder preparing and micro-nano Al 2o 3after powder and binding agent are configured according to above-mentioned ratio, pour in agitating ball mill, the resol of 3% heat curing-type is dissolved in cyclohexanone solvent and makes it be dissolved into resin solution, after stirring, pour in the powder mix of the required processing in ball mill, after being prepared according to 2:1 ratio of grinding media to material, the abrading-ball of sphere diameter 12mm joins in agitating ball mill, starting agitating ball mill, abundant stirring ball-milling through 25 hours, each component of powder mix and resin liquid are all evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into micro-nano combination powder,
(5) dry
The combination powder that ball milling is good is poured out from ball mill, then dry through 180 ℃;
(6) broken and screening
Dried combination powder is carried out to fragmentation, by powder shifter, sift out size range for+150 orders~-350 object powder is as finished powder, obtain required composition, desired particle size grade and don't the combination powder of solute segregation can occur.
Requirement by user is sieved, packing warehouse-in.
Embodiment bis-
A kind of micro-nano oxide particle strengthens Co-based alloy powder and preparation method thereof, this micro-nano oxide particle strengthens Co-based alloy powder and is comprised of matrix alloy powder and micro-nano oxide particle and binding agent, its proportioning is: 68% matrix alloy powder, 30% micro-nano ZrO 2, 2% epoxy adhesive is prepared into combination powder; Wherein the nano-particle content in micro-nano granules is 20~30%; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.6%C, 3%Si, 2.5%B, 16%Cr, 7%Cu, 1%Sn, 15%Fe, 0.15%MgO, 0.9%CaF 2, 0.25%CeO 2, 0.25%Y 3o 2, 0.25%La 2o 3, Ni surplus.
(2) add micro-nano oxide particle
Choose size range for the commercially available micro-nano ZrO of-300 object 2powder is as strengthening hard particles; Wherein the nano-particle content in micro-nano granules is 20~30%;
(3) add binding agent
Adopt the epoxy resin of heat curing-type to make binding agent, add methanol solvate, make it be dissolved into resin solution;
(4) stirring ball-milling
By the matrix alloy powder preparing and micro-nano ZrO 2after powder and binding agent are configured according to above-mentioned ratio, pour in agitating ball mill, the resol of 2% heat curing-type is dissolved in methanol solvate and makes it be dissolved into resin solution, after stirring, pour in the powder mix of the required processing in ball mill, after being prepared according to 3:1 ratio of grinding media to material, the abrading-ball of sphere diameter 15mm joins in agitating ball mill, abundant stirring ball-milling through 15 hours, each component of powder mix and resin liquid are all evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into micro-nano combination powder;
Its preparation method is identical with embodiment mono-.
Embodiment tri-
A kind of micro-nano oxide particle strengthens Co-based alloy powder and preparation method thereof, this micro-nano oxide particle strengthens Co-based alloy powder and is comprised of matrix alloy powder and micro-nano oxide particle and binding agent, its proportioning is: 68% matrix alloy powder, 30% micro-nano Al 2o 3with micro-nano ZrO 2the micro-nano mixture powder forming is done, and 2% epoxy adhesive is prepared into combination powder; Wherein the nano-particle content in micro-nano granules is 20~30%; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.4%C, 2.8%Si, 2.0%B, 18%Cr, 8%Cu, 0.7%Sn, 10%Fe, 0.2%MgO, 1.5%CaF 2, 0.3%CeO 2, 0.3%Y 3o 2, 0.3%La 2o 3, Ni surplus.
(2) add micro-nano oxide particle
Choose size range for the commercially available 50% micro-nano Al of-200 objects 2o 3with 50% micro-nano ZrO 2form micro-nano mixture powder as enhanced granule; Wherein the nano-particle content in micro-nano granules is 20~30%;
(3) add binding agent
Adopt water glass to make binding agent, add methanol solvate;
(4) stirring ball-milling
By the matrix alloy powder preparing and 50% micro-nano Al 2o 3with 50% micro-nano ZrO 2after mixed powder and binding agent are configured according to above-mentioned ratio, pour in agitating ball mill, 2.5% water glass is incorporated in methanol solvate, after stirring, pour in the powder mix of the required processing in ball mill, after being prepared according to 2.8:1 ratio of grinding media to material, the abrading-ball of sphere diameter 18mm joins in agitating ball mill, starting agitating ball mill, abundant stirring ball-milling through 32 hours, each component of powder mix and water glass liquid are all evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into micro-nano combination powder;
Its preparation method is identical with embodiment mono-.
The micro-nano oxide particle of the above composition that the present invention proposes strengthens Co-based alloy powder, be specially adapted to the laser melting coating on corresponding product surface, the hardness of its cladding layer is high, wear resistance is good, the tendency that produces cracking and other overlay defect is little, can prepare large thickness cladding layer, and laser melting and coating process is functional, than now, use the cost of cladding alloy powder low, can be suitable for application widely needs.Material of the present invention is applied has significant economic and social benefit.

Claims (1)

1. a micro-nano granules strengthens Co-based alloy powder and preparation method thereof, it is characterized in that: micro-nano oxide particle strengthens Co-based alloy powder and is comprised of matrix alloy powder and micro-nano oxide compound enhanced granule and binding agent, its proportioning is: 50~98% matrix alloy powder, 1~45% micro-nano Al 2o 3or micro-nano Cr 3c 2, micro-nano ZrO 2the micro-nano mixture powder of combination that one of them or two kinds are above, 1~5% binding agent is prepared into combination powder; Wherein the nano-particle content in micro-nano granules is 20~30%; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.4~0.8%C, 2~3%Si, 1~3%B, 12~18%Cr, 6~8%Cu, 0.5~1%Sn, 10~15%Fe, 0.1~1.2%MgO, 0.2~2%CaF 2, CeO 2, Y 3o 2, La 2o 3above combination≤0.9% of one of them or two kinds, Ni surplus and inevitably impurity elements; Its step of preparation process is:
Micro-nano oxide particle → interpolation binding agent → stirring ball-milling → combination the powder of matrix alloy powder preparation → add → dry → broken → screening; Concrete technology step is as follows:
(1) matrix alloy preparation
The technical process of matrix alloy powder preparation is: batching → melting → atomization → dry → screening;
Batching: raw material is pure nickel, Graphite Powder 99, FeCr, FeB, FeSi, Cu, Sn, re-si-mg alloy, Rare-Earth Ce;
Melting: the above-mentioned raw material preparing is carried out to melting in vacuum induction furnace or medium-frequency induction furnace, and temperature of fusion is about 1250 ℃-1350 ℃, controls carbon content and reaches requirement, after stokehold adjusting component is qualified, and 1200~1280 ℃ of tapping temperatures;
Atomization: adopt indifferent gas or hydraulic atomized, atomization aperture 5~10mm, atomizing pressure, 10~14MPa;
Dry: equipment used is coated infrared drier, and bake out temperature is 220 ℃~280 ℃;
Screening: sift out size range for+150 orders~-350 object powder is as finished powder by powder shifter;
(2) add micro-nano oxide particle
Choose size range for the commercially available micro-nano Al of+150 orders~-350 object 2o 3or micro-nano Cr 3c 2, micro-nano ZrO 2one of them or two kinds of above micro-nano mixture powder of combination are as strengthening hard particles; Wherein the nano-particle content in micro-nano granules is 20~30%;
(3) add binding agent
Adopt resol, epoxy resin or the water glass of heat curing-type to make binding agent, add pimelinketone or methanol solvate, make it be dissolved into resin solution;
(4) stirring ball-milling
By the matrix alloy powder preparing and micro-nano Al 2o 3or micro-nano Cr 3c 2, micro-nano ZrO 2after the combined hybrid body powder that one of them or two kinds are above and binding agent are configured according to required ratio, pour in agitating ball mill, in pimelinketone or methanol solvate, make it be dissolved into resin solution the resin dissolves of required dosage; After stirring, pour in the powder mix of required processing in ball mill, after being prepared according to 2:1~3:1 ratio of grinding media to material, the abrading-ball of sphere diameter 10~20mm joins in agitating ball mill, starting agitating ball mill, abundant stirring ball-milling through 5~60 hours, each component of powder mix and resin liquid are all evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into micro-nano combination powder;
(5) dry
The combination powder that ball milling is good is poured out from ball mill, then dry through 150 ℃~200 ℃;
(6) broken and screening
Dried combination powder is carried out to fragmentation, by powder shifter, sift out size range for+150 orders~-350 object powder is respectively as finished powder, obtain required composition, desired particle size grade and don't the combination powder of solute segregation can occur.
CN201310502656.9A 2013-10-22 2013-10-22 Micro-nano oxide particle enhanced nickel base alloy powder as well as preparation method thereof Pending CN103526077A (en)

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CN104674047A (en) * 2015-02-10 2015-06-03 北京交通大学 Bicontinuous-phase Ti3AlC2/Ni-base composite material and pressureless infiltration preparation method thereof
CN107723704A (en) * 2017-11-01 2018-02-23 上海业识科技有限公司 The laser surface cladding method of thermal power station's boiler water-wall tube
CN109332680A (en) * 2018-11-07 2019-02-15 南京航空航天大学 A kind of nano-oxide particles for high energy beam 3D printing/nickel base superalloy composite spherical powder and preparation method thereof
CN110923543A (en) * 2019-12-25 2020-03-27 苏州再超冶金制品有限公司 High-use-performance surface-densified powder alloy iron-based material
CN111926207A (en) * 2020-08-27 2020-11-13 北京科技大学 Method for preparing nickel-based alloy

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CN103008647A (en) * 2012-12-18 2013-04-03 江苏新亚特钢锻造有限公司 Laser cladding alloy powder enhanced with oxide particles and preparation method thereof
CN103014474A (en) * 2012-12-18 2013-04-03 江苏新亚特钢锻造有限公司 Oxide particle reinforced laser cladding nickel-base alloy powder and preparation method thereof
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CN110923543B (en) * 2019-12-25 2021-01-01 苏州再超冶金制品有限公司 High-use-performance surface-densified powder alloy iron-based material
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CN111926207B (en) * 2020-08-27 2021-12-14 北京科技大学 Method for preparing nickel-based alloy

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Application publication date: 20140122