CN101444981A - In-situ preparation of cobalt-base alloy gradient coating on aldary surface through laser induction, and method thereof - Google Patents
In-situ preparation of cobalt-base alloy gradient coating on aldary surface through laser induction, and method thereof Download PDFInfo
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- CN101444981A CN101444981A CNA2008102469244A CN200810246924A CN101444981A CN 101444981 A CN101444981 A CN 101444981A CN A2008102469244 A CNA2008102469244 A CN A2008102469244A CN 200810246924 A CN200810246924 A CN 200810246924A CN 101444981 A CN101444981 A CN 101444981A
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Abstract
The invention relates to in-situ preparation of a cobalt-base alloy gradient coating on an aldary surface through laser induction and a method thereof, and belongs to the material technical field. The gradient coating comprises a first coating, a second coating and a third coating, and the thickness of each coating is 0.04 to 0.10mm, 0.03 to 0.08mm and 0.07 to 0.13mm respectively. The preparation method comprises the steps as follows: the aldary surface is processed through activating treatment, Al, Co, C, Ni, Cr, Fe, Si, CrO3, Y2O3, Mo, W, MgO, B2O3 and graphite nodule milling are mixed and are prepared into a mixed materiel for the three coatings respectively; and the mixed materiel for the three coatings is spread on the aldary surface; and the ceramic particle reinforced cobalt-base alloy gradient coating is prepared through laser induction in-situ. The invention adopts the advanced technology for preparing an advanced heatproof wear-resistant gradient coating on the aldary surface, and has good application prospect and important economic significance.
Description
Technical field
The invention belongs to the material technology field, particularly a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating and method thereof.
Background technology
Copper and copper alloy have good thermal conductivity and corrosion resistance, are widely used in conducting-heat elements, as continuous cast mold, cast metal model etc., are one of main consumptive materials of metallurgy industry.But because intensity, the wearability of copper and copper alloy are relatively poor, particularly under 1500～1600 ℃ of high temperature friction environment, use, limited its application on engineering, so, copper alloy surface need prepare high-temperature wear resistant coating could improve its service life, reduces the production cost of enterprise.At present, the technology for preparing high-temperature wear resistant coating at copper alloy surface mainly contains methods such as plating, thermal spraying and multicomponewnt cementation, and its coating layer thickness is at 0.06～0.15mm.Because copper alloy matrix and Ni base and the physical property difference between the Co based high-temperature alloy coating material used always are big, the copper alloy high-temperature wear resistant coating of these process for treating surface commonly used preparations also exists and does not form between coating and the copper matrix that metallurgical interface combines, coming off appears in coating easily and problem such as coating abrasion performance is relatively poor.Press for research has metallurgical interface combination, pore-free crackle and particular tissues structure in the copper alloy surface preparation new technology with Strengthening and Toughening coating, so that improve the service life of coating, solve the problem that smelter copper alloy conducting-heat elements exists aborning.
Laser is one of advanced technology of preparation material surface high-performance coating.The outstanding feature of laser technology is to prepare the specific function coating that forms metallurgical binding with matrix, the thickness of coating can be controlled at 0.15～0.6mm scope as required, thereby significantly improves the performance such as wear-resisting, anti-corrosion, heat-resisting, anti-oxidant of substrate material surface.Factors such as the design of the wear resistance at elevated temperature of Metal Substrate face coat and the Strengthening and Toughening of coating structure, coating composition, institutional framework, interfacial structure and laser preparation technology are closely related.The raising of coating high-temp anti-wear performance can realize by the technology of the generation of original position in high temperature alloy coating ceramic particle reinforced metal base; In order to slow down the physics between matrix and the coating and the sudden change of mechanical property, improve the obdurability of coating, the preparation functionally gradient coating is an efficient ways.And walk the avenue to success that the compound technology of preparing route of induced with laser reaction in-situ is a preparation Metal Substrate surface high-performance abrasion-proof coating, the research of this respect at present is also seldom.
Summary of the invention
At above technical problem, the invention provides a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating and method thereof.
Copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating of the present invention is made up of first coating, second coating and the 3rd coating, and three coatings are combined as a gradient coating.The coating that wherein connects the copper alloy matrix surface is first coating, and its composition is Ni20～35% by weight percentage, C1～2%, Cr15～18%, Fe5～15%, Si2～3%, nanometer Al0.2～0.3%, CrO
30～0.16%, Y
2O
30.5～1.5%, Mo0～0.5%, W0～3%, MgO0～0.2%, surplus is Co; The thickness of first coating is 0.04～0.10mm.
Second coating connects first coating, and its composition is Ni12～16% by weight percentage, C2～3%, Cr20～25%, Fe5～15%, Si4～6%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～2%, surplus is Co; The thickness of second coating is 0.03～0.08mm.
The 3rd coating connects second coating, and its composition is Ni5～8% by weight percentage, C3～5%, Cr25～26%, Fe5～15%, Si7～8%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～3%, surplus is Co; The thickness of the 3rd coating is 0.07～0.13mm.
The gross thickness of gradient coating is 0.16～0.25mm.
The method of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating of the present invention may further comprise the steps:
1, copper alloy surface preliminary treatment: utilize sand-blast to remove the rusty scale of copper alloy surface, adopt the inorganic acid mixed solution to remove the greasy dirt and the corrosion of copper alloy surface; Copper alloy surface is carried out sandblast (perhaps 400# sand papering) roughening treatment, make copper alloy surface easily and coating form firm bonding; Copper alloy after the alligatoring is utilized organic solvent or organic solvent solution clean surface, till the cleaning surfaces no-sundries; At room temperature put into the H of 70～80g/l
2SO
4Soak 20～60s in the solution, carry out surface activation process; Clean with organic solvent or organic solvent solution, remove the sulfuric acid and the water of copper alloy surface, then copper alloy is dried up or natural air drying with hair-dryer.
Wherein the inorganic acid mixed solution is H
2SO
4With the mixed solution of HCl, H in the mixed solution
2SO
4Concentration is 200～300g/l, and HCl concentration is 100～120g/l.
The preliminary treatment of copper alloy surface can make that coating material and matrix are better to be combined, be unlikely to produce the induced with laser in-situ preparing coating peeling, crackle, defective such as peel off, be convenient to the carrying out for preparing.
2, coating material mixes: in order to make nanometer Al powder good dispersiveness can be arranged in alloy powder, earlier nanometer Al powder and Co powder are mixed, put into ball mill and add absolute ethyl alcohol, at rotating speed wet mixing 5～8h under the condition of 300～500r/min, abrasive material is made up of abrading-ball and spring wire, wherein the volume ratio of mixed metal powder and abrasive material is a mixed metal powder: abrasive material=5～8: 1, nanometer Al powder and Co powder are fully mixed be prepared into the master alloyed powder that contains nanometer Al, dry remove ethanol after, it is standby less than 250 purpose parts to filter out fineness.Wherein the mixed proportion of nanometer Al powder and Co powder is mixed by aforementioned ratio.
Wherein the consumption of absolute ethyl alcohol is as the criterion with submergence material and abrasive material during wet mixing.
By aforementioned ratio master alloyed powder and other powder being placed ball mill, is to do under the condition of 300～500r/min to mix 10～12h at rotating speed, makes it to mix, and filters out fineness and partly is prepared into mixed material less than 250 purposes.
Prepare the mixed material of first coating, second coating and the 3rd coating as stated above respectively, mixed material percentage by weight composition is Ni20～35% by the first coating mix material, C1～2%, Cr15～18%, Fe5～15%, Si2～3%, nanometer Al0.2～0.3%, CrO
30～0.16%, Y
2O
30.5～1.5%, Mo0～0.5%, W0～3%, MgO0～0.2%, surplus is Co; The second coating mix material is Ni12～16%, C2～3%, Cr20～25%, Fe5～15%, Si4～6%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～2%, surplus is Co; The 3rd coating mix material is Ni5～8%, C3～5%, Cr25～26%, Fe5～15%, Si7～8%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～3%, surplus is Co.
3, preparation first precoated shet: the first coating mix material and adhesive are mixed into paste or pasty state, and mixed proportion accounts for 30～50% of the first coating mix material by adhesive; After stirring, evenly be coated in and be prepared into first precoated shet on the pretreated copper alloy surface, and it is smooth that physics is carried out on the first precoated shet surface; In drying basin, place 13h～15h then, treat the dry hardening of first precoated shet after, controlling the first precoated shet thickness through surface rubbing is 0.2～0.5mm.
4, preparation first coating: the copper alloy that will have first precoated shet is put on the sample platform of laser instrument, carries out the former bit scan preparation of induced with laser, and laser technical parameters is: laser energy density 20～25J/mm
2, overlapping rate 20～35%.Form first coating of the large tracts of land overlap joint of surperficial no significant defect after laser scanning is finished, thickness is 0.04～0.10mm.
5, prepare gradient coating: with the second coating mix material set by step 3 method on first coating, be prepared into second precoated shet, controlling the second precoated shet thickness is 0.2～0.3mm, be put on the sample platform of laser instrument, adopt the method for step 4 to be prepared into second coating, thickness is 0.03～0.08mm.
With the 3rd coating mix material set by step 3 method on second coating, be prepared into the 3rd precoated shet, the thickness of controlling the 3rd precoated shet is 0.2～0.3mm, be put on the sample platform of laser instrument, adopt the method for step 4 to be prepared into the 3rd coating, thickness is 0.07～0.13mm.Three coating composition gradient coatings, thickness is 0.16～0.25mm.
Outer surface at gradient coating polishes processing, forms smooth surface.
Gradient coating of the present invention and preparation method thereof is applicable to metallic copper and acid bronze alloy.
Nanometer Al particle diameter is 20～100nm among the present invention, Co, C, Ni, Cr, Fe, Si, CrO
3, Y
2O
3, Mo, W, MgO, B
2O
3Be particle diameter less than 200 purpose powder with graphite.
Adhesive among the present invention comprises varnish, silicate cement, waterglass, cellulose acetate, acetone borax soln, transparent adhesive tape, paste or 504 glue etc.Wherein 504 glue sedimentary deposit thermal conductivity are best, can save laser energy during use.
Principle of the present invention is to utilize the Fast Heating and the cooling effect of laser, science design and optimization laser in-situ prepared in reaction technological parameter by coating composition, choose the heat resistanceheat resistant Co base alloy powder that contains nano-component of the optimal design close with performance with the copper base material component, by in the Co base alloy powder, adding an amount of nano particle, form micron order and nanoscale and mix new alloy powder system; The density and the thickness of control precoated shet, utilize the characteristic of nano particle low melting point, good fluidity, inflammable heat release, under the induced with laser effect, realize laser large tracts of land overlap joint, original position generates the institutional framework of ultra-fine brilliant disperse distribution ceramic particle phase composite toughening in coating.For eliminating problems such as the easy pore that exists of thick-layer, formation of crack, boundary defect, the gradient coating of design mix and structural change forms the continuous Strengthening and Toughening institutional framework from matrix to the high-temperature wear resistant coating surface.The induced with laser reaction in-situ prepares coating and meets second and strengthen mutually and refined crystalline strengthening mechanism, with the ceramic phase (W-C of reaction in-situ generation; Cr-C; Si-C) be core, the alloy liquid crystallization around driving, the alloy after the crystallization simultaneously wraps up ceramic phase, has controlled the ceramic phase polymerization, and makes its disperse be distributed in formation ceramic particle enhancing cobalt-based composite structure in the coating.Nanometer Al produces chemical heat with the O atomic reaction and provides internal energy for coating under the inducing action of laser, has remedied the laser energy loss that copper alloy heat conduction causes soon, has promoted the formation at the metallurgical interface of coating and the original position of ceramic particle to generate.Mo has stronger crystal grain thinning, increases toughness, improves the effect of plasticity, B
2O
3Improve the wetability of coating, reduced the surface tension of coating; Rare earth oxide Y
2O
3Adding, help eliminating the generation of crackle and gas hole defect in the coating; Graphite has the high temperature lubricating effect, can reduce the coefficient of friction of coating.These methods all help the formation of Strengthening and Toughening gradient coating, reach the purpose that improves copper alloy surface coating high-temp anti-wear performance and greasy property.
The design core of gradient layer of the present invention is: the main component in first coating will have good mutual soakage with matrix, also will have certain rigidity to play the effect of supporting second coating, the 3rd coating simultaneously; Second coating will keep with first coating higher soakage being arranged as far as possible, and for first coating and the 3rd coating provide bridge, hardness will increase simultaneously; The 3rd coating is whole gradient coating extexine, high rigidity, high-wearing feature and high chemical stability.The THICKNESS CONTROL of gradient coating is at 0.16～0.25mm, and thin layer helps the heat conduction of copper alloy matrix.First coated designs is to contain the multielement Co base coating alloy powder of quantitative nano Al powder, utilize the induced with laser in-situ preparation method, that prepares large tracts of land overlap joint at copper alloy surface has formed first coating of good interface metallurgical binding with copper alloy matrix, original position generates ultra-fine brilliant ceramic particle in the control coating, microhardness of coating is higher than 4 times of hardness of copper alloy (90HV), and coating flawless pore generates; On the basis of first coating preparation, laser preparation technology is optimized in Co base coating alloy powder utilization by the composition gradual change, and to prepare smooth surface on first coating smooth, pore-free and crackle, the interface is second coating of metallurgical binding, microhardness reaches the numerical value that is higher than first coating, and generated in-situ ceramic particle wild phase quantity increases in gradient in second coating; On the basis of second coating Co base coating, prepare the 3rd coating Co base coating of large tracts of land overlap joint by the composition gradual change, the interface forms metallurgical binding, ceramic particle quantity in the 3rd coating is more, coating surface is smooth, flawless and pore produce, and case hardness reaches more than 5 times of hardness of copper alloy (90HV).All interfaces of preparation gradient coating are metallurgical binding, the quantity of generated in-situ pottery enhancing particle, the hardness of coating and main intensified element Cr etc. increase progressively distribution in gradient, thereby form institutional framework with Strengthening and Toughening, reduce the coefficient of friction of coating, significantly improve the wear resistance at elevated temperature of copper alloy surface.
Copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating of the present invention and method thereof, the operating mode of using under the high temperature friction environment based on coating and the tissue and structure of coating are determining the thinking of its high temperature life, the gradient coating that design has ceramic particle reinforced metal base high-temperature wearable institutional framework.Become to be grouped on the basis with the laser preparation technology parameter optimizing coated powder, utilize the laser large-area preparation to have the gradient coating of the metallurgical interface combination of three layers of heterogeneity and structure; The main tissue of gradient coating is that (generated in-situ main ceramic phase is Cr-C and WC to α-CoCr2 for Ni, O) 4 alloy phases, and Fe-Ni, Cr-Ni-Fe-C exist wherein with the form of solid solution phase
1-XCarbide.The diameter of most ceramic particles that the induced with laser reaction in-situ generates in the gradient coating to 0.3 mu m range, has formed the second thin brilliant Co base complex tissue structure coating that strengthens mutually in tens nanometers.The amounts of particles that distributes in each layering of gradient coating presents the distribution that is increased gradually by first coating to the, three coatings, helps alleviating the humidification that the crackle tendency improves particle simultaneously.The average microhardness of gradient coating increases in gradient, and outermost hardness has been brought up to copper alloy matrix (90HV) 5～9.8 times; Coating layer thickness is 0.16～0.25mm, and the abrasion loss of gradient coating is 1/3～1/6 of a copper alloy matrix, has good anti-wear performance, simultaneously because the gradient coating thinner thickness is little to the heat conductivility influence of matrix copper alloy.Laser is a kind of clean energy resource, environmentally safe; Laser energy and sweep speed can accurately be controlled, can realize industrial automation preparation and raise the efficiency for copper alloy surface, the present invention is the advanced technology of copper and the advanced coating of having strong resistance to heat and hard wearing of copper alloy surface preparation thereof, has a good application prospect and important economic implications.
Description of drawings
Fig. 1 is a copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating schematic diagram of the present invention, and A is a copper alloy collective among the figure, and B is first coating, and C is second coating, and D is the 3rd coating, and E is the gradient coating outer surface.
Fig. 2 is the sem photograph of the gradient coating in the embodiment of the invention 1.
Fig. 3 is the X-ray diffraction analysis figure as a result of the gradient coating phase composition in the embodiment of the invention 1, and 1 is Cr among the figure
7C
3, 2 is C, 3 is WC
1-x, 4 is CoCr
2(Ni, O)
4, 5 is FeNi, and 6 is Cr-Ni-Fe-C, and 7 is MoNi.
Fig. 4 is the sem photograph of the gradient coating in the embodiment of the invention 2.
Fig. 5 is the gradient coating hardness scatter chart in the embodiment of the invention 2, and a is first coating among the figure, and b is second coating, and c is the 3rd coating.
Fig. 6 is the ceramic particle sem photograph that original position forms in the gradient coating in the embodiment of the invention 3.
Fig. 7 is for graphitiferous coating in the copper matrix in the embodiment of the invention 3, the gradient coating and do not have the wear extent curve map of equadag coating, and d is the copper matrix among the figure, and e is no equadag coating, and f is the graphitiferous coating.
The specific embodiment
The Co that adopts in the embodiment of the invention, C, Ni, Cr, Fe, Si, CrO
3, Y
2O
3, Mo, W, MgO, B
2O
3Be chemical reagent with graphite, granularity is less than 200 orders.
The nanometer aluminium powder purity that adopts in the embodiment of the invention is greater than 99.5%, particle diameter 20～100nm.
The copper alloy composition that adopts in the invention process is by weight being Cu: Cr: P=99.9: 0.07: 0.03.
The sulfuric acid solution that adopts in the embodiment of the invention is by acid of reagent bright sulfur and deionized water preparation; The inorganic acid mixed solution is by analytical pure sulfuric acid and analyze pure hydrochloric acid and the deionized water preparation.
The cleaning organic solvent solution that adopts in the embodiment of the invention is acetone soln or alcoholic solution.
The absolute ethyl alcohol that adopts in the embodiment of the invention is the pure absolute ethyl alcohol of reagent.
The laser instrument that adopts in the embodiment of the invention is the Nd:YAG laser instrument.
The hardness measurement method is in the embodiment of the invention: adopt the 40MVDTM micro Vickers to measure microhardness, distribute along the gradient coating thickness direction, load is 25g, and the load time is 10s, makes a call at 5 and averages.
The adhesive of selecting for use in the embodiment of the invention is 504 glue.
In the embodiment of the invention during ball milling wet mixing consumption of absolute ethyl alcohol be as the criterion with submergence material and abrasive material.
It below is the preferred embodiment of the present invention.
Utilize sand-blast to remove the rusty scale of copper alloy surface, adopt the inorganic acid mixed solution to remove the greasy dirt and the corrosion of copper alloy surface; Utilize sandblast that copper alloy surface is carried out roughening treatment, make copper alloy surface easily and coating form firm bonding; Copper alloy after the alligatoring is utilized the acetone soln clean surface, till the cleaning surfaces no-sundries; At room temperature put into the H of 70g/l
2SO
4Soak 20s in the solution, carry out surface activation process; Clean with acetone soln then, remove the sulfuric acid and the water of copper alloy surface, then copper alloy is dried up with hair-dryer.
Wherein the inorganic acid mixed solution is H
2SO
4With the mixed solution of HCl, H in the mixed solution
2SO
4Concentration is 200g/l, and HCl concentration is 120g/l.
Nanometer Al powder and Co powder are mixed, put into ball mill and add absolute ethyl alcohol, at rotating speed wet mixing 5h under the condition of 500r/min, wherein the volume ratio of mixed metal powder and abrasive material is a mixed metal powder: abrasive material=8: 1, nanometer Al powder and Co powder are fully mixed be prepared into the master alloyed powder that contains nanometer Al, behind the dry removal ethanol, filter out fineness less than 250 purpose parts.With master alloyed powder and Ni, C, Cr, Fe, Si and Y
2O
3Powder place ball mill, be to do under the condition of 500r/min to mix 10h at rotating speed, make it to mix, filter out fineness and partly be prepared into the first coating mix material less than 250 purposes.The composition of the first coating mix material is Ni35% by weight percentage, C1%, Cr15%, Fe5%, Si2%, nanometer Al0.2%, Y
2O
30.5%, surplus is Co.
The first coating mix material is mixed with 504 glue, and mixed proportion accounts for 40% of the first coating mix material by 504 glue; After stirring, evenly be coated in and be prepared into first precoated shet on the pretreated copper alloy surface, and it is smooth that physics is carried out on the first precoated shet surface; In drying basin, place 13h then, treat the dry hardening of first precoated shet after, controlling the first precoated shet thickness through surface rubbing is 0.3mm.
The copper alloy that will have first precoated shet is put on the sample platform of laser instrument, carries out the former bit scan preparation of induced with laser, and laser technical parameters is: laser energy density 22J/mm
2, overlapping rate 25～30%.Form first coating of the large tracts of land overlap joint of surperficial no significant defect after laser scanning is finished, thickness is 0.06mm.
Preparation method by the first coating mix material prepares the second coating mix material, and the composition of the second coating mix material is Ni12% by weight percentage, C2%, Cr25%, Fe5%, Si4%, nanometer Al0.3%, Y
2O
30.5%, surplus is Co.
The second coating mix material is prepared into second precoated shet by the preparation method of first precoated shet at first coating surface, and controlling the second precoated shet thickness is 0.2mm, is put on the sample platform of laser instrument laser energy density 23J/mm
2, other adopt the preparation method of first coating to be prepared into second coating, and thickness is 0.03mm.
Preparation method by the first coating mix material prepares the 3rd coating mix material, and the composition of the 3rd coating mix material is Ni5% by weight percentage, C3%, Cr26%, Fe5%, Si7%, nanometer Al0.3%, Y
2O
30.5%, surplus is Co.
The 3rd coating mix material is prepared into the 3rd precoated shet by the preparation method of first precoated shet at second coating surface, and the thickness of controlling the 3rd precoated shet is 0.2mm, is put on the sample platform of laser instrument laser energy density 24J/mm
2, other adopt the preparation method of first coating to be prepared into the 3rd coating, thickness is 0.07mm.Three coating composition gradient coatings, thickness is 0.16mm.
Outer surface at gradient coating polishes processing, forms smooth surface.
The sem photograph of having prepared three layers of gradient coating with heterogeneity and structure as shown in Figure 2, the interface does not have macroscopic cracking produce in conjunction with good between each coating in the coating.
The main tissue of gradient coating is α-CoCr
2(Ni, O)
4Alloy phase, and Fe-Ni, Cr-Ni-Fe-C exist wherein with the form of solid solution phase, generated in-situ main ceramic phase is Cr
2C
3And WC
1-XCarbide; Figure is as shown in Figure 3 as a result for the X-ray diffraction analysis of gradient coating phase composition.
Most diameters of the ceramic particle that the induced with laser reaction in-situ generates in the gradient coating are at 40nm～0.3 mu m range, formed the second thin brilliant Co base complex tissue structure coating that strengthens mutually, the amounts of particles that distributes in each layering of gradient coating presents the distribution that is increased gradually by first coating to the, three coatings, helps alleviating the humidification that the crackle tendency improves particle simultaneously.
It is 5 times of copper alloy matrix (90HV) that the outermost average microhardness of gradient coating has reached 450HV, show that with quenching bearing steel (case hardness HRC60) friction experiment in 30 minutes the abrasion loss of gradient coating is that 0.008g (loads 40N, 400r/min, 30min), the ceramic particle that proves the laser in-situ prepared in reaction strengthens the cobalt-based gradient coating and has good anti-wear performance.
Utilize sand-blast to remove the rusty scale of copper alloy surface, adopt the inorganic acid mixed solution to remove the greasy dirt and the corrosion of copper alloy surface; Utilize sandblast that copper alloy surface is carried out roughening treatment, make copper alloy surface easily and coating form firm bonding; Copper alloy after the alligatoring is utilized the acetone soln clean surface, till the cleaning surfaces no-sundries; At room temperature put into the H of 75g/l
2SO
4Soak 40s in the solution, carry out surface activation process; Clean with acetone soln then, remove the sulfuric acid and the water of copper alloy surface, then copper alloy is dried up with hair-dryer.
Wherein the inorganic acid mixed solution is H
2SO
4With the mixed solution of HCl, H in the mixed solution
2SO
4Concentration is 250g/l, and HCl concentration is 110g/l.
Nanometer Al powder and Co powder are mixed, put into ball mill and add absolute ethyl alcohol, at rotating speed wet mixing 6h under the condition of 400r/min, wherein the volume ratio of mixed metal powder and abrasive material is a mixed metal powder: abrasive material=6: 1, nanometer Al powder and Co powder are fully mixed be prepared into the master alloyed powder that contains nanometer Al, behind the dry removal ethanol, filter out fineness less than 250 purpose parts.With master alloyed powder and Ni, C, Cr, Fe, Si, CrO
3, Y
2O
3, Mo, W and MgO powder place ball mill, be to do under the condition of 400r/min to mix 11h at rotating speed, make it to mix, filter out fineness and partly be prepared into the first coating mix material less than 250 purposes.The composition of the first coating mix material is Ni20% by weight percentage, C2%, Cr18%, Fe15%, Si3%, nanometer Al0.3%, CrO
30.16%, Y
2O
31.5%, Mo0.5%, W3%, MgO0.2%, surplus is Co.
The first coating mix material is mixed with 504 glue, and mixed proportion accounts for 30% of the first coating mix material by 504 glue; After stirring, evenly be coated in and be prepared into first precoated shet on the pretreated copper alloy surface, and it is smooth that physics is carried out on the first precoated shet surface; After placement 14h treated the dry hardening of first precoated shet in drying basin then, controlling the first precoated shet thickness through surface rubbing was 0.5mm.
The copper alloy that will have first precoated shet is put on the sample platform of laser instrument, carries out laser scanning, and laser technical parameters is: laser energy density 24J/mm
2, overlapping rate 25～30%.Form first coating of the large tracts of land overlap joint of surperficial no significant defect after laser scanning is finished, thickness is 0.10mm.
Preparation method by the first coating mix material prepares the second coating mix material, and the composition of the second coating mix material is Ni16% by weight percentage, C3%, Cr20%, Fe15%, Si6%, nanometer Al0.5%, CrO
30.3%, Y
2O
31.5%, Mo1.2%, W8%, MgO0.2%, B
2O
32.5%, graphite 2%, surplus is Co.
The second coating mix material is prepared into second precoated shet by the preparation method of first precoated shet at first coating surface, controlling the second precoated shet thickness is 0.25mm, be put on the sample platform of laser instrument, adopt the preparation method of first coating to be prepared into second coating, thickness is 0.04mm.
Preparation method by the first coating mix material prepares the 3rd coating mix material, and the composition of the 3rd coating mix material is Ni8% by weight percentage, C5%, Cr25%, Fe15%, Si8%, nanometer Al0.5%, CrO
30.3%, Y
2O
31.5%, Mo1.2%, W8%, MgO0.2%, B
2O
32.5%, graphite 3%, surplus is Co.
The 3rd coating mix material is prepared into the 3rd precoated shet by the preparation method of first precoated shet at second coating surface, the thickness of controlling the 3rd precoated shet is 0.28mm, be put on the sample platform of laser instrument, adopt the preparation method of first coating to be prepared into the 3rd coating, thickness is 0.08mm.Three coating composition gradient coatings, thickness is 0.22mm.
Outer surface at gradient coating polishes processing, forms smooth surface.
Copper alloy surface prepared with matrix be good metallurgical binding large tracts of land overlap joint gradient coating sem photograph as shown in Figure 4.The generation of smooth no obvious pore of surfacing and crackle has generated Cr in the gradient coating
3C
2, alloy phase such as Cr-Ni-Fe-C, the generation of heterogeneous alloy has improved the intensity of gradient coating, makes that gradient coating is inner to become as a whole.It is 5 times of hardness of copper alloy (90HV) that first microhardness of coating reaches 478HV, prepare on the good basis in first coating, prepared the second coating Co base composite coating by the induced with laser reaction in-situ, smooth no obvious pore of surfacing and crackle occur, second microhardness of coating has had further raising than first coating, realized the gradient gradual change, Al in second coating
0.34Co
0.41Cr
0.21W
0.04, Ni
3The generation of alloy phases such as B has improved the intensity and the toughness of coating.On the basis of second coating Co base coating, prepare the 3rd coating Co base composite coating that large tracts of land overlaps by the composition gradual change, more, the more disperse of ceramic particle in the 3rd coating; In coating, formed Fe
13Mo
2B
5, Cr-Co-Mo, FeCr
0.29Ni
0.16C
0.06Deng alloy phase, formed the second Co base complex tissue structure coating that strengthens mutually, the size of generated in-situ main particle is at 40nm～0.3 mu m range.
The preparation method has realized that three layers of cobalt-based coating of copper matrix surface present gradient in composition, tissue and thermophysical property and distribute, and it is 9.8 times of copper alloy microhardness that outermost microhardness is up to 896HV, as shown in Figure 5.Gradient coating is thick to be 0.25mm.Gradient coating when wearing and tearing 60 minutes the time abrasion loss of coating be that (50N 400r/min), only is 1/6 of a copper alloy abrasion loss to 0.009g, and gradient coating has the excellent abrasive energy.
Embodiment 3
Utilize sand-blast to remove the rusty scale of copper alloy surface, adopt the inorganic acid mixed solution to remove the greasy dirt and the corrosion of copper alloy surface; Utilize sandblast that copper alloy surface is carried out roughening treatment, make copper alloy surface easily and coating form firm bonding; Copper alloy after the alligatoring is utilized the alcoholic solution clean surface, till the cleaning surfaces no-sundries; At room temperature put into the H of 80g/l
2SO
4Soak 60s in the solution, carry out surface activation process; Clean with acetone soln then, remove the sulfuric acid and the water of copper alloy surface, then copper alloy is dried up with hair-dryer.
Wherein the inorganic acid mixed solution is H
2SO
4With the mixed solution of HCl, H in the mixed solution
2SO
4Concentration is 300g/l, and HCl concentration is 100g/l.
Nanometer Al powder and Co powder are mixed, put into ball mill and add absolute ethyl alcohol, at rotating speed wet mixing 8h under the condition of 300r/min, wherein the volume ratio of mixed metal powder and abrasive material is a mixed metal powder: abrasive material=5: 1, nanometer Al powder and Co powder are fully mixed be prepared into the master alloyed powder that contains nanometer Al, behind the dry removal ethanol, filter out fineness less than 250 purpose parts.With master alloyed powder and Ni, C, Cr, Fe, Si, CrO
3, Y
2O
3, Mo, W and MgO powder place ball mill, be to do under the condition of 300r/min to mix 12h at rotating speed, make it to mix, filter out fineness and partly be prepared into the first coating mix material less than 250 purposes.The composition of the first coating mix material is Ni25% by weight percentage, C1.5%, Cr16%, Fe10%, Si2.5%, nanometer Al0.3%, CrO
30.1%, Y
2O
31.0%, Mo0.3%, W2%, MgO0.1%, surplus is Co.
The first coating mix material is mixed with 504 glue, and mixed proportion accounts for 50% of the first coating mix material by 504 glue; After stirring, evenly be coated in and be prepared into first precoated shet on the pretreated copper alloy surface, and it is smooth that physics is carried out on the first precoated shet surface; In drying basin, place 15h then, treat the dry hardening of first precoated shet after, controlling the first precoated shet thickness through surface rubbing is 0.2mm.
The copper alloy that will have first precoated shet is put on the sample platform of laser instrument, and design laser scanning computer control figure carries out laser scanning, and laser technical parameters is: laser energy density 25J/mm
2, overlapping rate 25～30%.Form first coating of the large tracts of land overlap joint of surperficial no significant defect after laser scanning is finished, thickness is 0.04mm.
Preparation method by the first coating mix material prepares the second coating mix material, and the composition of the second coating mix material is Ni14% by weight percentage, C2.5%, Cr22%, Fe8%, Si5%, nanometer Al0.4%, CrO
30.2%, Y
2O
31.0%, Mo1.0%, W4%, MgO0.1%, B
2O
31.5%, graphite 1%, surplus is Co.
The second coating mix material is prepared into second precoated shet by the preparation method of first precoated shet at first coating surface, and controlling the second precoated shet thickness is 0.3mm, is put on the sample platform of laser instrument laser energy density 24J/mm
2, other adopt the preparation method of first coating to be prepared into second coating, and thickness is 0.08mm.
Preparation method by the first coating mix material prepares the 3rd coating mix material, and the composition of the 3rd coating mix material is Ni7% by weight percentage, C4%, Cr25%, Fe12%, Si7.5%, nanometer Al0.4%, CrO
30.1%, Y
2O
31.0%, Mo0.8%, W6%, MgO0.1%, B
2O
32.0%, graphite 2%, surplus is Co.
The 3rd coating mix material is prepared into the 3rd precoated shet by the preparation method of first precoated shet at second coating surface, the thickness of controlling the 3rd precoated shet is 0.3mm, be put on the sample platform of laser instrument, adopt the preparation method of first coating to be prepared into the 3rd coating, thickness is 0.13mm.Three coating composition gradient coatings, thickness is 0.25mm.
Outer surface at gradient coating polishes processing, forms smooth surface.
Three layers of Co base wear-resistant gradient coating that the original position hard particles strengthens have successfully been prepared on copper alloy (composition is Cu:Cr:P=99.9:0.07:0.03) surface.In the gradient coating of preparation, first coating has formed metallurgical interface with matrix and has combined, and the interface is in conjunction with good between the two, and flawless, gas hole defect produce; The main of second coating and the 3rd coating is CoCr mutually
2(Ni, O)
4Alloy phase also has multiple compound phase such as generated in-situ Cr-C, W-C and graphite to form simultaneously, and the size of ceramic particle is at 40nm～0.30 mu m range, as shown in Figure 6.
The generated in-situ ceramic phase of the 3rd coating has significantly than first coating and second coating and increases, and tissue and the main Cr that strengthens present graded.It is 5.8 times of matrix that the 3rd coating hardness of gradient coating reaches 523HV, and the obvious gradient that hard first coating to the, three coatings of gradient coating present from low to high distributes; The gradient coating coefficient of friction of graphitiferous is half of 0 copper alloy matrix, and the wear extent of gradient coating is that (22min), the gradient coating for preparing as the figure proof has good wear-resisting and certain self-lubricating property to 0.0054g for 40N, 250r/min.
Claims (7)
1, a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating, it is characterized in that: this gradient coating is made up of first coating, second coating and the 3rd coating, the coating that connects the copper alloy matrix surface is first coating, its composition is Ni20～35% by weight percentage, Cl～2%, Cr15～18%, Fe5～15%, Si2～3%, nanometer Al0.2～0.3%, CrO
30～0.16%, Y
2O
30.5～1.5%, Mo0～0.5%, W0～3%, MgO0～0.2%, surplus is Co; The thickness of first coating is that 0.04～0.10mm, second coating connects first coating, and its composition is Ni12～16% by weight percentage, C2～3%, Cr20～25%, Fe5～15%, Si4～6%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～2%, surplus is Co; The thickness of second coating is 0.03～0.08mm; The 3rd coating connects second coating, and its composition is Ni5～8% by weight percentage, C3～5%, Cr25～26%, Fe5～15%, Si7～8%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～3%, surplus is Co; The thickness of the 3rd coating is 0.07～0.13mm.
2, a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating according to claim 1 is characterized in that described gradient coating thickness is 0.16～0.25mm.
3, the method for the described a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating of claim 1, it is characterized in that carrying out according to the following steps: (1) utilizes sand-blast to remove the rusty scale of copper alloy surface, adopts the inorganic acid mixed solution to remove the greasy dirt and the corrosion of copper alloy surface; Copper alloy surface is carried out roughening treatment, make copper alloy surface easily and coating form firm bonding; Copper alloy after the alligatoring is utilized organic solvent or organic solvent solution clean surface, till the cleaning surfaces no-sundries; At room temperature put into the H of 70～80g/l
2SO
4Soak 20～60s in the solution, carry out surface activation process; Clean with organic solvent or organic solvent solution, remove the sulfuric acid and the water of copper alloy surface, then copper alloy is dried up or natural air drying with hair-dryer; (2) nanometer Al powder and Co powder are mixed, put into ball mill and add absolute ethyl alcohol, at rotating speed wet mixing 5～8h under the condition of 300～500r/min, wherein the volume ratio of mixed metal powder and abrasive material is a mixed metal powder: abrasive material=5～8: 1, nanometer Al powder and Co powder are fully mixed be prepared into the master alloyed powder that contains nanometer Al, dry remove ethanol after, it is standby less than 250 purpose parts to filter out fineness; Master alloyed powder and other powder are placed ball mill, be to do under the condition of 300～500r/min to mix 10～12h at rotating speed, make it to mix, filter out fineness and be prepared into the first coating mix material, the second coating mix material and the 3rd coating mix material respectively less than 250 purposes part; Wherein the first coating mix material composition is Ni20～35% by weight percentage, Cl～2%, Cr15～18%, Fe5～15%, Si2～3%, nanometer Al0.2～0.3%, CrO
30～0.16%, Y
2O
30.5～1.5%, Mo0～0.5%, W0～3%, MgO0～0.2%, surplus is Co; The second coating mix material composition is Ni12～16% by weight percentage, C2～3%, Cr20～25%, Fe5～15%, Si4～6%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～2%, surplus is Co; The 3rd coating mix material composition is Ni5～8% by weight percentage, C3～5%, Cr25～26%, Fe5～15%, Si7～8%, nanometer Al0.3～0.5%, CrO
30～0.3%, Y
2O
30.5～1.5%, Mo0～1.2%, W0～8%, MgO0～0.2%, B
2O
30～2.5%, graphite 0～3%, surplus is Co; (3) the first coating mix material is mixed with adhesive, mixed proportion accounts for 30～40% of the first coating mix material by adhesive; Stir into a paste, evenly be coated in and be prepared into first precoated shet on the pretreated copper alloy surface, and it is smooth that physics is carried out on the first precoated shet surface; In drying basin, place 13h～15h then, treat the dry hardening of first precoated shet after, controlling the first precoated shet thickness through surface rubbing is 0.2～0.5mm; (4) copper alloy that will have first precoated shet is put on the sample platform of laser instrument, carries out the former bit scan preparation of induced with laser, and laser technical parameters is: laser energy density 20～25J/mm
2, overlapping rate 20～35%; After finishing, the laser preparation forms first coating of the large tracts of land overlap joint of surperficial no significant defect; (5) with the second coating mix material set by step the method for (3) on first coating, be prepared into second precoated shet, controlling the second precoated shet thickness is 0.2～0.3mm, is put on the sample platform of laser instrument, adopts the method for step (4) to be prepared into second coating; With the 3rd coating mix material set by step the method for (3) on second coating, be prepared into the 3rd precoated shet, the thickness of controlling the 3rd precoated shet is 0.2～0.3mm, is put on the sample platform of laser instrument, adopts the method for step (4) to be prepared into the 3rd coating; Three coating composition gradient coatings, thickness is 0.16～0.25mm.
4, the method for a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating according to claim 3 is characterized in that described inorganic acid mixed solution is H
2SO
4With the mixed solution of HCl, H in the mixed solution
2SO
4Concentration is 200～300g/l, and HCl concentration is 100～120g/l.
5, the method for a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating according to claim 3 is characterized in that described adhesive is varnish, silicate cement, waterglass, cellulose acetate, acetone borax soln, transparent adhesive tape, paste or 504 glue.
6, the method for a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating according to claim 3, the consumption of absolute ethyl alcohol is as the criterion with submergence ball milling material when it is characterized in that wet mixing.
7, the method for a kind of copper alloy surface induced with laser in-situ preparing cobalt-base alloys gradient coating according to claim 3 is characterized in that described nanometer Al particle diameter is 20～100nm, described Co, C, Ni, Cr, Fe, Si, CrO
3, Y
2O
3, Mo, W, MgO, B
2O
3Be particle diameter less than 200 purpose powder with graphite.
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