CN103831222B - A kind of preparation of carbide surface non-laminar aluminum oxide/titanium carbide coating - Google Patents

A kind of preparation of carbide surface non-laminar aluminum oxide/titanium carbide coating Download PDF

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CN103831222B
CN103831222B CN201410100936.1A CN201410100936A CN103831222B CN 103831222 B CN103831222 B CN 103831222B CN 201410100936 A CN201410100936 A CN 201410100936A CN 103831222 B CN103831222 B CN 103831222B
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CN103831222A (en
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杨梅
龙剑平
邱克辉
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Chengdu Univeristy of Technology
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Abstract

The invention discloses a kind of preparation method of carbide surface non-laminar aluminum oxide/titanium carbide coating, it is characterized in that adopting Liquid preparation methods to go out Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol, be then spin-coated on through solid-phase sintering density reach 90% ~ 95% carbide alloy billet surface formed Al 2o 3/ TiO 2layer, the CO/CH in recycling liquid sintering process 4carbothermic reduction reaction occurs for carburizing atmosphere and top layer makes TiO 2be converted into TiC, finally produce non-laminar Al at carbide surface 2o 3/ TiC.The Al that the present invention manufactures 2o 3/ TiC coating is homogeneous composite coating, and each coated grains is Al 2o 3/ TiC core/shell structure, the problem that the layer structure avoiding traditional vapour deposition formation easily lost efficacy because interlayer difference is huge, and also technical process is simple, is easy to control.

Description

A kind of preparation of carbide surface non-laminar aluminum oxide/titanium carbide coating
Technical field
The present invention relates to a kind of preparation method of coating, particularly carbide surface non-laminar Al 2o 3/ TiC coating production, belongs to Surface Engineering field.
Background technology
Coating technology is the milestone that hard closes in alloy development history, and hard alloy substrate applies one or more layers TiC, TiN, TiCN, Al 2o 3, the film such as TiAlN constitutes coated cutting tool, its obdurability is ensured by matrix, and high rigidity and wearability are solved by coating.Coating decreases the crescent hollow abrasion of carbide alloy in working angles as chemical barrier and thermodynamic barrier, cutter life increases substantially, and current coated cutting tool accounts for hard alloy cutter more than 80%.
In numerous coating materials, Al 2o 3coating at high temperature has good heat endurance, chemical stability, high rigidity and mechanical strength, anti-oxidant wearing and tearing and anti-diffusive wear performance, is excellent coating material.But, Al 2o 3physical property and hard alloy substrate difference huge, bond strength is therebetween not high, does not generally directly use, and usually with the TiC higher with carbide matrix material bond strength xn 1-xthe bottom of (x=0 ~ 1) making coatings or separate layer, at present, Al 2o 3/ TiC xn 1-xthe collocation of (x=0 ~ 1) coating obtains application widely in high-speed cutting field.Patent 02158373.0 discloses the carbide alloy of a kind of coating sintering, comprise a hard alloy substrate, the ground floor adjacent with this cemented carbide body, described ground floor contains Ti (C, N), thickness is about 3 to about 20 μm, the alumina layer adjacent with described ground floor, and this alumina layer contains α-Al 2o 3or κ-Al 2o 3, thickness is about 1 to about 15 μm and the farther layer containing one or more carbide, carbonitride or carboxyl nitride in Ti, Zr and Hf adjacent with this alumina layer, and the thickness of described farther layer is about 1 to 15 μm.One is reduced frictional layer, containing γ-Al 2o 3, κ-Al 2o 3one or more with in millimicro crystallization Ti (C, N), thickness is about 1 to about 5 μm, can adjoin with farther layer.The employing such as M.Fallqvist CVD has prepared the κ-Al that multilayer Ti (C, N) thin layer separates on WC-9 (Nb, Ti, Ta) C-5.5Co hard alloy substrate 2o 3coating (M.Fallqvist, M.Olsson, S.Ruppi.Abrasivewearofmultilayer κ-Al 2o 3-Ti (C, N) CVDcoatingsoncementedcarbide.Wear, 2007,263 (1-6): 74-80).The TiN/ κ – Al that S.Canovic etc. separate by the TiN layer (50 and 600nm) that CVD has prepared two-layer different-thickness 2o 3coating S.Canovic, S.Ruppi, J.Rohrer, A.Vojvodic, C.Ruberto, P.Hyl-dgaard, M.Halvarsson.TEMandDFTinvestigationofCVDTiN/ κ – Al 2o 3multilayercoatings.Surface & CoatingsTechnology, 2007,202 (3): 522-531).A.Riedl etc. adopt LPCVD method at the first depositing Ti CN of WC-4TiC-8TaC/NbC-11Co carbide surface, then depositing Al 2o 3, coating layer thickness is respectively 8 and 10 μm, and gas component is respectively TiCl 4– CH 3cN – H 2– N 2and AlCl 3– CO – CO 2– H 2– H 2s, depositing temperature is respectively 900 and 1000 DEG C, and gas pressure is respectively 80 and 100mbar(A.Riedl, N.Schalk, C.Czettl, B.Sartory, C.Mitterer.TribologicalpropertiesofAl 2o 3hardcoatingsmodifiedbymechanicalblastingandpolishingpost-treatment.2012, Wear, 289,9-16).X.M.Chen etc. prepare CVDTiN/TiCN/ κ-Al at WC-5.5 (Ti, Ta, Nb) C-6Co carbide surface 2o 3(α-Al 2o 3) coating, the depositing temperature of each layer is 950-1050 DEG C, 800-900 DEG C and 950-1050 DEG C respectively; Sedimentation time is respectively 0.5 – 1h, 1 – 4h and 2 – 6h; Gas pressure is respectively 10 – 50kPa, 5 – 20kPa and 5 – 20kPa(X.MChen, H.Q.Liu, Q.H.Guo, S.P.Sun.OxidationbehaviorofWC – CohardmetalwithdesignedmultilayercoatingsbyCVD.Internati onalJournalofRefractoryMetalsandHardMaterials, 2013,31,171-178).
Visible, the Al of preparation at present 2o 3/ TiC coating is many layer structures (as shown in Figure 1), namely separates Al with TiC 2o 3, and can repeated deposition multilayer according to design requirement.Each layer of this layered coating structures is the pure Al of two dimension 2o 3, each interlayer two dimension interface there is composition, structure, not the mating of physical and mechanical property in layer or pure TiC layer, very unfavorable for the bond strength between coating.On the other hand, CVD method prepares the shortcomings such as coating also exists apparatus expensive, technical sophistication, technique are loaded down with trivial details, and technical merit requires high, restive; And these methods are all first sinter out hard alloy substrate, and then carry out coating process, therefore carbide matrix is known from experience through twice heating cooling procedure, and therefore the preparation process of coated carbides also becomes complicated.
Summary of the invention
The present invention is directed to the carbide surface Al of preparation at present 2o 3/ TiC coating is that layer structure is unfavorable for Coating combination, and complex process controls difficulty, and after sintering, the mode of coating makes hard alloy substrate through the problem of twice heating cooling procedure, proposes first to adopt Liquid preparation methods to go out Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol, is then spin-coated on the carbide alloy billet surface after solid-phase sintering and forms Al 2o 3/ TiO 2layer, the CO/CH in recycling liquid sintering process 4carbothermic reduction reaction occurs for carburizing atmosphere and top layer makes TiO 2be converted into TiC, finally produce non-laminar Al at carbide surface 2o 3/ TiC.
Carbide surface non-laminar Al of the present invention 2o 3the preparation method of/TiC coating, is characterized in that comprising following steps successively:
(1) Al (OH) 3/ Ti (OH) 4prepared by core/shell structure colloidal sol: successively by Tween 80, polysorbate60, n-butanol, and cyclohexane adds in deionized water; By volume percentage composition Tween 80 accounts for 15% ~ 25%, and polysorbate60 accounts for 5% ~ 10%, and n-butanol accounts for 5% ~ 15%, and cyclohexane accounts for 5% ~ 12%, and all the other are deionized water; At 60 ~ 90 DEG C, stir 3 ~ 10h with magnetic stirring apparatus, then place 10 ~ 24h, obtain water in oil microemulsion; By AlCl 3join in water in oil microemulsion, make its concentration expressed in percentage by volume be 0.5% ~ 2.5%, then add ammoniacal liquor adjustment solution ph to 8 ~ 9, at 20 ~ 60 DEG C, stir 1 ~ 6h with magnetic stirring apparatus, then place 6 ~ 12h, form Al (OH) 3colloidal sol; Add C again 16h 36tiO 4, make its concentration expressed in percentage by volume be AlCl 35% ~ 45% of concentration expressed in percentage by volume, and add ammoniacal liquor adjust ph to 8 ~ 9, at 40 ~ 90 DEG C, stir 1 ~ 6h with magnetic stirring apparatus, then place 6 ~ 12h, generate Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol;
(2) hard alloy green body solid-phase sintering: take various material powder batching, TiC accounts for 0 ~ 15%, TaC and accounts for 0 ~ 15%, NbC and account for 0 ~ 10%, Co and account for 4 ~ 15% by weight percentage, and all the other are WC; Mixed-powder through ball milling, filtration, drying, mix forming agent, compressingly obtain hard alloy green body; Hard alloy green body is warmed up to 1250 ~ 1350 DEG C in vacuum sintering furnace, and vacuum is 3 ~ 10Pa, and is incubated 2 ~ 4h to complete solid-phase sintering, and forming density is the base substrate of 90% ~ 95%;
(3) spin coating and carbide alloy billet surface Al 2o 3/ TiO 2core/shell structure generates: by Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol is spin-coated on the carbide alloy billet surface after solid-phase sintering, during spin coating, every layer turns 20s under the rotating speed of 550r/min, 20s is turned again with the rotating speed of 1100r/min, every layer be painted with after at 115 ~ 230 DEG C, cure 1h and one deck under being coated with again after being cooled to 20 ~ 30 DEG C, the spin coating number of plies is 3 ~ 6 layers, forms Al in carbide alloy billet surface 2o 3/ TiO 2core/shell structure;
(4) liquid-phase sintering manufactures Al 2o 3/ TiC coated carbides: there is Al on surface 2o 3/ TiO 2carbide alloy base substrate CH in low pressure atmosphere sintering furnace of core/shell structure 4sinter under/CO atmosphere, CH 4/ CO mixture pressure is 1 ~ 3MPa, CH 4: CO mol ratio is 1:2, and reaction heating-up temperature is 1400 DEG C ~ 1500 DEG C, and temperature retention time is the Al of 0.5h, carbide alloy billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; Be filled with argon gas after insulation terminates and get rid of CH 4/ CO gas, maintenance argon pressure is 3 ~ 5MPa, and sintering temperature is constant, then is incubated 1 ~ 3h, realizes hard alloy substrate liquid-phase sintering densified, prepares surface and has Al 2o 3the coated carbides of/TiC composite coating.
Carbide surface non-laminar Al of the present invention 2o 3the preparation method of/TiC coating, it is further characterized in that:
(1) Tween 80, polysorbate60, n-butanol, cyclohexane, AlCl 3, C 16h 36tiO 4with ammoniacal liquor be analyze pure; Preparation Al (OH) 3/ Ti (OH) 4during core/shell structure colloidal sol, the speed of magnetic agitation is 20 ~ 50r/min;
(2) when prepared by hard alloy green body, Ball-milling Time is 24 ~ 72h, filters employing 400 eye mesh screen, adopts 85 ~ 100 DEG C of dryings, mix buna forming agent, make type at 300 ~ 500MPa pressure in the ratio of 70 ~ 90ml/kg;
(3), during hard alloy green body solid-phase sintering, programming rate is 5 ~ 15 DEG C/min;
(4) liquid-phase sintering terminate after cooling rate be 5 ~ 15 DEG C/min.
The invention has the advantages that: Al prepared by (1) the present invention 2o 3/ TiC coating is homogeneous composite coating, and each coated grains is Al 2o 3/ TiC core/shell structure, the problem that the layer structure avoiding traditional vapour deposition formation easily lost efficacy because interlayer difference is huge.(2) utilize heterogeneous forming core principle in liquid phase, make Ti(OH) 4coated Al (OH) 3colloid surface, forms Al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol, recycling sintering carburizing atmosphere is converted into Al 2o 3/ TiC composite coating, technique is simple, is easy to control, need not gradation vapour deposition.(3) after hard alloy substrate solid-phase sintering, density reaches 90% ~ 95%, and intensity also can increase substantially, then there will not be surface hydrolysis to be oxidized and defect when carrying out collosol coating; And basic contraction completely, can not cause the breakage of face coat after its solid-phase sintering because of dimensional contraction excessive during liquid-phase sintering after spin coating.(4) Al 2o 3/ TiC composite coating is core/shell structure, is conducive to improving the bond strength between coating.(5) in liquid sintering process with CH 4/ CO is that carbon source realizes surface TiO 2to the conversion of TiC, avoid the destruction to Carbon balance in hard alloy substrate.
Accompanying drawing explanation
Fig. 1 tradition stratiform and non-laminar coating structure schematic diagram of the present invention
Detailed description of the invention
Example 1: head successively by Tween 80, polysorbate60, n-butanol, cyclohexane adds in deionized water; By volume percentage composition Tween 80 accounts for 16%, and polysorbate60 accounts for 6%, and n-butanol accounts for 7%, and cyclohexane accounts for 5%, and all the other are deionized water; At 605 DEG C, stir 4h with magnetic stirring apparatus, the speed of magnetic agitation is 25r/min, then places 14h, obtains water in oil microemulsion.By AlCl 3join in water in oil microemulsion, make its concentration expressed in percentage by volume be 0.7%, then add ammoniacal liquor adjustment solution ph to 8, at 28 DEG C, stir 2h with magnetic stirring apparatus, the speed of magnetic agitation is 30r/min, then places 8h, forms Al (OH) 3colloidal sol; Add C again 16h 36tiO 4, make its concentration expressed in percentage by volume be 0.07%, be equivalent to AlCl 310% of concentration expressed in percentage by volume, and add ammoniacal liquor adjust ph to 8.5, at 45 DEG C, stir 2h with magnetic stirring apparatus, the speed of magnetic agitation is 40r/min, then places 6h, generates Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol; Tween 80 used, polysorbate60, n-butanol, cyclohexane, AlCl 3, C 16h 36tiO 4with ammoniacal liquor be analyze pure.Then take various material powder batching, TiC accounts for 2%, TaC and accounts for 2%, Co and account for 7% by weight percentage, and all the other are WC; Mixed-powder is through 36h ball milling, and 400 eye mesh screens filter, and adopt 85 DEG C of dryings, mix buna forming agent, make type obtain hard alloy green body at 320MPa pressure in the ratio of 75ml/kg; Hard alloy green body is warmed up to 1300 DEG C in vacuum sintering furnace, and programming rate is 5 DEG C/min, and vacuum is 4Pa, and is incubated 2h to complete solid-phase sintering, and forming density is the base substrate of 91%.Again by Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol is spin-coated on the carbide alloy billet surface after solid-phase sintering, during spin coating, every layer turns 20s under the rotating speed of 550r/min, 20s is turned again with the rotating speed of 1100r/min, every layer be painted with after at 130 DEG C, cure 1h and one deck under being coated with again after being cooled to 25 DEG C, the spin coating number of plies is 3 layers, forms Al in carbide alloy billet surface 2o 3/ TiO 2core/shell structure.Finally, surface there is Al 2o 3/ TiO 2carbide alloy base substrate CH in low pressure atmosphere sintering furnace of core/shell structure 4sinter under/CO atmosphere, CH 4/ CO mixture pressure is 1MPa, CH 4: CO mol ratio is 1:2, and reaction heating-up temperature is 1440 DEG C, and temperature retention time is the Al of 0.5h, carbide alloy billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; Be filled with argon gas after insulation terminates and get rid of CH 4/ CO gas, maintenance argon pressure is 3MPa, and sintering temperature is constant, then is incubated 1h, realizes hard alloy substrate liquid-phase sintering densified, prepares surface and has Al 2o 3the coated carbides of/TiC composite coating; Cooling rate after liquid-phase sintering terminates is 5 DEG C/min.
Example 2: head successively by Tween 80, polysorbate60, n-butanol, cyclohexane adds in deionized water; By volume percentage composition Tween 80 accounts for 20%, and polysorbate60 accounts for 8%, and n-butanol accounts for 15%, and cyclohexane accounts for 8%, and all the other are deionized water; At 80 DEG C, stir 8h with magnetic stirring apparatus, the speed of magnetic agitation is 50r/min, then places 24h, obtains water in oil microemulsion.By AlCl 3join in water in oil microemulsion, make its concentration expressed in percentage by volume be 2.4%, then add ammoniacal liquor adjustment solution ph to 8.7, at 50 DEG C, stir 5h with magnetic stirring apparatus, the speed of magnetic agitation is 45r/min, then places 12h, forms Al (OH) 3colloidal sol; Add C again 16h 36tiO 4, make its concentration expressed in percentage by volume be 0.96%, be equivalent to AlCl 340% of concentration expressed in percentage by volume, and add ammoniacal liquor adjust ph to 9, at 90 DEG C, stir 5h with magnetic stirring apparatus, the speed of magnetic agitation is 50r/min, then places 11h, generates Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol; Tween 80 used, polysorbate60, n-butanol, cyclohexane, AlCl 3, C 16h 36tiO 4with ammoniacal liquor be analyze pure.Then take various material powder batching, TaC accounts for 3%, NbC and accounts for 2%, Co and account for 15% by weight percentage, and all the other are WC; Mixed-powder is through 72h ball milling, and 400 eye mesh screens filter, and adopt 100 DEG C of dryings, mix buna forming agent, make type obtain hard alloy green body at 400MPa pressure in the ratio of 80ml/kg; Hard alloy green body is warmed up to 1250 DEG C in vacuum sintering furnace, and programming rate is 10 DEG C/min, and vacuum is 7Pa, and is incubated 3h to complete solid-phase sintering, and forming density is the base substrate of 93%.Again by Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol is spin-coated on the carbide alloy billet surface after solid-phase sintering, during spin coating, every layer turns 20s under the rotating speed of 550r/min, 20s is turned again with the rotating speed of 1100r/min, every layer be painted with after at 210 DEG C, cure 1h and one deck under being coated with again after being cooled to 27 DEG C, the spin coating number of plies is 6 layers, forms Al in carbide alloy billet surface 2o 3/ TiO 2core/shell structure.Finally, surface there is Al 2o 3/ TiO 2carbide alloy base substrate CH in low pressure atmosphere sintering furnace of core/shell structure 4sinter under/CO atmosphere, CH 4/ CO mixture pressure is 3MPa, CH 4: CO mol ratio is 1:2, and reaction heating-up temperature is 1400 DEG C, and temperature retention time is the Al of 0.5h, carbide alloy billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; Be filled with argon gas after insulation terminates and get rid of CH 4/ CO gas, maintenance argon pressure is 5MPa, and sintering temperature is constant, then is incubated 2h, realizes hard alloy substrate liquid-phase sintering densified, prepares surface and has Al 2o 3the coated carbides of/TiC composite coating; Cooling rate after liquid-phase sintering terminates is 13 DEG C/min.

Claims (2)

1. a carbide surface non-laminar Al 2o 3the preparation method of/TiC coating, is characterized in that comprising following steps successively:
(1) Al (OH) 3/ Ti (OH) 4prepared by core/shell structure colloidal sol: successively by Tween 80, polysorbate60, n-butanol, and cyclohexane adds in deionized water; By volume percentage composition Tween 80 accounts for 15% ~ 25%, and polysorbate60 accounts for 5% ~ 10%, and n-butanol accounts for 5% ~ 15%, and cyclohexane accounts for 5% ~ 12%, and all the other are deionized water; At 60 ~ 90 DEG C, stir 3 ~ 10h with magnetic stirring apparatus, then place 10 ~ 24h, obtain water in oil microemulsion; By AlCl 3join in water in oil microemulsion, make its concentration expressed in percentage by volume be 0.5% ~ 2.5%, then add ammoniacal liquor adjustment solution ph to 8 ~ 9, at 20 ~ 60 DEG C, stir 1 ~ 6h with magnetic stirring apparatus, then place 6 ~ 12h, form Al (OH) 3colloidal sol; Add C again 16h 36tiO 4, make its concentration expressed in percentage by volume be AlCl 35% ~ 45% of concentration expressed in percentage by volume, and add ammoniacal liquor adjust ph to 8 ~ 9, at 40 ~ 90 DEG C, stir 1 ~ 6h with magnetic stirring apparatus, then place 6 ~ 12h, generate Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol;
(2) hard alloy green body solid-phase sintering: take various material powder batching, TiC accounts for 0 ~ 15%, TaC and accounts for 0 ~ 15%, NbC and account for 0 ~ 10%, Co and account for 4 ~ 15% by weight percentage, and all the other are WC; Mixed-powder through ball milling, filtration, drying, mix forming agent, compressingly obtain hard alloy green body; Hard alloy green body is warmed up to 1250 ~ 1350 DEG C in vacuum sintering furnace, and vacuum is 3 ~ 10Pa, and is incubated 2 ~ 4h to complete solid-phase sintering, and forming density is the base substrate of 90% ~ 95%;
(3) spin coating and carbide alloy billet surface Al 2o 3/ TiO 2core/shell structure generates: by Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol is spin-coated on the carbide alloy billet surface after solid-phase sintering, during spin coating, every layer turns 20s under the rotating speed of 550r/min, 20s is turned again with the rotating speed of 1100r/min, every layer be painted with after at 115 ~ 230 DEG C, cure 1h and one deck under being coated with again after being cooled to 20 ~ 30 DEG C, the spin coating number of plies is 3 ~ 6 layers, forms Al in carbide alloy billet surface 2o 3/ TiO 2core/shell structure;
(4) liquid-phase sintering manufactures Al 2o 3/ TiC coated carbides: there is Al on surface 2o 3/ TiO 2carbide alloy base substrate CH in low pressure atmosphere sintering furnace of core/shell structure 4sinter under/CO atmosphere, CH 4/ CO mixture pressure is 1 ~ 3MPa, CH 4: CO mol ratio is 1:2, and reaction heating-up temperature is 1400 DEG C ~ 1500 DEG C, and temperature retention time is the Al of 0.5h, carbide alloy billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; Be filled with argon gas after insulation terminates and get rid of CH 4/ CO gas, maintenance argon pressure is 3 ~ 5MPa, and sintering temperature is constant, then is incubated 1 ~ 3h, realizes hard alloy substrate liquid-phase sintering densified, prepares surface and has Al 2o 3the coated carbides of/TiC composite coating.
2. carbide surface non-laminar Al according to claim 1 2o 3the preparation method of/TiC coating, it is further characterized in that:
(1) Tween 80, polysorbate60, n-butanol, cyclohexane, AlCl 3, C 16h 36tiO 4with ammoniacal liquor be analyze pure; Preparation Al (OH) 3/ Ti (OH) 4during core/shell structure colloidal sol, the speed of magnetic agitation is 20 ~ 50r/min;
(2) when prepared by hard alloy green body, Ball-milling Time is 24 ~ 72h, filters employing 400 eye mesh screen, adopts 85 ~ 100 DEG C of dryings, mix buna forming agent, make type at 300 ~ 500MPa pressure in the ratio of 70 ~ 90ml/kg;
(3), during hard alloy green body solid-phase sintering, programming rate is 5 ~ 15 DEG C/min;
(4) liquid-phase sintering terminate after cooling rate be 5 ~ 15 DEG C/min.
CN201410100936.1A 2014-03-19 2014-03-19 A kind of preparation of carbide surface non-laminar aluminum oxide/titanium carbide coating Expired - Fee Related CN103831222B (en)

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