CN103820695A - Method for preparing Al2O3/TiC coating hard alloy based on liquid phase sintering process - Google Patents

Method for preparing Al2O3/TiC coating hard alloy based on liquid phase sintering process Download PDF

Info

Publication number
CN103820695A
CN103820695A CN201410100937.6A CN201410100937A CN103820695A CN 103820695 A CN103820695 A CN 103820695A CN 201410100937 A CN201410100937 A CN 201410100937A CN 103820695 A CN103820695 A CN 103820695A
Authority
CN
China
Prior art keywords
sintering
wimet
tic
core
shell structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410100937.6A
Other languages
Chinese (zh)
Other versions
CN103820695B (en
Inventor
杨梅
龙剑平
邱克辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Univeristy of Technology
Original Assignee
Chengdu Univeristy of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu Univeristy of Technology filed Critical Chengdu Univeristy of Technology
Priority to CN201410100937.6A priority Critical patent/CN103820695B/en
Publication of CN103820695A publication Critical patent/CN103820695A/en
Application granted granted Critical
Publication of CN103820695B publication Critical patent/CN103820695B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Powder Metallurgy (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

The invention discloses a method for preparing an Al2O3/TiC coating hard alloy based on a liquid phase sintering process. The method is characterized by comprising the following steps: firstly, preparing Al(OH)3/Ti(OH)4 core/shell structure sol by adopting a liquid phase method, and then spinning the sol on a hard alloy blank surface of which the solid-phase sintering density can be up to 85-95%, and forming an Al2O3/TiO2 layer; carrying out carbothermic reduction reaction on the surface layer by using a CO atmosphere in the liquid-phase sintering process, so that the TiO2 is transformed into TiC; and finally, manufacturing the Al2O3/TiC coating hard alloy. The method is simple in technological process, and easy to control, the problem of step-by-step vapor deposition of two coatings in the manufacturing process of the Al2O3/TiC coating hard alloy, and the problem of step-by-step execution of coating treatment and substrate preparation are avoided, and the Al2O3/TiC coating hard alloy is prepared in one step on the basis of the liquid phase sintering process.

Description

Based on the Al of liquid sintering process 2o 3/ TiC coated carbides preparation method
Technical field
The present invention relates to a kind of preparation method of coated carbides, particularly Al 2o 3the preparation method of/TiC coated carbides, belongs to powder metallurgy and Hardmetal materials field.
Background technology
Wimet is that the iron family metals such as Co are binding agent take the infusibility such as WC, TiC transition metal carbide as base, the multiphase solid material that adopts powder metallurgy process to be prepared into.Since nineteen twenty-three Germany's invention WC-6%Co invention, through the development of nearly 90 years, Wimet has replaced rapid steel became current topmost cutter material, was described as " tooth of industry ".The appearance of coating technology particularly occurring the seventies in last century, make coating after cutter life improve 2～5 times.On hard alloy substrate, apply one or more layers metal or nonmetallic compound film has formed coated cutting tool, its obdurability is guaranteed by matrix, and high rigidity and wear resistance are solved by coating.Coating has reduced the crescent hollow abrasion of Wimet in working angles as chemical barrier and thermodynamic barrier, along with the requirement of production to high-level efficiency, high precision and high reliability, Cutting-Tool Coating Technology is paid much attention to, and coated cutting tool accounts for inserted tool more than 70% at present.At present, the coated material (and combination) of applying on inserted tool has tens kinds, topmost TiC, TiN, TiCN, the Al of comprising 2o 3, TiAlN etc.Wherein Al 2o 3coating at high temperature has good thermostability, chemical stability, high rigidity and physical strength, anti-oxidant wearing and tearing and anti-diffusive wear performance, and TiC xn 1-x(x=0～1) coating not only self performance is excellent but also be well typically used as the bottom of coating, Al with matrix bonding properties 2o 3/ TiC xn 1-xthe collocation of (x=0～1) coating has obtained application very widely in high speed cutting field.
Traditional chemical vapour deposition (CVD) method and physical vapor deposition (PVD) method are at Al 2o 3/ TiC xn 1-xin (x=0～1) coating manufacture, obtained success, S. Canovic etc. use CVD legal system for the Al separating with 20nmTiC or TiN 2o 3coating, and the TiN/ κ – Al that separates of the TiN layer of two-layer different thickness (50 and 600nm) 2o 3coating.A. Riedl etc. adopts LPCVD method at the first depositing Ti CN of WC-4TiC-8TaC/NbC-11Co carbide surface, then depositing Al 2o 3, coat-thickness is respectively 8 and 10 μ m, and gaseous fraction 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 ℃, and gaseous tension is respectively 80 and 100mbar.X.M. Chen etc. prepares CVD TiN/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 respectively 950-1050 ℃, 800-900 ℃ and 950-1050 ℃; Depositing time is respectively 0.5 – 1 h, 1 – 4 h and 2 – 6 h; Gaseous tension is respectively 10 ~ 50 kPa, 5 ~ 20 kPa and 5 ~ 20 kPa.
But, Al 2o 3and TiC xn 1-xthe physical and mechanical property of layer is widely different, and while adopting traditional vapour deposition process, their depositing temperature, gaseous fraction, pressure are all not identical, disposable acquisition under the same conditions.Therefore, coating procedure needs proceed step by step, and the control of above-mentioned coating process parameter is very difficult.And these methods are all that first sintering goes out hard alloy substrate, and then carry out coating processing, therefore carbide matrix is known from experience through twice heating process of cooling, and it is complicated that therefore the preparation process of coated carbides also becomes.In continuing to optimize vapour deposition process, develop new coated carbides preparation method and have great importance undoubtedly.
Summary of the invention
The present invention is directed to current Al 2o 3two kinds of coating substeps vapour deposition in/TiC coated carbides manufacturing processed, hard alloy substrate preparation is processed proceed step by step with coating, and complex technical process and unmanageable problem propose 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 Wimet billet surface that density is 85%～95% after solid state sintering and forms Al 2o 3/ TiO 2layer, carbothermic reduction reaction occurs for the CO atmosphere in recycling liquid sintering process and top layer makes TiO 2be converted into TiC, finally produce Al 2o 3/ TiC coated carbides.
Al based on liquid sintering process of the present invention 2o 3the preparation method of/TiC coated carbides, is characterized in that comprising successively following steps:
(1) Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol preparation: by Al (NO 3) 3being made into concentration expressed in percentage by volume with deionized water is 0.5%～3% solution, adds ammoniacal liquor regulator solution pH value to 8～9, stirs 1～6h with magnetic stirring apparatus at 20～60 ℃, then places 6～12h, forms Al (OH) 3colloidal sol; Add again TiCl 4, making its concentration expressed in percentage by volume is Al (NO 3) 35%～45% of concentration expressed in percentage by volume, and add ammoniacal liquor to regulate pH value to 8～9, at 40～90 ℃, stir 1～6h with magnetic stirring apparatus, then place 6～12h, generation Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol;
(2) Wimet green compact solid state sintering: take various raw material powders batching, TiC accounts for 0～15%, TaC and accounts for 0～15%, NbC and account for 0～10%, Co and account for 4～12% by weight percentage, and all the other are WC; Mixed powder through ball milling, filtration, be dried, mix forming agent, compression moulding obtains Wimet green compact; Wimet green compact are warmed up to 1150～1300 ℃ in vacuum sintering furnace, and vacuum tightness is 3～10Pa, and are incubated 1～3h to complete solid state sintering, the base substrate that formation density is 85%～95%;
(3) spin coating and Wimet 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 Wimet billet surface after solid state sintering, when spin coating, every layer turns 15s under the rotating speed of 550r/min, turn 25s with the rotating speed of 1100r/min again, every layer be coated with again after curing 1h and be cooled to 20～30 ℃ at 115～230 ℃ after being painted with under one deck, the spin coating number of plies is 3～6 layers, forms Al in Wimet billet surface 2o 3/ TiO 2core/shell structure;
(4) Al is manufactured in liquid phase sintering 2o 3/ TiC coated carbides: there is to Al on surface 2o 3/ TiO 2the Wimet base substrate of core/shell structure sintering under CO atmosphere in low pressure atmosphere sintering oven, gaseous tension is 1～3MPa, and temperature is 1400 ℃～1500 ℃, and soaking time is 0.5h, the Al of Wimet billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; After insulation finishes, be filled with argon gas and get rid of 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 densification, prepares surface and has Al 2o 3the coated carbides of/TiC compound coating.
Al based on liquid sintering process of the present invention 2o 3the preparation method of/TiC coated carbides, it is further characterized in that:
(1) Al (NO 3) 3, TiCl 4be analytical pure with ammoniacal liquor; Preparation Al (OH) 3/ Ti (OH) 4when core/shell structure colloidal sol, the speed of magnetic agitation is 20～50r/min;
(2) when prepared by Wimet green compact, Ball-milling Time is 24～72h, filters and adopts 400 eye mesh screens, adopts 85～100 ℃ to be dried, and mixes sodium butadiene rubber forming agent, compression moulding under 300～500MPa pressure in the ratio of 70～90ml/kg;
(3), when Wimet green compact solid state sintering, heat-up rate is 5～15 ℃/min;
(4) cooling rate of liquid phase sintering after finishing is 5～15 ℃/min.
The invention has the advantages that: (1) utilizes heterogeneous forming core principle in liquid phase, makes 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 compound coating, technique is simple, is easy to control, need not gradation vapour deposition.(2) after hard alloy substrate solid state sintering, density and intensity improve, then carry out collosol coating and there will not be surface hydrolysis oxidation and damaged; And basic contraction completely after its solid state sintering, can be because of liquid phase sintering after spin coating time, excessive dimensional contraction causes the breakage of top coat.(3) Al 2o 3/ TiC compound coating is core/shell structure, is conducive to improve the bonding strength between coating.(4) in liquid sintering process, realize surface TiO take CO as carbon source 2to the conversion of TiC, avoid the destruction to carbon balance in hard alloy substrate.(5) based on liquid sintering process, two kinds of coatings are without substep preparation, and coating and matrix manufacturing processed also combine.
Accompanying drawing explanation
Fig. 1 the inventive method and conventional gas-phase sedimentation are prepared Al 2o 3/ TiC coated carbides process schematic representation
embodiment.
Example 1: first by Al (NO 3) 3being made into concentration expressed in percentage by volume with deionized water is 0.8% solution, adds ammoniacal liquor regulator solution pH value to 8, stirs 2h with magnetic stirring apparatus at 25 ℃, and the speed of magnetic agitation is 25r/mi, then places 8h, forms Al (OH) 3colloidal sol; Add again TiCl 4, make its concentration expressed in percentage by volume for being 0.16%, be equivalent to Al (NO 3) 320% of concentration expressed in percentage by volume, and add ammoniacal liquor to regulate pH value to 8.2 stirs 1h with magnetic stirring apparatus at 50 ℃, and the speed of magnetic agitation is 25r/min, then places 10h, generation Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol, Al (NO 3) 3, TiCl 4be analytical pure with ammoniacal liquor.Take various raw material powders batching, TiC accounts for 3%, TaC and accounts for 2%, NbC and account for 2%, Co and account for 10% by weight percentage again, and all the other are WC; Mixed powder through 56h ball milling, 400 eye mesh screens filter, 90 ℃ dry, mix in the ratio of 70ml/kg that sodium butadiene rubber forming agent is mixed forming agent, compression moulding obtains Wimet green compact under 350MPa pressure; Wimet green compact are warmed up to 1290 ℃ in vacuum sintering furnace, and heat-up rate is 6 ℃/min, and vacuum tightness is 3Pa, and are incubated 1h to complete solid state sintering, the base substrate that formation density is 88%.By Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol is spin-coated on the Wimet billet surface after solid state sintering, when spin coating, every layer turns 15s under the rotating speed of 550r/min, turn 25s with the rotating speed of 1100r/min again, every layer at 150 ℃, cure 1h after being painted with after and be cooled to 25 ℃ after be coated with again under one deck, the spin coating number of plies is 6 layers, forms Al in Wimet billet surface 2o 3/ TiO 2core/shell structure.Finally, there is to Al on surface 2o 3/ TiO 2the Wimet base substrate of core/shell structure sintering under CO atmosphere in low pressure atmosphere sintering oven, gaseous tension is 1MPa, and temperature is 1440 ℃, and soaking time is 0.5h, the Al of Wimet billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; After insulation finishes, be filled with argon gas and get rid of CO gas, maintenance argon pressure is 4MPa, and sintering temperature is constant, then is incubated 1h, realizes hard alloy substrate liquid phase sintering densification, and the cooling rate after liquid phase sintering finishes is 10 ℃/min, finally prepares surface and has Al 2o 3the coated carbides of/TiC compound coating.
Example 2: first by Al (NO 3) 3being made into concentration expressed in percentage by volume with deionized water is 3% solution, adds ammoniacal liquor regulator solution pH value to 9, stirs 5h with magnetic stirring apparatus at 50 ℃, and the speed of magnetic agitation is 50r/mi, then places 10h, forms Al (OH) 3colloidal sol; Add again TiCl 4, make its concentration expressed in percentage by volume for being 1.2%, be equivalent to Al (NO 3) 340% of concentration expressed in percentage by volume, and add ammoniacal liquor to regulate pH value to 8.4 stirs 4h with magnetic stirring apparatus at 70 ℃, and the speed of magnetic agitation is 40r/min, then places 11h, generation Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol, Al (NO 3) 3, TiCl 4be analytical pure with ammoniacal liquor.Take various raw material powder batchings, TaC accounts for 3%, Co and accounts for 8% by weight percentage again, and all the other are WC; Mixed powder through 48h ball milling, 400 eye mesh screens filter 95 ℃ dry, mix in the ratio of 80ml/kg that sodium butadiene rubber forming agent is mixed forming agent, compression moulding obtains Wimet green compact under 300MPa pressure; Wimet green compact are warmed up to 1250 ℃ in vacuum sintering furnace, and heat-up rate is 12 ℃/min, and vacuum tightness is 6Pa, and are incubated 2h to complete solid state sintering, the base substrate that formation density is 91%.By Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol is spin-coated on the Wimet billet surface after solid state sintering, when spin coating, every layer turns 15s under the rotating speed of 550r/min, turn 25s with the rotating speed of 1100r/min again, every layer at 200 ℃, cure 1h after being painted with after and be cooled to 27 ℃ after be coated with again under one deck, the spin coating number of plies is 4 layers, forms Al in Wimet billet surface 2o 3/ TiO 2core/shell structure.Finally, there is to Al on surface 2o 3/ TiO 2the Wimet base substrate of core/shell structure sintering under CO atmosphere in low pressure atmosphere sintering oven, gaseous tension is 3MPa, and temperature is 1420 ℃, and soaking time is 0.5h, the Al of Wimet billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; After insulation finishes, be filled with argon gas and get rid of CO gas, maintenance argon pressure is 5MPa, and sintering temperature is constant, then is incubated 1h, realizes hard alloy substrate liquid phase sintering densification, and the cooling rate after liquid phase sintering finishes is 5 ℃/min, finally prepares surface and has Al 2o 3the coated carbides of/TiC compound coating.

Claims (2)

1. the Al based on liquid sintering process 2o 3the preparation method of/TiC coated carbides, is characterized in that comprising successively following steps:
(1) Al (OH) 3/ Ti (OH) 4core/shell structure colloidal sol preparation: by Al (NO 3) 3being made into concentration expressed in percentage by volume with deionized water is 0.5%～3% solution, adds ammoniacal liquor regulator solution pH value to 8～9, stirs 1～6h with magnetic stirring apparatus at 20～60 ℃, then places 6～12h, forms Al (OH) 3colloidal sol; Add again TiCl 4, making its concentration expressed in percentage by volume is Al (NO 3) 35%～45% of concentration expressed in percentage by volume, and add ammoniacal liquor to regulate pH value to 8～9, at 40～90 ℃, stir 1～6h with magnetic stirring apparatus, then place 6～12h, generation Ti(OH) 4coated Al (OH) 3al (OH) 3/ Ti(OH) 4core/shell structure colloidal sol;
(2) Wimet green compact solid state sintering: take various raw material powders batching, TiC accounts for 0～15%, TaC and accounts for 0～15%, NbC and account for 0～10%, Co and account for 4～12% by weight percentage, and all the other are WC; Mixed powder through ball milling, filtration, be dried, mix forming agent, compression moulding obtains Wimet green compact; Wimet green compact are warmed up to 1150～1300 ℃ in vacuum sintering furnace, and vacuum tightness is 3～10Pa, and are incubated 1～3h to complete solid state sintering, the base substrate that formation density is 85%～95%;
(3) spin coating and Wimet 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 Wimet billet surface after solid state sintering, when spin coating, every layer turns 15s under the rotating speed of 550r/min, turn 25s with the rotating speed of 1100r/min again, every layer be coated with again after curing 1h and be cooled to 20～30 ℃ at 115～230 ℃ after being painted with under one deck, the spin coating number of plies is 3～6 layers, forms Al in Wimet billet surface 2o 3/ TiO 2core/shell structure;
(4) Al is manufactured in liquid phase sintering 2o 3/ TiC coated carbides: there is to Al on surface 2o 3/ TiO 2the Wimet base substrate of core/shell structure sintering under CO atmosphere in low pressure atmosphere sintering oven, gaseous tension is 1～3MPa, and temperature is 1400 ℃～1500 ℃, and soaking time is 0.5h, the Al of Wimet billet surface 2o 3/ TiO 2there is carbothermic reduction reaction and be transformed into Al 2o 3/ TiC coating; After insulation finishes, be filled with argon gas and get rid of 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 densification, prepares surface and has Al 2o 3the coated carbides of/TiC compound coating.
2. the Al based on liquid sintering process according to claim 1 2o 3the preparation method of/TiC coated carbides, it is further characterized in that:
(1) Al (NO 3) 3, TiCl 4be analytical pure with ammoniacal liquor; Preparation Al (OH) 3/ Ti (OH) 4when core/shell structure colloidal sol, the speed of magnetic agitation is 20～50r/min;
(2) when prepared by Wimet green compact, Ball-milling Time is 24～72h, filters and adopts 400 eye mesh screens, adopts 85～100 ℃ to be dried, and mixes sodium butadiene rubber forming agent, compression moulding under 300～500MPa pressure in the ratio of 70～90ml/kg;
(3), when Wimet green compact solid state sintering, heat-up rate is 5～15 ℃/min;
(4) cooling rate of liquid phase sintering after finishing is 5～15 ℃/min.
CN201410100937.6A 2014-03-19 2014-03-19 Based on the Al of liquid sintering process 2o 3/ TiC coated carbides preparation method Expired - Fee Related CN103820695B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410100937.6A CN103820695B (en) 2014-03-19 2014-03-19 Based on the Al of liquid sintering process 2o 3/ TiC coated carbides preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410100937.6A CN103820695B (en) 2014-03-19 2014-03-19 Based on the Al of liquid sintering process 2o 3/ TiC coated carbides preparation method

Publications (2)

Publication Number Publication Date
CN103820695A true CN103820695A (en) 2014-05-28
CN103820695B CN103820695B (en) 2016-02-10

Family

ID=50755978

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410100937.6A Expired - Fee Related CN103820695B (en) 2014-03-19 2014-03-19 Based on the Al of liquid sintering process 2o 3/ TiC coated carbides preparation method

Country Status (1)

Country Link
CN (1) CN103820695B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105296779A (en) * 2015-09-28 2016-02-03 济南大学 Titanium/aluminum oxide interface reaction control and optimization method
CN111172372A (en) * 2020-01-15 2020-05-19 晋城鸿刃科技有限公司 Method for processing hard alloy carburized product
CN114591084A (en) * 2022-02-17 2022-06-07 惠州学院 Method for preparing compact TiC ceramic at low temperature rapidly

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0598369A (en) * 1991-10-08 1993-04-20 Sumitomo Electric Ind Ltd Production of sintered hard alloy
JPH0874057A (en) * 1994-09-05 1996-03-19 Toyo Kohan Co Ltd Sintered compact coated with diamond by vapor phase synthesis
CN102174680A (en) * 2010-12-31 2011-09-07 陕西科技大学 A (Ti, zr)2AlC/Al2O3solid solution composite material and its preparation method
CN102268661A (en) * 2011-07-04 2011-12-07 成都理工大学 Method for preparing Al2O3/TiC composite coating hard alloy
CN102390852A (en) * 2011-08-16 2012-03-28 桂林理工大学 Method for preparing high-purity superfine Alpha-Al2O3 powder from microemulsion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0598369A (en) * 1991-10-08 1993-04-20 Sumitomo Electric Ind Ltd Production of sintered hard alloy
JPH0874057A (en) * 1994-09-05 1996-03-19 Toyo Kohan Co Ltd Sintered compact coated with diamond by vapor phase synthesis
CN102174680A (en) * 2010-12-31 2011-09-07 陕西科技大学 A (Ti, zr)2AlC/Al2O3solid solution composite material and its preparation method
CN102268661A (en) * 2011-07-04 2011-12-07 成都理工大学 Method for preparing Al2O3/TiC composite coating hard alloy
CN102390852A (en) * 2011-08-16 2012-03-28 桂林理工大学 Method for preparing high-purity superfine Alpha-Al2O3 powder from microemulsion

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105296779A (en) * 2015-09-28 2016-02-03 济南大学 Titanium/aluminum oxide interface reaction control and optimization method
CN111172372A (en) * 2020-01-15 2020-05-19 晋城鸿刃科技有限公司 Method for processing hard alloy carburized product
CN114591084A (en) * 2022-02-17 2022-06-07 惠州学院 Method for preparing compact TiC ceramic at low temperature rapidly
CN114591084B (en) * 2022-02-17 2023-08-18 惠州学院 Method for rapidly preparing compact TiC ceramic at low temperature

Also Published As

Publication number Publication date
CN103820695B (en) 2016-02-10

Similar Documents

Publication Publication Date Title
CN103290406B (en) Laser cladding in-situ synthesis ceramic phase reinforced Fe-base cladding layer and preparation method thereof
CN109161711B (en) Superfine crystal gradient hard alloy with double-gradient-layer structure on surface and preparation method thereof
CN102268661B (en) Method for preparing Al2O3/TiC composite coating hard alloy
CN102251234B (en) Method for preparing Al2O3 coated hard alloy based on sol-gel method
CN106191608B (en) A kind of hard alloy in low cobalt of high temperature resistant, wear resistant corrosion resistant and preparation method thereof
CN103741000B (en) Ultra-fine Grained gradient hard alloy of a kind of rich surface cobalt and preparation method thereof
CN105499576A (en) Method for preparing porous titanium-aluminium alloy through powder metallurgy
CN103820695B (en) Based on the Al of liquid sintering process 2o 3/ TiC coated carbides preparation method
CN101830092A (en) Method for preparing corrosion-resistant colored decorative film
CN103464764B (en) Metal matrix wear-resistant corrosion-resistant surface coating composite and preparation method thereof
WO2015192815A1 (en) Tungsten carbide-cubic boron nitride composite material and preparation method thereof
CN104120457A (en) Preparing method of metal-carbide-containing multi-layer multi-component composite material
CN104630589B (en) A kind of composite hard alloy material of tungsten carbide cladding and preparation method thereof
CN106011581A (en) Vanadium-containing non-magnetic Ti(C, N)-based metal ceramic and preparation method thereof
CN111235453A (en) Hard alloy with high-entropy alloy layer on surface and preparation method thereof
CN110306092A (en) A kind of Graded-structure Cemented Carbides and its preparation method and application
CN108480621A (en) A method of shaping rhenium component using spherical rhenium powder
CN109437909A (en) Tungsten carbide composite and preparation method thereof
CN103831222B (en) A kind of preparation of carbide surface non-laminar aluminum oxide/titanium carbide coating
CN106944628B (en) A kind of scrap hard alloy recycling prepares superfine WC-Co composite powder method
CN103691959A (en) Composite structure hard alloy gear and preparation method thereof
CN104131206A (en) Titanium carbonitride-based hard alloy high-speed wire guide wheel material and preparation method thereof
CN105777205A (en) Preparing method of abrasion-resistant and corrosion-resistant transparent aluminum oxide ceramic tube
CN103586474A (en) Method for manufacturing powder metallurgy shaped charge liner for oil-gas well jet cutter
Ogihara et al. Synthesis of super hard Ni–B/diamond composite coatings by wet processes

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160210

Termination date: 20180319