Oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and preparation method thereof
Technical field
The invention belongs to the cobalt-base alloys technical field, relate to a kind of oxide particle and strengthen cladding alloy powder and preparation method thereof, particularly a kind of oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and preparation method thereof, and this high abrasion oxide particle strengthens Co-based alloy powder and is applicable to laser melting coating high abrasion operating mode parts.
Background technology
In the daily life and industrial production in modern times, the attrition and attack meeting of metal material appears at every field, one of two large major ways that destroy component of machine, engineering component, corrosion will cause a large amount of consumption of machine components, and wearing and tearing then are to cause one of major reason of machine components inefficacy.They have also wasted ample resources in a large amount of metal materials of loss, occupy very large proportion in economic loss.
The inefficacy of the engineering component that high temperature, burn into friction and wear cause occurs in the surface mostly, and this phenomenon impels the material science worker to the very big concern of material surface, and impels the fast development of material surface modifying technology.People wish to make material surface obtain higher, specific serviceability when material monolithic keeps enough toughness and intensity, as wear-resisting, anti-corrosion and anti-oxidant etc.
It is reported that at present, in whole world industrialized country, the energy that consumes in wearing and tearing accounts for 1/2nd of gross energy, 60%~80% component of machine is arranged approximately owing to wear and tear and lost efficacy.A highly developed industrialized country, the annual economic loss that causes because of wearing and tearing almost accounts for 1%~2% of total value of production in national economy.For example, the U.S. every year on average since the economic loss that causes of wearing and tearing up to 20,000,000,000 dollars; The economic loss that Britain is caused by wearing and tearing every year on average is above 51,500 ten thousand pounds.In China, the economic loss that is 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 every year in China in wearing and tearing, and economic loss reaches 200~30,000,000,000 yuan more than.Thus, the effect of attrition of metal material performance quality and the service life of machine components, and then affects the competitiveness of these machine components on market.
Simultaneously, the metal erosion problem also spreads all over the national economy every field, from the industrial and agricultural production that is applied to of most advanced branches of science technology, and the manufacturing that is applied to national defense industry from daily life, the place of every use metal material all exists etching problem in varying degrees.According to relevant expert's statistics, the whole world each minute half just has one ton of steel to be etched into iron rust.For example, 1975, the economic loss that U.S. every year is caused by corrosion accounted for 4.9% of total value of production in national economy up to 82,000,000,000 dollars; Nineteen ninety-five, the U.S. is because the economic loss straight line that corrosion causes rises to 3,000 hundred million dollars.Statistics shows, in a country that industry is flourishing, the economic loss that causes because of corrosion accounts for 2%~4% of total value of production in national economy, surpasses the summation of the loss that all natural calamities such as floods, fire, earthquake and ancient measure of length, equal to 8 cun wind cause.Although China only is a developing country, because the loss that corrosion brings is also considerable, annual about 5,000 hundred million yuans, account for about 6% of Chinese national economy total output value.The economic loss that is only caused by corrosion in oil and gas field every year is with regard to about 10,000,000,000 yuan, and coal industry is about 55.6 hundred million yuan by the fund waste that corrosion causes every year, then nearly 1,700,000,000 yuan of the corrosion loss in power system every year.
Therefore, from limited natural resources and energy resources, modern demand of industrial production component of machine has enough wear and corrosion behaviors, can extremely work long hours under the rugged environment at high temperature, high load capacity etc., and the attrition and attack problem that therefore solves metal is extremely urgent.
Wear-resisting, anti-corrosion, the high temperature resistant and anti-oxidation characteristics of the obdurability that the laser melting coating ceramic technology can be high with metal, good manufacturability and ceramic material excellence combines, being the surface strengthening technology of most worthy and competitiveness, also is one of focus of laser melting and coating technique development.
Laser melting coating is the technology of emerging a, fast development, it is under the high-energy-density laser beam irradiation, the matrix surface skim melts simultaneously with the alloy that adds as required, forming thickness is 10~1000 μ m surface melting layers, the process that rapid solidification requires to satisfy a certain property, be a new technology of the multidisciplinary intersection such as material reciprocation and rapid solidification moulding in set laser heat fused, the molten bath, this technology obtains more careful research aspect surface treatment.
Because local surfaces is subjected to heat density large, spot diameter is little, and heated time is short, so the fusion zone is very little on the surface of the work, it is few to pass to the inside workpiece heat, has very large thermograde in the fusion zone, and cooling velocity can reach 10
4~10
9℃/s.Just because of rapid solidification, give the characteristics 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 (dilution rate 5~8%), and only at the very limited phase diffusion zone of reflow zone and the intersection existence of matrix, and this diffusion region realizes that just the metallurgical binding of coat and matrix is necessary.It can be coated in high performance alloy powder on the common material (workpiece), thereby obtains the face coat (such as good coatings such as heat-resisting, anti-corrosion, wear-resisting, shock resistances) of excellent specific property.
Compare with traditional surface modification (thermal spraying, plasma spraying etc.) technology, it mainly contains following advantage: the interface is metallurgical binding; Organize superfine; Cladding layer homogeneous chemical composition and dilution factor are low; Coating thickness is controlled; The heat distortion is little; Realize that easily constituency cladding and technical process easily realize automation.In process for modifying surface, laser melting coating has become relatively more active research field.
The 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 commercial Application from laboratory research, will have powerful vitality in following material surface modifying field.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, so available matrix material is very extensive, such as carbon steel, steel alloy, cast iron and aluminium alloy, copper alloy, nickel base superalloy etc.In addition, the material scientific research personnel has also developed amorphous 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-alloy steel, high-temperature alloy surface modification also has report, yet the application laser melting coating is repaired the practical engineering application of some components of machine and is but awaited further popularization, main cause is that the problems such as crackle, coating be inhomogeneous are often arranged in the laser cladding process, 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 with sheet metal, sintered metal product, steel band and welding rod etc. as cladding material, wherein alloy powder is most widely used in laser melting and coating technique.
Practical service environment condition depending on workpiece is different, and is also different to the performance requirement of surface coating.The 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 the requirement part is wear-resisting, the member of heat and corrosion resistant and thermal fatigue resistance, and required laser power density is higher than the summary of cladding ferrous alloy; The 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 non-oxidizability.
Wear-resistant coating is to study to such an extent that also be maximum a kind the earliest in the laser melting coating ceramic coating.Although Ni is basic, Co is basic, the basic self-fluxing alloy of Fe itself just has good wear-resisting, anti-corrosion, heat resistance, utilize their laser cladding layer carry out material surface strengthening the research report oneself through a lot.But under the serious condition of slip, impact wear and abrasive wear, simple Ni base, basic, the not competent instructions for use of the basic self-melting alloy of Fe of Co.
Composite is a kind of novel surface peening engineering material, and metal and metal, metal and pottery, pottery be with ceramic etc., between the alloy powder and the range of choice of the collocation between alloy powder and the pottery very extensive.Recent domestic has been carried out various dystectic carbide, nitride, boride and the ceramic oxide particle that adds certain content in the alloy powder system of above-mentioned laser melting coating for this reason, make cermet composite coating even pure ceramic coating, to improve the wearability of cladding layer.
Can prepare high performance composite coating although adopt composite to carry out laser melting coating, but at present domesticly mostly still be in the research in laboratory, and its preparation technology adopts the WC powder of nickel-based self-fluxing alloy with certain content mixed in the laboratory, then add saturated turpentine oil or homemade organic binder bond, furnishing slip or paste, precoating is overlying on the workpiece, then carries out laser melting coating or sintering.Its hard particles that adds is large, density is different from parent metal, and the distribution of particle in cladding layer is often inhomogeneous, usually presents gradient and distributes; The wetability of added granular materials and matrix, stability, the coefficient of expansion and chemical reactivity etc. all cause the inhomogeneities of the microstructure and property of cladding layer.And prepared combination powder since each constituent element proportion differ greatly, thereby in storage, transportation and use procedure and easily produce segregation.Can't carry out the commercialization supply, there is not yet at present particle in market 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 objective of the invention is to avoid above-mentioned deficiency of the prior art, develop and a kind ofly can satisfy that required a kind of oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and preparation method thereof under the serious abrasive wear working condition of engineering machinery.
For achieving the above object, the present invention can realize with corresponding technology of preparing scheme by design and the interpolation hard compounds of following basic chemical composition:
A kind of oxide particle provided by the present invention strengthens laser melting coating high abrasion Co-based alloy powder and is comprised of matrix alloy powder and oxide enhancing particle and binding agent, and its proportioning is: 50~98% matrix alloy powder, 1~45% Al
2O
3Or Cr
3C
2, ZrO
2One of them or the combined hybrid body powder more than two kinds, 1~5% binding agent is prepared into the combination powder; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.1~0.4%C, 3.5~5.5%Si, 1.5~3%B, 1.6~2.5%Mn, 1.0~3.0%Cr, 0.5~2%W, 2.0~3.0%Mo, 0.5~3%Ni, 0.1~0.4%Nb,<15%Fe, 0.1~1.2%MgO, 0.2~2%CaF
2, CeO
2, Y
3O
2, La
2O
3One of them or the combination more than two kinds≤0.9%, Co surplus and inevitable impurity element.
Oxide particle provided by the present invention strengthens laser melting coating high abrasion Co-based alloy powder and preparation method thereof, and its step of preparation process is:
Matrix alloy powder preparation → interpolation oxide particle → interpolation binding agent → stirring ball-milling → combination powder → drying → fragmentation → screening; The concrete technology step is as follows:
(1) matrix alloy preparation
The technological process of matrix alloy powder preparation is: batching → melting → atomizing → drying → screening;
Batching: raw material is pure cobalt, graphite powder, FeCr, FeB, FeSi, W, Nb, Ni, La
2O, Y;
Melting: the above-mentioned raw material for preparing is carried out melting in vaccum sensitive stove or intermediate frequency furnace, fusion temperature is about 1250 ℃-1350 ℃, and the control carbon content reaches requirement, after the stokehold adjusting component is qualified, and 1200~1280 ℃ of tapping temperatures;
Atomizing: adopt indifferent gas or hydraulic atomized, atomizing aperture 5~10mm, atomizing pressure, 10~14MPa;
Dry: device therefor is coated infrared drier, and bake out temperature is 220 ℃~280 ℃;
Screening: sifting out particle size range by sieving machine is that+150 orders~-350 purpose powder are as finished powder;
(2) add oxide particle
Choose particle size range and be+150 orders~commercially available Al of-350 purposes
2O
3Or Cr
3C
2, ZrO
2One of them or the combined hybrid body powder more than two kinds are as strengthening hard particles;
(3) add binding agent
Adopt phenolic resins, epoxy resin or the waterglass of heat curing-type to make binding agent, add cyclohexanone or methanol solvate, make it be dissolved into resin solution;
(4) stirring ball-milling
With matrix alloy powder and the Al for preparing
2O
3Or Cr
3C
2, ZrO
2After one of them or the combined hybrid body powder more than two kinds and binding agent are configured according to required ratio, pour in the agitating ball mill, make it be dissolved into resin solution in cyclohexanone or methanol solvate the resin dissolves of required dosage; Pour into after stirring in the mixed powder of required processing in the ball mill, join in the agitating ball mill after the abrading-ball of sphere diameter 10~20mm prepared according to 2: 1~3: 1 ratios of grinding media to material, the starting agitating ball mill, abundant stirring ball-milling through 5~60 hours, each component of mixed powder and resin liquid all are evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into the combination powder;
(5) drying
The combination powder that ball milling is good is poured out from ball mill, then through 150 ℃~200 ℃ dryings;
(6) broken and screening
The combination powder that drying is good carries out fragmentation, by sieving machine sift out particle size range for+150 orders~-350 purpose powder respectively as finished powder, namely get required composition, desired particle size grade and don't the combination powder of solute segregation can occur.
Beneficial effect
Compared with prior art, the present invention has following advantage:
1) oxide particle of the present invention strengthens the existing higher toughness of laser melting coating high abrasion Co-based alloy powder, high hardness, have again excellent wearability and corrosion resistance, its abrasive wear resistance can be 10 times of rich chromium cast iron, and its corrosion resistance and 1Cr18Ni9Ti are suitable.Be applicable to laser melting coating HI high impact, high abrasion operating mode parts.
2) oxide particle of the present invention strengthens the laser melting and coating process performance that laser melting coating high abrasion Co-based alloy powder has excellence, and the laser cladding layer after processing has the advantages such as flawless, pore-free, free from admixture, dense structure, grain refinement.
3) the oxide particle enhancing laser melting coating high abrasion Co-based alloy powder through technique preparation of the present invention can wrap up each constituent element powder particle, and is bonded together; Have enough adhesion strengths, can prevent effectively that composition powder from producing segregation owing to each constituent element proportion differs greatly in storage, transportation and use procedure.
4) oxide particle of the present invention strengthens laser melting coating high abrasion 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 that need not preheating and subsequent heat treatment, can obtain the flawless Laser Clad Alloy Coatings of the large thickness of large tracts of land, cladding layer intensity, hardness and wearability are high, plasticity and toughness are good, and than existing most of used for hot spraying self-fluxing alloy powders and existing most of laser melting coatings alloy powder cost decrease.Can reduce the consumption of strategic rare element, significantly reduce the laser melting coating cost.
The specific embodiment
The invention will be further described below in conjunction with the specific embodiment.
Embodiment one
A kind of laser melting coating high abrasion oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and preparation method thereof, this oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and is comprised of matrix alloy powder and oxide hard particle and binding agent, its proportioning is: 60% matrix alloy powder, 37% Al
2O
3, 3% phenolic resin adhesive is prepared into the combination powder; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.3%C, 4%Si, 2.5%B, 2.6%Cr, 1.5%W, 2.2%Mn, 0.3%Nb, 2.5%Ni, 13%Fe, 0.1%MgO, 0.5%CaF
2, 0.2%CeO
2, 0.2%Y
3O
2, 0.2%La
2O
3, the Co surplus.
Its manufacturing technology steps:
Matrix alloy powder preparation → interpolation oxide particle → interpolation binding agent → stirring ball-milling → combination powder → drying → fragmentation → screening; The concrete technology step is as follows:
(1) matrix alloy preparation
The technological process of matrix alloy powder preparation is: batching → melting → atomizing → drying → screening;
Batching: raw material is pure nickel, graphite powder, FeCr, FeB, FeSi, Cu, Sn, Rare Earth Y, Rare-Earth Ce; By above-mentioned percentage by weight proportioning, be ready to make the raw material of parent metal powder.
Melting: start the vacuum induction intermediate frequency furnace, by the requirement of smelting technology, put into metal and begin melting, the metal of general easy oxidation was put in the later stage of fusing.Fusion temperature is controlled at 1250-1300 ℃ approximately; After the metal of this stove all melts in stove, carry out slag making, remove the impurity in the molten metal, then enter refining period and carry out refining, add deoxidier before the cast and carry out deoxidation, the control carbon content reaches requirement, after the stokehold adjusting component was qualified, tapping temperature was controlled at 1200~1250 ℃.
Atomizing: the alloy liquid that melting is qualified is poured in the cone bottom pour ladle, begin to carry out the atomizing of metal dust, opening high pressure inert gas bottle, will be from the gases at high pressure of gas cylinder as air knife, be to become the molten metal bath stream of a thread to cut atomizing after the constraint of leting slip a remark of 5~10mm by the aperture to fusing, atomizing pressure 10~14MPa, the molten drop that the metal atomization poling is small, final set becomes alloy powder.Metal dust 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 content of powder.Normal nebulisation time is about 5~20 minutes.
Dry: device therefor is coated infrared drier, about 250 ℃ of bake out temperature, and dried metal dust, the chemical examination of chemical analysis is carried out in first sampling, changes next procedure over to after qualified.
Screening: sifting out particle size range by sieving machine is that+150 orders~-350 purpose powder are as finished powder.
(2) add oxide particle
Choose particle size range and be the commercially available Al of-250 purposes
2O
3Powder is as strengthening particle;
(3) add binding agent
Adopt the phenolic resins of heat curing-type to make binding agent, add cyclohexanone solvent, make it be dissolved into resin solution;
(4) stirring ball-milling
With matrix alloy powder and the Al for preparing
2O
3After powder and binding agent are configured according to above-mentioned ratio, pour in the agitating ball mill, the phenolic resins of 3% heat curing-type is dissolved in makes it be dissolved into resin solution in the cyclohexanone solvent, pour into after stirring in the mixed powder of the required processing in the ball mill, join in the agitating ball mill after the abrading-ball of sphere diameter 15mm prepared according to 2: 1 ratios of grinding media to material, abundant stirring ball-milling through 35 hours, each component of mixed powder and resin liquid all are evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into the combination powder;
(5) drying
The combination powder that ball milling is good is poured out from ball mill, then through 180 ℃ of dryings;
(6) broken and screening
The combination powder that drying is good carries out fragmentation, by sieving machine sift out particle size range for+150 orders~-350 purpose powder as finished powder, namely get required composition, desired particle size grade and don't the combination powder of solute segregation can occur.
Requirement by the user is sieved, the packing warehouse-in.
Embodiment two
A kind of laser melting coating high abrasion oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and preparation method thereof, this oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and is comprised of matrix alloy powder and oxide particle and binding agent, its proportioning is: 68% matrix alloy powder, 30% ZrO
2, 2% epoxy adhesive is prepared into the combination powder; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.2%C, 5%Si, 3%B, 1.5%Cr, 2.0%W, 2.5%Mn, 0.2%Nb, 3%Ni, 12%Fe, 0.15%MgO, 0.9%CaF
2, 0.25%CeO
2, 0.25%Y
3O
2, 0.25%La
2O
3, the Co surplus.
(2) add carbide particle
Choose particle size range and be the commercially available ZrQ of-300 purposes
2Powder is as strengthening hard particles;
(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
With matrix alloy powder and the ZrO for preparing
2After powder and binding agent are configured according to above-mentioned ratio, pour in the agitating ball mill, the phenolic resins of 2% heat curing-type is dissolved in makes it be dissolved into resin solution in the methanol solvate, pour into after stirring in the mixed powder of the required processing in the ball mill, join in the agitating ball mill after the abrading-ball of sphere diameter 12mm prepared according to 2.5: 1 ratios of grinding media to material, abundant stirring ball-milling through 5~60 hours, abundant stirring ball-milling through 26 hours, each component of mixed powder and resin liquid all are evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into the combination powder;
Its preparation method is identical with embodiment one.
Embodiment three
A kind of laser melting coating high abrasion oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and preparation method thereof, this laser melting coating high abrasion oxide particle strengthens laser melting coating high abrasion Co-based alloy powder and is comprised of matrix alloy powder and oxide hard particle and binding agent, its proportioning is: 68% matrix alloy powder, 30% Al
2O
3And ZrO
2Form the mixture powder do, 2% epoxy adhesive is prepared into the combination powder; Wherein the chemical composition of matrix alloy and mass percent thereof are;
0.4%C, 2.8%Si, 2.0%B, 3%Cr, 2.5%W, 1.8%Mn, 0.25%Nb, 2.0%Ni, 10%Fe, 0.2%MgO, 1.5%CaF
2, 0.3%CeO
2, 0.3%Y
3O
2, 0.3%La
2O
3, the Co surplus.
(2) add oxide particle
Choose particle size range and be the commercially available 50%Al of-200 purposes
2O
3And 50%ZrO
2Form the mixture powder as strengthening hard particles;
(3) add binding agent
Adopt waterglass to make binding agent, add methanol solvate;
(4) stirring ball-milling
With matrix alloy powder and the Al for preparing
2O
3And ZrO
2After the mixture powder that forms and binding agent are configured according to above-mentioned ratio, pour in the agitating ball mill, 2.5% waterglass is incorporated in the methanol solvate, pour into after stirring in the mixed powder of the required processing in the ball mill, join in the agitating ball mill after the abrading-ball of sphere diameter 18mm prepared according to 2.8: 1 ratios of grinding media to material, the starting agitating ball mill, abundant stirring ball-milling through 18 hours, each component of mixed powder and waterglass liquid all are evenly distributed, each constituent element powder particle is wrapped up, and be bonded together, be prepared into the combination powder;
Its preparation method is identical with embodiment one.
The laser melting coating high abrasion oxide particle of the above composition that the present invention proposes strengthens laser melting coating high abrasion Co-based alloy powder, be specially adapted to the laser melting coating on corresponding product surface, the hardness of its cladding layer is high, wearability is good, the tendency that produces cracking and other overlay defective is little, can prepare large thickness cladding layer, and laser melting and coating process is functional, use the cost of cladding alloy powder low than now, can be suitable for to use widely needs.Material of the present invention is applied has significant economic and social benefit.