CN104294072A - Fast preparation method for gradient hard alloy/metal ceramic - Google Patents
Fast preparation method for gradient hard alloy/metal ceramic Download PDFInfo
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Abstract
The invention relates to a fast preparation method for a gradient hard alloy/metal ceramic. The fast preparation method comprises the following steps: by taking more or all elements of WC, TiCN, TiC, TaC/NbC, Mo2c, VC, Cr2C3, Co and Ni which are quantitative as raw materials, mixing in a certain proportion to prepare a mixed material and ball-milling, sieving and moulding to prepare a blank; and by using a microwave medium with the frequency of 300MHz-8GHz as a heat source, absorbing microwave energy by the blank and simultaneously adding a certain a mount of thin nitrogen to be ionized under microwave to generate microwave plasmas so as to achieve the process of quickly heating and nitriding the surface. The method overcomes the defects that by the conventional heating manner, a relatively long time is required to heat and insulate to form a required gradient structure and the preparation period is long and the energy consumption is high. The method is widely applied to titanium-containing hard alloys with a microwave absorption property and nitriding treatment of metal ceramics.
Description
Technical field
The present invention relates to a kind of high reliability of preparation fast gradient hard alloy/ceramic-metallic method, particularly relate to a kind of gradient hard alloy/ceramic-metallic fast preparation method based on microwave-microwave plasma mixture heating.
Background technology
The development of the development of machining, particularly High Speed Machining, the environment residing for cutter is more complicated, has higher requirement to the obdurability of cutting tool and wear resistance.The mid-90 in last century, (the K.Tsuda such as Nomura, A.Ikegaya, K.Isobe et al.Development of functionally graded sintered hard materials [J], Powder Metallurgy, 1996,39 (4): 296-300) original position diffusion technique is adopted to prepare the Graded-structure Cemented Carbides of rich surface Emission in Cubic (TiCN, TiN), both the intensity of Wimet had been maintained, surface is made again to have the wear resistance of Emission in Cubic, its cutting ability and TiC/TiCN/TiN/A1
2o
3multi-layer composite coatings is substantially suitable.The proposition of the Graded-structure Cemented Carbides of rich surface Emission in Cubic, makes material have the higher core of strength and toughness and the higher surface of wear resistance, and the development solving modern cutting technology is well to the requirement of cutter high strength and high-wearing feature.(the ChenLimin such as Lengauer, Walter Lengauer, Klaus Dreyer.Advances in modern nitrogen-containing hardmetals and cermets [J], International Journal of Refractory Metals and Hard Materials, 2000,6 (13): 343-351; K.Dreyer, D.Kassel, H.-W.Daub et al.Functionallygraded hardmetals and cermets:preparation, performance and production scale up [C], 2001,15th International Plansee Seminar, 768-783.) original position diffusion is carried out to comparatively systematic research for the formation mutually of the functionally gradient mechanically resistant material of rich surface Emission in Cubic, metallurgical reaction, liquid phase forming temperature, degassing temperature and microtexture etc., and have rated its cutting ability.Chinese patent CN102134660A discloses functionally gradient cemented carbide of a kind of rich surface Emission in Cubic and preparation method thereof, and its preparation process is also the method based on original position diffusion.This type of prepares the Graded-structure Cemented Carbides/sintering metal of rich surface Emission in Cubic by original position method of diffusion, and its preparation efficiency and surface layer thickness affect by N rate of diffusion in heat-processed.For the preparation of the preparation method of the functionally gradient cemented carbide of rich surface Emission in Cubic in above-mentioned document, the heater means adopted, all conventional nitrogen atmosphere sintering, it utilizes the heating member heatings such as graphite, by modes such as radiation, convection current, conduction, material from outward appearance to inner essence is heated up, pass into the nitrogen of certain pressure in suitable temperature, time simultaneously, this type of heating exist heat up and soaking time longer, the time formed needed for gradient-structure is also longer, preparation cycle is relative also longer, the more high defect of energy consumption.
Summary of the invention
For above-mentioned situation, the object of this invention is to provide a kind of gradient hard alloy/ceramic-metallic fast preparation method based on microwave-microwave plasma mixture heating, it can realize the rapid heating to blank, is easy to again control grain growing; And simple process is reliable, processing ease, production efficiency is high, with short production cycle, and capital contribution is few, economical and practical, energy-efficient, safety and sanitation, and clean low consumption, non-environmental-pollution, is convenient to penetration and promotion.
To achieve these goals, a kind of gradient hard alloy/ceramic-metallic fast preparation method, it comprises the following steps:
(I), prepare burden, select WC, TiCN, TiC, TaC/NbC, Mo
2c, VC, Cr
2c
3, in Co and Ni several or all to make raw material stand-by, the mass percent of each raw material is as follows:
WC?10％～89％，TiCN?5％～51％，TiC?0～30％，Mo
2C?0～15％，VC?0～2％，Cr
2C
3?0～2％，
TaC/NbC?0～10％，Co4％～15％，Ni?0～8％；
(II), raw material mixing, get by mass percentage above-mentioned several or all raw material carry out Homogeneous phase mixing, stand-by;
(III), stand-by raw material tinning, default abrasive parameters;
(IV), mixture sieves;
(V), base is become;
(VI), sinter.
To achieve these goals, its further step is:
The ball mill that the raw mill of step (III) is selected is QM-1SP4 type ball mill;
The sphere diameter that the raw mill of step (III) is selected is Φ 5 sintered carbide ball, and ratio of grinding media to material is 5 ~ 10:1;
The rotational speed of ball-mill that the raw mill of step (III) is selected is 250 ~ 300rpm, and Ball-milling Time is 60 ~ 150 hours;
It is select sieve aperture to be 200 object screens that the mixture of step (IV) sieves;
It is that the mixture after sieving directly loads in mould that the one-tenth base of step (V) makes, and makes blank under 300 ~ 350MPa pressure;
The sintering of step (VI) is: 1. loaded by the blank of compression molding in MW-L0316HV high vacuum microwave oven; 2. microwave-medium is 2.45GHz frequency; 3. extract vacuum in body of heater out, make vacuum tightness not higher than 1 × 10
-2pa; 4. start microwave source, enter microwave-microwave plasma Hybrid Heating;
The microwave heating process of step (VI) is by preheating, pass into gas, intensification, insulation temperature control operation are carried out;
The microwave heating process of step (VI) is by preheating 6 ~ 10 minutes, passes into 0.1 ~ 8 × 10 when temperature reaches 450 ~ 650 DEG C
4pa gas, carries out insulation temperature control when being warming up to 1400 ~ 1500 DEG C, and the insulation temperature control time is 5 ~ 30 minutes;
The microwave heating process of step (VI), the gas atmosphere passed into is pure nitrogen gas or nitrogen and hydrogen or nitrogen and argon gas.
A kind of gradient hard alloy/ceramic-metallic fast preparation method of the present invention, it adopts and gets quantitative WC, TiCN, TiC, TaC/NbC, Mo
2c, VC, Cr
2c
3, several or whole elements in Co, Ni make raw material, are made into compound by a certain percentage, make blank through ball milling-sieve-mold pressing; Make thermal source with 300MHz ~ 8GHz frequency microwave medium, make the oxides adsorb microwave energy in blank, and add a certain amount of thin nitrogen simultaneously and ionize under microwave and produce microwave plasma and completing and be rapidly heated and surfaces nitrided process; Which overcoming traditional heating mode needs the longer time to heat up and insulation, the gradient-structure needed for could being formed, and preparation cycle is long, the defect that energy consumption is high.
The beneficial effect that the present invention is produced compared to existing technology:
A () the present invention is in conjunction with microwave and microwave plasma Hybrid Heating, make material rapid temperature increases at short notice, form fine and close blank, make plasma source (nitrogen) participate in the reaction process of material simultaneously, utilize the feature that Ti and N avidity is high, form Emission in Cubic (TiCN, TiN) at material surface, thus prepare gradient hard alloy/cermet material;
B () the present invention application 2.45GHz frequency microwave medium makes thermal source, the microwave plasma generated after microwave kind is excited by microwave and gas heats blank rapidly, reaches energy-conservation, efficient object;
C () present invention reduces the sintering time needed for the heating of conventional resistive stove, and technique is simple, easy and simple to handle, homogeneous heating is reliable, heat-up rate is fast, and sintering time is short, and equipment investment is few, with short production cycle, high-efficiency energy-saving pollution-free, be easy to realize scale production, business potential is large, market outlook are very considerable, great popularization.
The present invention can be widely used in the nitriding treatment of the metal, pottery and composition thereof with microwave absorbing property.
Below in conjunction with drawings and Examples, the present invention is further detailed explanation.
Accompanying drawing explanation
Fig. 1 is the heating curve figure of embodiment 1 in the present invention.
Fig. 2 is the surface of embodiment 1 and the X-ray diffractogram in cross section in the present invention.
Fig. 3 is the scanning electron microscope diagram of the cross section of embodiment 1 in the present invention.
Embodiment
Shown in accompanying drawing, the ultimate principle of a kind of gradient hard alloy of the present invention/ceramic-metallic fast preparation method: it adopts and gets quantitative wolfram varbide-WC, titanium carbonitride-TiCN, titanium carbide-TiC, tantalum carbide-TaC, niobium carbide-NbC, molybdenum carbide-Mo
2c, vanadium carbide-VC, chromium carbide-Cr
2c
3, several or whole elements/compounds in cobalt-Co, nickel-Ni make raw material, are made into mixture in mass ratio, make blank through ball milling-sieve-mold pressing, heat-processed is undertaken by preheating, intensification, insulation, temperature control operation; During heating, thermal source is made with 2.45GHz frequency microwave medium, first carry out initial stage microwave preheating heating, a certain amount of nitrogen is passed into when being heated to certain temperature, make it ionize under microwave produce microwave plasma and make compound bulk material rapid temperature increases, the Nitrogen ion collision of highly ionized and impact compound body surface, and the feature of promotion chemical reaction that microwave has, accelerate the reaction of nitrogen-N and titanium carbide-TiC, while making chemical combination material rapid temperature increases, form the gradient hard alloy/cermet material of rich surface Emission in Cubic; Meanwhile, microwave is a kind of body type of heating in heat-processed, and simultaneously the compaction process of combination materials inside and outsidely to occur; Which overcome conventional heating methods thermo-efficiency low, the time is long, the unsound defect of agglomerated material, is a kind of gradient hard alloy/ceramic-metallic sintering technology of great potential.
By reference to the accompanying drawings, total embodiment of the present invention.A kind of gradient hard alloy/ceramic-metallic fast preparation method, first selected 2.45GHz frequency microwave medium stove is done to heat, sinter thermal source, WC 10% ~ 89%, TiCN 5% ~ 51%, TiC 0 ~ 30%, Mo in mass ratio
2c 0 ~ 15%, VC 0% ~ 2%, Cr
2c
30% ~ 2%, TaC/NbC 0 ~ 10%, Co 3%-15%, the percentage total amount of Ni 0%-8%, determine the ratio of TiCN and other additive, again Wimet/sintering metal is fully mixed by ball milling, after ball milling, mixture particle particle diameter is normal distribution with 0.5 ~ 0.6 μm, raw material loads in QM-1SP4 type ball mill stainless steel jar mill by the ratio of grinding media to material of 5 ~ 10:1, select Φ 5 sintered carbide ball, then set rotational speed of ball-mill as 250 ~ 300rpm, if Ball-milling Time is 60 ~ 150 hours, get the mixture after ball milling and cross 200 mesh sieves, mixture after sieving is put into mould, blank is made under 300 ~ 350MPa pressure, blank enters microwave oven and sinters, setting microwave preheating, heating, intensification, parameters in insulating process, heating utilizes the absorption of mixture to microwave to reach heat-dissipating early stage, and preheating simultaneously 6 ~ 10 minutes, when temperature reaches 450 ~ 650 DEG C, pass into 0.1 ~ 8 × 10
4pa gas, increases microwave power, and produce microwave plasma, temperature is increased to rapidly 1400 ~ 1500 DEG C, carries out insulation temperature control 5 ~ 30 minutes after intensification, then stops heating, allows material furnace cooling.
With reference to accompanying drawing, a kind of fast preparation method of gradient metal ceramic, it take sintering metal as raw material, adopts microwave-microwave plasma mixture heating, and by the control of atmosphere, prepares the gradient metal ceramic material of the high reliability of rich surface Emission in Cubic fast.With WC, TiCN, TiC, TaC/NbC, Mo
2c, VC, Cr
2c
3, several in Co, Ni or all make raw material, be made into mixture in mass ratio, and make blank through ball milling-sieve-mold pressing, then make finished product through sintering, its operation steps is:
(I) quantitative TiCN, TiC, WC, Mo is got
2c, VC, Cr
2c
3, powder in TaC/NbC, Co, Ni, be made into raw material according to following mass ratio, stand-by;
WC?10％～89％，TiCN?5％～51％，TiC?0～30％，Mo
2C?0～15％，VC?0％～2％，Cr
2C
30％～2％，TaC/NbC?0～10％，Co4％～15％，Ni?0％～8％；
(II) get stand-by raw material to load in QM-1SP4 type ball mill stainless steel jar mill, select Φ 5 sintered carbide ball, ratio of grinding media to material is 5 ~ 10:1, and rotational speed of ball-mill is 250 ~ 300rpm, and Ball-milling Time is 60 ~ 150 hours;
(III) mixture got after ball milling sieves, and sieve aperture is 200 orders;
(IV) get the mixture after sieving and put into mould, under 300 ~ 350MPa pressure, make blank;
(V) get the above-mentioned blank through compression molding to load in MW-L0316HV high vacuum microwave oven, microwave-medium is 2.45GHz frequency, opens mechanical pump, diffusion pump successively, extracts vacuum in body of heater out, makes vacuum tightness not higher than 1 × 10
-2pa, then starts microwave source, enters microwave-microwave plasma Hybrid Heating, sintering circuit;
(VI) heat-processed is undertaken by preheating, intensification, insulation, temperature control operation;
(VII) preheating 6 ~ 10 minutes under room temperature, passes into 0.1 ~ 8 × 10 when temperature reaches 450 ~ 650 DEG C
4pa gas, make to generate microwave plasma in microwave oven, carry out insulation temperature control when being warming up to 1400 ~ 1500 DEG C, the insulation temperature control time is 5 ~ 30 minutes, and then furnace cooling obtains gradient hard alloy/ceramic-metal combination.
In conjunction with following table, the percent mass proportioning component embodiment of each raw material is respectively in table.
Embodiment 1
(I) a certain amount of TiCN, WC, Mo is got
2c, NbC/TaC, Co, Ni, VC, Cr
2c
3, be made into raw material by 1 hurdle component in table, stand-by;
(II) get stand-by raw material to load in QM-1SP4 type ball mill stainless steel jar mill, select Φ 5 sintered carbide ball, if ratio of grinding media to material 10:1, rotational speed of ball-mill 250rpm, Ball-milling Time 90 hours;
(III) mixture got after ball milling crosses 200 mesh sieves;
(IV) get the mixture after sieving and put into mould, under 300MPa pressure, make blank;
(V) get the above-mentioned blank through compression molding to load in MW-L0316HV high vacuum microwave oven, if microwave-medium 2.45GHz frequency, open mechanical pump, diffusion pump successively, extract vacuum in body of heater out, make vacuum tightness not higher than 1 × 10
-2pa, then starts microwave source, enters microwave-microwave plasma Hybrid Heating, sintering circuit;
(VI) preheating 7 minutes under room temperature, passes into 6 × 10 when temperature reaches 500 DEG C
4pa nitrogen, make to generate microwave plasma in microwave oven, heat up and take 60 minutes, carry out insulation temperature control when being warming up to 1430 DEG C, insulation temperature control 15 minutes, then furnace cooling obtains gradient metal ceramic finished product.
Embodiment 2
(I) get a certain amount of WC, TiC, Co, be made into raw material by 2 hurdle components in table, stand-by;
(II) get stand-by raw material to load in QM-1SP4 type ball mill stainless steel jar mill, select Φ 5 sintered carbide ball, if ratio of grinding media to material 10:1, rotational speed of ball-mill 250rpm, Ball-milling Time 60 hours;
(III) mixture got after ball milling crosses 200 mesh sieves;
(IV) get the mixture after sieving and put into mould, under 350MPa pressure, make blank;
(V) get the above-mentioned blank through compression molding to load in MW-L0316HV high vacuum microwave oven, if microwave-medium 2.45GHz frequency, open mechanical pump, diffusion pump successively, extract vacuum in body of heater out, make vacuum tightness not higher than 1 × 10
-2pa, then starts microwave source, enters microwave-microwave plasma Hybrid Heating, sintering circuit;
(VI) preheating 7 minutes under room temperature, passes into 8 × 10 when temperature reaches 500 DEG C
4pa nitrogen, make to generate microwave plasma in microwave oven, carry out insulation temperature control when being warming up to 1430 DEG C, insulation temperature control 30 minutes, then furnace cooling obtains gradient hard alloy finished product.
Embodiment 3
(I) get a certain amount of WC, TiC, Co, be made into raw material by 3 hurdle components in table, stand-by;
(II) get stand-by raw material to load in QM-1SP4 type ball mill stainless steel jar mill, select Φ 5 sintered carbide ball, if ratio of grinding media to material 10:1, rotational speed of ball-mill 250rpm, Ball-milling Time 60 hours;
(III) mixture got after ball milling crosses 200 mesh sieves;
(IV) get the mixture after sieving and put into mould, under 350MPa pressure, make blank;
(V) get the above-mentioned blank through compression molding to load in MW-L0316HV high vacuum microwave oven, if microwave-medium 2.45GHz frequency, open mechanical pump, diffusion pump successively, extract vacuum in body of heater out, make vacuum tightness not higher than 1 × 10
-2pa, then starts microwave source, enters microwave-microwave plasma Hybrid Heating, sintering circuit;
(VI) preheating 8 minutes under room temperature, passes into 6 × 10 when temperature reaches 500 DEG C
4pa nitrogen, make to generate microwave plasma in microwave oven, carry out insulation temperature control when being warming up to 1430 DEG C, insulation temperature control 20 minutes, then furnace cooling obtains gradient hard alloy finished product.
Embodiment 4
(I) a certain amount of TiCN, WC, Mo is got
2c, NbC/TaC, Co, Ni, be made into raw material by 4 hurdle components in table, stand-by;
(II) get stand-by raw material to load in QM-1SP4 type ball mill stainless steel jar mill, select Φ 5 sintered carbide ball, if ratio of grinding media to material 10:1, rotational speed of ball-mill 250rpm, Ball-milling Time 90 hours;
(III) mixture got after ball milling crosses 200 mesh sieves;
(IV) get the mixture after sieving and put into mould, under 300MPa pressure, make blank;
(V) get the above-mentioned blank through compression molding to load in MW-L0316HV high vacuum microwave oven, if microwave-medium 2.45GHz frequency, open mechanical pump, diffusion pump successively, extract vacuum in body of heater out, make vacuum tightness not higher than 1 × 10
-2pa, then starts microwave source, enters microwave-microwave plasma Hybrid Heating, sintering circuit;
(VI) preheating 8 minutes under room temperature, passes into 6 × 10 when temperature reaches 500 DEG C
4pa nitrogen, make to generate microwave plasma in microwave oven, carry out insulation temperature control when being warming up to 1430 DEG C, insulation temperature control 30 minutes, then furnace cooling obtains gradient hard alloy finished product.
Embodiment 5
(I) get a certain amount of WC, TiC, Co, be made into raw material by 5 hurdle components in table, stand-by;
(II) get stand-by raw material to load in QM-1SP4 type ball mill stainless steel jar mill, select Φ 5 sintered carbide ball, if ratio of grinding media to material 10:1, rotational speed of ball-mill 250rpm, Ball-milling Time 90 hours;
(III) mixture got after ball milling crosses 200 mesh sieves;
(IV) get the mixture after sieving and put into mould, under 300MPa pressure, make blank;
(V) get the above-mentioned blank through compression molding to load in MW-L0316HV high vacuum microwave oven, if microwave-medium 2.45GHz frequency, open mechanical pump, diffusion pump successively, extract vacuum in body of heater out, make vacuum tightness not higher than 1 × 10
-2pa, then starts microwave source, enters microwave-microwave plasma Hybrid Heating, sintering circuit;
(VI) preheating 8 minutes under room temperature, passes into 8 × 10 when temperature reaches 500 DEG C
4pa nitrogen, make to generate microwave plasma in microwave oven, carry out insulation temperature control when being warming up to 1430 DEG C, insulation temperature control 15 minutes, then furnace cooling obtains gradient hard alloy finished product.
Below be only preferred embodiment of the present invention, according to above-mentioned design of the present invention, those skilled in the art also can make various amendment and conversion to this.Such as, the change etc. of ball milling parameter, compacting pressure.But similar this conversion and amendment all belong to essence of the present invention.
Claims (10)
1. gradient hard alloy/ceramic-metallic fast preparation method, is characterized in that it comprises the following steps:
(I), prepare burden, select WC, TiCN, TiC, TaC/NbC, Mo
2c, VC, Cr
2c
3, in Co and Ni several or all to make raw material stand-by, the mass percent of each raw material is as follows:
WC?10％～89％，TiCN?5％～51％，TiC?0～30％，Mo
2C?0～15％，VC?0～2％，Cr
2C
30～2％，
TaC/NbC?0～10％，Co?4％～15％，Ni?0～8％；
(II), raw material mixing, get by mass percentage above-mentioned several or all raw material carry out Homogeneous phase mixing, stand-by;
(III), stand-by raw material tinning, default abrasive parameters;
(IV), mixture sieves;
(V), base is become;
(VI), sinter.
2. a kind of gradient hard alloy according to claim 1/ceramic-metallic fast preparation method, is characterized in that the ball mill that the raw mill of step (III) is selected is QM-1SP4 type ball mill.
3. a kind of gradient hard alloy according to claim 1/ceramic-metallic fast preparation method, it is characterized in that the sphere diameter that the raw mill of step (III) is selected is Φ 5 sintered carbide ball, ratio of grinding media to material is 5 ~ 10:1.
4. a kind of gradient hard alloy according to claim 1/ceramic-metallic fast preparation method, it is characterized in that the rotational speed of ball-mill that the raw mill of step (III) is selected is 250 ~ 300rpm, Ball-milling Time is 60 ~ 150 hours.
5. a kind of gradient hard alloy according to claim 1/ceramic-metallic fast preparation method, it is characterized in that the mixture of step (IV) sieves is select sieve aperture to be 200 object screens.
6. a kind of gradient hard alloy according to claim 1/ceramic-metallic fast preparation method, it is characterized in that the one-tenth base of step (V) makes is that the mixture after sieving directly loads in mould, makes blank under 300 ~ 350MPa pressure.
7. a kind of gradient hard alloy according to claim 1/ceramic-metallic fast preparation method, is characterized in that the sintering of step (VI) is: 1. loaded by the blank of compression molding in MW-L0316HV high vacuum microwave oven; 2. microwave-medium is 2.45GHz frequency; 3. extract vacuum in body of heater out, make vacuum tightness not higher than 1 × 10
-2pa; 4. start microwave source, enter microwave-microwave plasma Hybrid Heating.
8. a kind of gradient hard alloy according to claim 7/ceramic-metallic fast preparation method, it is characterized in that the microwave heating process of step (VI) be by preheating, pass into gas, intensification, insulation temperature control operation carry out.
9. a kind of gradient hard alloy according to claim 7/ceramic-metallic fast preparation method, is characterized in that the microwave heating process of step (VI) is by preheating 6 ~ 10 minutes, passes into 0.1 ~ 8 × 10 when temperature reaches 450 ~ 650 DEG C
4pa gas, carries out insulation temperature control when being warming up to 1400 ~ 1500 DEG C, and the insulation temperature control time is 5 ~ 30 minutes.
10. a kind of gradient hard alloy according to claim 7/ceramic-metallic fast preparation method, is characterized in that the microwave heating process of step (VI), and the gas atmosphere passed into is pure nitrogen gas or nitrogen and hydrogen or nitrogen and argon gas.
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| CN104878267A (en) * | 2015-05-29 | 2015-09-02 | 南京理工大学 | TiCN-base metal ceramic tool material and its microwave sintering process |
| CN104988373A (en) * | 2015-08-06 | 2015-10-21 | 广东工业大学 | Surface-hardened gradient cemented carbide and preparation method thereof |
| CN105177388A (en) * | 2015-08-31 | 2015-12-23 | 苏州西凌铂睿特种材料有限公司 | Hard alloy material |
| CN105177390A (en) * | 2015-08-28 | 2015-12-23 | 北京科技大学 | Metal ceramics and preparation method thereof |
| CN107881389A (en) * | 2017-11-06 | 2018-04-06 | 株洲科力特新材料有限公司 | Ti (C, N) based ceramic metals and for preparing its preparation method |
| CN107916357A (en) * | 2017-10-31 | 2018-04-17 | 自贡硬质合金有限责任公司 | A kind of gradient hard alloy of heterogeneous texture and preparation method thereof |
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| CN113355578A (en) * | 2021-06-10 | 2021-09-07 | 河南工业大学 | Preparation method of Ti (C, N) -based metal ceramic |
| CN115198156A (en) * | 2022-07-05 | 2022-10-18 | 哈尔滨工业大学 | High-strength and high-toughness ultrafine-grained Ti (C, N) -based cermet and preparation method thereof |
| CN115198157A (en) * | 2022-07-05 | 2022-10-18 | 哈尔滨工业大学 | Grain growth induced pressureless sintering ultra-fine grain Ti (C, N) -based cermet densification method |
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