CN106756391A - A kind of WC Co hard alloy preparation methods with duplex grain structure - Google Patents
A kind of WC Co hard alloy preparation methods with duplex grain structure Download PDFInfo
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- CN106756391A CN106756391A CN201611135743.5A CN201611135743A CN106756391A CN 106756391 A CN106756391 A CN 106756391A CN 201611135743 A CN201611135743 A CN 201611135743A CN 106756391 A CN106756391 A CN 106756391A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
- C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
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Abstract
The invention discloses a kind of WC Co hard alloy preparation methods with duplex grain structure.Decentralized processing is carried out to flaky graphite powder first, then with the flaky graphite powder after decentralized processing, WC powder, WO3Powder, Co powder are configured to compound for primary raw material, through ball milling, addition forming agent, compressing and degreasing process, high temperature sintering are finally carried out in vacuum sintering furnace, obtain the WC Co hard alloy with duplex grain structure.Duplex grain structure hard alloy prepared by the method, its little particle hard phase is introduced directly into by thin WC, and bulky grain hard phase is by WO3Pass through carbothermic reduction reaction in situ with flaky graphite powder to generate.The microscopic structure of resulting materials is uniform, while having bending strength higher, hardness and fracture toughness.It is primary raw material that the preparation method uses tungstic acid with low cost and flaky graphite powder, and cost is greatly reduced, and process is simple, and energy consumption is relatively low, has broad application prospects.
Description
Technical field
The present invention relates to a kind of WC-Co hard alloy preparation method with duplex grain structure, belong to PM technique neck
Domain.
Background technology
WC-Co hard alloy because with hardness is high, wearability is good, red hardness is high and chemical stability preferably etc. it is a series of excellent
Good characteristic, has been widely used as cutting element, geology and mine instrument, mould, constitutional detail, wear part, high-temperature-resistant structure part etc.,
It is described as " tooth of modern industry ".However, being constantly present between the hardness and toughness of Hardmetal materials is difficult to what is reconciled
Contradiction.When the WC grain in material is thinner, its hardness and intensity are higher, and wearability is preferable, but toughness is substantially relatively low；And work as
When WC grain in material is thicker, its toughness is preferable, but its hardness and wearability are then decreased obviously.Therefore, it is the different realities of adaptation
The demand of border operating mode, otherwise prepare Ultra-fine Grained (0.2-0.5 μm of crystallite dimension) or nanocrystalline (crystallite dimension<0.2 μm) hard conjunction
Gold, to meet the operating mode higher to intensity and hardness requirement；Prepare coarse-grain (2.6-6.0 μm of crystallite dimension) or super coarse-grain
(crystallite dimension>6.0 μm) hard alloy, to meet the operating mode higher to toughness reguirements.Above-mentioned deficiency is constrained to a certain extent
The development of hard alloy.
To solve the contradiction between Cemented Carbide Hardness and toughness, current industrial quarters mainly uses following two methods：One
It is prepares coating hard alloy to plant.But, the technological requirement of prepares coating hard alloy is high, and equipment investment is huge so that production
It is relatively costly；It is another then be to prepare Graded-structure Cemented Carbides.And the tedious process of Graded-structure Cemented Carbides is prepared, production
It is relatively costly.Liu Chao et al. (preparation of mixed crystal WC-8Co hard alloy and performance study, Central South University, 2014) is reported and passed through
By varigrained WC powder collocation dispensing, the duplex grain structure that can prepare a kind of hard-phase particles size in bimodal distribution is hard
Matter alloy, this material has two kinds of performance advantages of hard alloy of thickness concurrently, and inside and outside performance is consistent.However, due to thickness two
Plant difference in solubility of the WC powder in Binder Phase Co larger, most of fine grained WC can be preferential molten in liquid sintering process
Solution, and separated out in large particle surface, grown up so as to cause coarse-grained WC easily to be reunited so that this material prepared by the method
Material is difficult to obtain uniform microscopic structure, and its hard phase Size Distribution even can deviate script design requirement, so so far
Industrial production is not used successfully to.
In view of the foregoing, it is necessary to prepared by the duplex grain structure WC-Co hard alloy for developing a kind of high-performance and low-cost
Method.
The content of the invention
The present invention is solution the deficiencies in the prior art, there is provided prepared by a kind of WC-Co hard alloy with duplex grain structure
Method, to obtain even tissue and the preferable duplex grain structure hard alloy of comprehensive mechanical property.
Realize that concrete scheme of the invention is as follows：
A kind of WC-Co hard alloy preparation method with duplex grain structure, comprises the following steps：
Step (1)：Decentralized processing is carried out to flaky graphite powder using ultrasonic vibration method；
Step (2)：With by the flaky graphite powder of decentralized processing, WC powder, WO3Powder, Co powder are that raw material prepares compound,
Component including following mass fraction, W is 65.60-76.31, and C is 9.83-12.09, and O is 6.50-10.07, and Co is 5.07-
12.33；
Step (3)：By above-mentioned compound after ball milling, drying, adding forming agent, compressing, degreasing process, it is placed in true
It is sintered in empty stove, obtains the WC-Co hard alloy with duplex grain structure；
Described to be sintered in completing in a complete thermal cycle, vacuum is higher than 1.0Pa, first by the pressed compact after degreasing after
The continuous speed with 5 DEG C/min is warming up to 600 DEG C, is slowly heated up with 0.8 DEG C/min in 600-800 DEG C of stage；Then with 4 DEG C/min
Speed be warming up to 1160-1200 DEG C, and in this temperature 90-150min；The last speed with 3 DEG C/min is warming up to
1370-1410 DEG C, it is incubated 30-50min.
Further, it refers to be placed in flaky graphite powder to carry out decentralized processing to flaky graphite powder in the step (1)
In the ultrasonic vibration instrument of 1.2kw, decentralized medium is absolute ethyl alcohol, and purity >=99.5% of ethanol used, jitter time is 40-
60min。
Further, the C of addition is reducing WO completely in the step (2)3And by after the generation WC that is carbonized, should also make sintering
Remaining total C content is between (6.13%-0.079 × Co%) and (6.13%-0.058 × Co%) in body, to ensure
Finally tissue is in normal two-phase section to obtain alloy, and wherein Co% is the mass fraction of Co in corresponding component system.
Further, the ball milling in the step (3) refers to that material is placed in tumbling ball mill, and drum's speed of rotation is 30-
50rpm, ratio of grinding media to material is 5:1, the time is 12~18h.
Further, pressing pressure used by compressing operation is 150-200MPa in the step (3).
To realize this purpose, C in carbide alloy mixture after the O in removing tungstic acid, in should also making sintered body
Between (6.13%-0.079 × Co%) and (6.13%-0.058 × Co%), wherein Co% is phase to remaining total C content
Answer the mass fraction of Co in component system, with ensure gained alloy finally tissue in normal two-phase section, do not formed to tissue and
The η phases of the harmful third phase of performance, such as remaining graphite-phase or fragility.All the time, oxide is considered as having in hard alloy
Evil impurity, because they can make the angle of wetting between hard phase and Binder Phase become big in liquid sintering process, reduces its wetting
Property, so that deteriorate materials microstructure and performance, so all reducing the oxygen in powder as far as possible when hard alloy is prepared at present
Content.Although the present invention is with WO3Substantial amounts of O is have also been introduced while the form introducing portion W of powder, but by introducing corresponding content
Flaky graphite powder and rationally control sintering process can make O between 600-800 DEG C by reacting WO3+ 3C → W+3CO is complete
Full removing, and by WO3In-situ reducing is W.And now sintered body still in early stage the solid-phase sintering stage, its relative density compared with
Low, hole is in perforate state, and the gas for reacting generation can be escaped smoothly under vacuum.In the follow-up sintering stage, with
The continuation of temperature is raised, and reduction gained W powder may proceed to that following reaction occurs with remaining flaky graphite powder and Co powder order：
9W+3Co+4C→Co3W9C4；
6W+6Co+C→Co6W6C；
4W+2Co+C→Co2W4C；
2Co3W9C4+C→3Co2W4C+6WC；
W+C→WC；
2W+C→W2C；
3Co2W4C+5C→2Co3W3C+6WC；
Co3W9C4+3C→Co3W3C+6WC；Co3W3C+3C→3WC+3Co；
W2C+C→2WC。
The stage can make to lack carbon phase and flaky graphite powder reaction generation WC, and this kind of WC can heredity scarce carbon phase and flakey
The shape characteristic of graphite, eventually forms the coarse-grained WC crystal grain with obvious platy character.On the other hand, due to a large amount of graphite powders
Introducing so that the solution modeling process of little particle WC is largely suppressed, most of small after final liquid-phase sintering
Grain WC still retains original pattern and particle diameter substantially.Meanwhile, the reducibility gas CO discharged in carbothermic reduction process can make it
More thorough, the boundary between purification ceramic phase and metallic binding phase of the absorption oxygen removal on its original powder WC powder and Co powder surface
Face, is effectively improved the microscopic structure of alloy, strengthens the bond strength of boundary, and the purpose of its obdurability is improved so as to reach.
To realize this purpose, preparation method has following features：It is sintered in entering in vacuum drying oven of the vacuum higher than 1.0Pa
OK, including three phases.The pressed compact after degreasing is continued first be warming up to 600 DEG C with the speed of 5 DEG C/min, at 600-800 DEG C
Stage is slowly heated up with 0.8 DEG C/min, it is therefore an objective to carry out carbothermic reduction reaction, oxygen fully contained in removing tungstic acid, together
When enable the gas of generation to pass through perforate to be escaped from sintered body；Then 1160- is warming up to the speed of 4 DEG C/min
1200 DEG C, and in this temperature 90-150min, it is therefore an objective to make the carbon thermal reduction further carbonization of gained tungsten powder be carbonization
Tungsten；The last speed with 3 DEG C/min is warming up to burns 1370-1410 DEG C of temperature eventually, is incubated 30-50min, it is therefore an objective to carry out final
Liquid-phase sintering simultaneously obtains fine and close duplex grain structure sintered body.
Beneficial effect of the present invention is：
(1) the reducibility gas CO that carbon thermal reduction is produced can purify the interface between WC hard phases and Co Binder Phases, effectively
Improve the microscopic structure of alloy, strengthen the bond strength of boundary, therefore obtained duplex grain structure Mathematical Analysis of Al-li Alloy Containing Rare Earth is more equal
Even, comprehensive mechanical performance is more preferable；
(2) it is primary raw material that the present invention uses tungstic acid with low cost and carbon dust, and coarse granule tabular WC is in solid phase
Sintering stage in-situ preparation, can significantly reduce production cost and energy consumption, and technical process is simple；
(3) present invention only needs conventional equipment to production equipment without particular/special requirement, is conducive to commercial introduction application；
Specific embodiment
Technique effect of the invention is further illustrated below in conjunction with example.The raw material that following instance is used is WC powder, WO3
Powder, Co powder and flaky graphite powder.
Table 1 is 4 kinds of compounds of component prescription.It is prepared into mixing using 3 kinds of different technological parameters in embodiment 1-3
Crystal structure hard alloy, and its bending strength, hardness and palmqvist fracture toughnesses are determined respectively.
1 four kinds of component prescriptions of compound of table
| Composition | W | C | O | Co |
| 1# | 74.56 | 12.09 | 8.28 | 5.07 |
| 2# | 76.31 | 10.12 | 6.50 | 7.07 |
| 3# | 73.06 | 9.83 | 6.50 | 10.61 |
| 4# | 65.60 | 12.00 | 10.07 | 12.33 |
Embodiment 1：
1st, decentralized processing is carried out to flaky graphite powder using ultrasonic vibration method, is carried out in the ultrasonic vibration instrument of 1.2kw,
Decentralized medium is absolute ethyl alcohol, and purity >=99.5% of ethanol used, jitter time is 40min；
2nd, 4 kinds of compounds are weighed respectively according to table 1, graphite powder first forms suspension through above-mentioned decentralized processing, then again will
WC、WO3It is added thereto to form mixed liquor with Co powder；
3rd, ball milling, ball milling operation is carried out in tumbling ball mill, and drum's speed of rotation is 50rpm, and ratio of grinding media to material is 5:1, when
Between be 12h；
4th, forming agent is added, forming agent used is 15wt.% gasoline paraffin solution, and addition is compound 12wt.%；
5th, compressing, pressure used is 150MPa；
6th, degreasing：Using hydrogen dewaxing method, carried out in sintering furnace, the programming rate between 150-450 DEG C is 0.5
℃/min；
7th, sinter, carried out in vacuum drying oven of the vacuum higher than 1.0Pa, including three phases：First by the pressure after degreasing
Base continues to be warming up to 600 DEG C with the speed of 5 DEG C/min, is slowly heated up with 0.8 DEG C/min in 600-800 DEG C of stage；Then with 4
DEG C/speed of min is warming up to 1160 DEG C, and in this temperature 150min；The last speed with 3 DEG C/min is warming up to 1410
DEG C, 30min is incubated, obtain the WC-Co hard alloy with duplex grain structure.
Under above-mentioned preparation process condition, the performance of the cermet of heterogeneity proportioning is shown in Table 2.
The performance of the different metal ceramics that table 2 is prepared using technique 1
| Composition | 1# | 2# | 3# | 4# |
| Bending strength σb(MPa) | 2479 | 2664 | 2752 | 2968 |
| Hardness (HRA) | 91.5 | 90.8 | 89.6 | 88.2 |
| Fracture toughness (MPam1/2) | 15.8 | 17.7 | 22.3 | 26.5 |
Embodiment 2：
1st, decentralized processing is carried out to flaky graphite powder using ultrasonic vibration method, is carried out in the ultrasonic vibration instrument of 1.2kw,
Decentralized medium is absolute ethyl alcohol, and purity >=99.5% of ethanol used, jitter time is 50min；
2nd, 4 kinds of compounds are weighed respectively according to table 1, graphite powder first forms suspension through above-mentioned decentralized processing, then again will
WC、WO3It is added thereto to form mixed liquor with Co powder；
3rd, ball milling, ball milling operation is carried out in tumbling ball mill, and drum's speed of rotation is 40rpm, and ratio of grinding media to material is 5:1, when
Between be 15h；
4th, forming agent is added, forming agent used is 15wt.% gasoline paraffin solution, and addition is compound 12wt.%；
5th, compressing, pressure used is 180MPa；
6th, degreasing：Using hydrogen dewaxing method, carried out in sintering furnace, the programming rate between 150-450 DEG C is 0.5
℃/min；
7th, sinter, carried out in vacuum drying oven of the vacuum higher than 1.0Pa, including three phases：First by the pressure after degreasing
Base continues to be warming up to 600 DEG C with the speed of 5 DEG C/min, is slowly heated up with 0.8 DEG C/min in 600-800 DEG C of stage；Then with 4
DEG C/speed of min is warming up to 1180 DEG C, and in this temperature 120min；The last speed with 3 DEG C/min is warming up to 1390
DEG C, 40min is incubated, obtain the WC-Co hard alloy with duplex grain structure.
Under above-mentioned preparation process condition, the performance of the cermet of heterogeneity proportioning is shown in Table 3.
The performance of the different metal ceramics that table 3 is prepared using technique 2
| Composition | 1# | 2# | 3# | 4# |
| Bending strength σb(MPa) | 2456 | 2687 | 2801 | 2977 |
| Hardness (HRA) | 91.3 | 90.6 | 89.5 | 88.3 |
| Fracture toughness (MPam1/2) | 15.6 | 18.2 | 22.6 | 26.3 |
Embodiment 3：
1st, decentralized processing is carried out to flaky graphite powder using ultrasonic vibration method, is carried out in the ultrasonic vibration instrument of 1.2kw,
Decentralized medium is absolute ethyl alcohol, and purity >=99.5% of ethanol used, jitter time is 60min；
2nd, 4 kinds of compounds are weighed respectively according to table 1, graphite powder first forms suspension through above-mentioned decentralized processing, then again will
WC、WO3It is added thereto to form mixed liquor with Co powder；
3rd, ball milling, ball milling operation is carried out in tumbling ball mill, and drum's speed of rotation is 30rpm, and ratio of grinding media to material is 5:1, when
Between be 18h；
4th, forming agent is added, forming agent used is 15wt.% gasoline paraffin solution, and addition is compound 12wt.%；
5th, compressing, pressure used is 200MPa；
6th, degreasing：Using hydrogen dewaxing method, carried out in sintering furnace, the programming rate between 150-450 DEG C is 0.5
℃/min；
7th, sinter, carried out in vacuum drying oven of the vacuum higher than 1.0Pa, including three phases：First by the pressure after degreasing
Base continues to be warming up to 600 DEG C with the speed of 5 DEG C/min, is slowly heated up with 0.8 DEG C/min in 600-800 DEG C of stage；Then with 4
DEG C/speed of min is warming up to 1200 DEG C, and in this temperature 90min；The last speed with 3 DEG C/min is warming up to 1370 DEG C,
Insulation 50min, obtains the WC-Co hard alloy with duplex grain structure.
Under above-mentioned preparation process condition, the performance of the cermet of heterogeneity proportioning is shown in Table 4.
The performance of the different metal ceramics that table 4 is prepared using technique 3
| Composition | 1# | 2# | 3# | 4# |
| Bending strength σb(MPa) | 2433 | 2658 | 2773 | 2982 |
| Hardness (HRA) | 91.4 | 90.5 | 89.3 | 88.0 |
| Fracture toughness (MPam1/2) | 16.0 | 17.9 | 22.8 | 27.1 |
In this letter of authorization span, the technological parameter in the first two stage of sintering process to performance impact relatively
Greatly, only when the carbon thermal reduction in above-mentioned stage and carbonisation carry out complete, the hard alloy of above-mentioned each component prescription can be obtained
Obtain relatively good comprehensive mechanical property.In a word, in this power book span, its performance impact to hard alloy has
Limit.
The above embodiments are intended to illustrate the present invention, rather than limitation, therefore with it is of the invention
Any change in claims suitable implication and scope, is all considered as being included within the scope of the claims.
Concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, some improvement can also be made, this
A little improvement also should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of WC-Co hard alloy preparation method with duplex grain structure, it is characterised in that comprise the following steps：
Step (1)：Decentralized processing is carried out to flaky graphite powder using ultrasonic vibration method；
Step (2)：With by the flaky graphite powder of decentralized processing, WC powder, WO3Powder, Co powder are that raw material prepares compound, including
The component of following mass fraction, W is 65.60-76.31, and C is 9.83-12.09, and O is 6.50-10.07, and Co is 5.07-12.33；
Step (3)：By above-mentioned compound after ball milling, drying, adding forming agent, compressing, degreasing process, vacuum drying oven is placed in
In be sintered, obtain the WC-Co hard alloy with duplex grain structure；
Described to be sintered in completing in a complete thermal cycle, vacuum is higher than 1.0Pa, first by the pressed compact after degreasing continue with
The speed of 5 DEG C/min is warming up to 600 DEG C, is slowly heated up with 0.8 DEG C/min in 600-800 DEG C of stage；Then with the speed of 4 DEG C/min
Rate is warming up to 1160-1200 DEG C, and in this temperature 90-150min；The last speed with 3 DEG C/min is warming up to 1370-
1410 DEG C, it is incubated 30-50min.
2. the WC-Co hard alloy preparation method with duplex grain structure according to claim 1, it is characterised in that：It is described
It refers to that flaky graphite powder is placed in the ultrasonic vibration instrument of 1.2kw to carry out decentralized processing to flaky graphite powder in step (1),
Decentralized medium is absolute ethyl alcohol, and purity >=99.5% of ethanol used, jitter time is 40-60min.
3. the WC-Co hard alloy preparation method with duplex grain structure according to claim 1, it is characterised in that：It is described
The C of addition is reducing WO completely in step (2)3And by the way that after the generation WC that is carbonized, remaining total C content is situated between in should also making sintered body
Between (6.13%-0.079 × Co%) and (6.13%-0.058 × Co%), to ensure that finally tissue is in just gained alloy
Normal two-phase section, wherein Co% is the mass fraction of Co in corresponding component system.
4. the WC-Co hard alloy preparation method with duplex grain structure according to claim 1, it is characterised in that：It is described
Ball milling in step (3) refers to that material is placed in tumbling ball mill, and drum's speed of rotation is 30-50rpm, and ratio of grinding media to material is 5:1, when
Between be 12~18h.
5. the WC-Co hard alloy preparation method with duplex grain structure according to claim 1, it is characterised in that：It is described
Pressing pressure used by compressing operation is 150-200MPa in step (3).
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Cited By (8)
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| CN108526477A (en) * | 2018-05-03 | 2018-09-14 | 南京寒锐钴业股份有限公司 | A kind of preparation method of WC-Co hard alloy mixture |
| CN109706360A (en) * | 2019-01-30 | 2019-05-03 | 南京航空航天大学 | A kind of preparation method of high-strength tenacity heterogeneous texture WC-TiC-Co hard alloy |
| CN109778046A (en) * | 2019-01-30 | 2019-05-21 | 南京航空航天大学 | A kind of preparation method of low-cost and high-performance duplex grain structure WC-Co hard alloy |
| CN111485156A (en) * | 2020-04-28 | 2020-08-04 | 李启龙 | Preparation method of wear-resistant tungsten carbide alloy material |
| CN111826568A (en) * | 2020-07-09 | 2020-10-27 | 南昌航空大学 | Preparation method of WC-6 Co-graphite self-lubricating hard alloy |
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| CN112941352A (en) * | 2021-01-27 | 2021-06-11 | 崇义章源钨业股份有限公司 | Hard alloy and preparation method thereof |
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| CN108526477A (en) * | 2018-05-03 | 2018-09-14 | 南京寒锐钴业股份有限公司 | A kind of preparation method of WC-Co hard alloy mixture |
| CN109706360A (en) * | 2019-01-30 | 2019-05-03 | 南京航空航天大学 | A kind of preparation method of high-strength tenacity heterogeneous texture WC-TiC-Co hard alloy |
| CN109778046A (en) * | 2019-01-30 | 2019-05-21 | 南京航空航天大学 | A kind of preparation method of low-cost and high-performance duplex grain structure WC-Co hard alloy |
| CN111485156A (en) * | 2020-04-28 | 2020-08-04 | 李启龙 | Preparation method of wear-resistant tungsten carbide alloy material |
| CN111826568A (en) * | 2020-07-09 | 2020-10-27 | 南昌航空大学 | Preparation method of WC-6 Co-graphite self-lubricating hard alloy |
| CN111850369A (en) * | 2020-07-09 | 2020-10-30 | 南昌航空大学 | Method for preparing WC-6 Ni-graphite self-lubricating hard cutter material by mechanical alloying |
| CN112941352A (en) * | 2021-01-27 | 2021-06-11 | 崇义章源钨业股份有限公司 | Hard alloy and preparation method thereof |
| CN112941352B (en) * | 2021-01-27 | 2022-06-21 | 崇义章源钨业股份有限公司 | Hard alloy and preparation method thereof |
| CN114752835A (en) * | 2022-03-18 | 2022-07-15 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
| CN114752835B (en) * | 2022-03-18 | 2022-10-25 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
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