CN108486398B - Preparation method of tungsten carbide-cobalt hard alloy - Google Patents
Preparation method of tungsten carbide-cobalt hard alloy Download PDFInfo
- Publication number
- CN108486398B CN108486398B CN201810526357.1A CN201810526357A CN108486398B CN 108486398 B CN108486398 B CN 108486398B CN 201810526357 A CN201810526357 A CN 201810526357A CN 108486398 B CN108486398 B CN 108486398B
- Authority
- CN
- China
- Prior art keywords
- powder
- cobalt
- tungsten
- hard alloy
- carbon
- 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.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- 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
- C22C29/067—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 comprising a particular metallic binder
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a method for preparing tungsten carbide-cobalt hard alloy by one step of in-situ synthesis by utilizing discharge plasma, which takes tungsten powder, cobalt powder, carbon black, glucose and paraffin as raw materials, ball-milling and mixing the tungsten powder, the cobalt powder, the carbon black and the glucose according to a proportion, drying and sieving for later use; heating and dissolving paraffin by absolute ethyl alcohol, pouring ultrafine-grained tungsten-cobalt-carbon mixed powder, and continuously heating in a water bath and stirring until the absolute ethyl alcohol is volatilized; drying, sieving, loading into high-strength graphite mould, sintering by discharge plasma, and controlling heating rate, pressurizing rate and holding time to obtain the WC crystal grain-controllable compact tungsten carbide-cobalt hard alloy material. The method can effectively shorten the preparation process of the hard alloy and improve the comprehensive performance of the alloy.
Description
Technical Field
The invention relates to a preparation method of tungsten carbide-cobalt hard alloy, in particular to a method for preparing tungsten carbide-cobalt hard alloy by one step of discharge plasma in-situ synthesis, belonging to the field of material preparation.
Background
Tungsten carbide-cobalt cemented carbides consist mainly of a hard, wear resistant WC phase and a Co phase with good toughness. When the conventional vacuum and low-pressure sintering technology is used for preparing the hard alloy, in order to ensure that the densification is close to the best and eliminate pores as much as possible, the sintering temperature is required to exceed the eutectic temperature of a W-Co-C system of 1320 ℃ and be kept for a long time, the WC phase can be dissolved and separated out, and WC crystal grains grow; meanwhile, at the high temperature, solid-phase sintering is easy to occur among WC particles, and the particles are bonded and grown to influence the structure and the performance of the alloy; in addition, the traditional WC raw material is generated through the carbonization reaction of W powder and C, the preparation process is long, and the defect accumulation is easy to form.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing a tungsten carbide-cobalt hard alloy material by one-step sintering through in-situ synthesis of discharge plasma, which comprises the following steps:
(1) weighing W powder, Co powder, carbon black and glucose, mixing and ball-milling, wherein the ball-milling process parameters are as follows: the ball-material ratio is 3:1-10:1, the ball milling time is 24-96h, the ball milling medium is absolute ethyl alcohol, the ball milling tank and the milling balls are made of hard alloy materials, and the mixed powder after ball milling is subjected to vacuum drying and sieving to prepare ultrafine crystal tungsten-cobalt-carbon mixed powder;
(2) adding paraffin into absolute ethyl alcohol, heating to 60-80 ℃ in a water bath, continuously stirring until the paraffin is dissolved, pouring the superfine crystal tungsten-cobalt-carbon mixed powder prepared in the step (1), and continuously heating in the water bath and stirring until the solvent is evaporated to form viscous slurry; vacuum drying and sieving the slurry to obtain tungsten-cobalt-carbon mixed powder;
(3) and (3) loading the tungsten-cobalt-carbon mixed powder prepared in the step (2) into a high-strength graphite mould, and placing the high-strength graphite mould into discharge plasma sintering equipment for in-situ synthesis densification sintering, wherein the sintering process parameters are as follows: sintering pressure is 40-100MPa, heating rate is 20-100 ℃/min, heating from room temperature to 800-.
Preferably, the mass fraction of the W powder in the total amount of the raw materials (total amount of raw materials = mass of W powder + mass of Co powder + total mass of carbon black and carbon element contained in glucose) is 81.7-89.2%; the Co powder accounts for 5-13% of the total weight of the raw materials; the carbon black and the glucose are used in amounts of 5.3 to 5.8 percent by mass of the total mass of the carbon elements in the carbon black and the glucose, based on the mass of the carbon elements in the carbon black and the glucose, wherein the molar ratio of the carbon black to the C element in the glucose is 1:0 to 1: 1; the mass percentage of the dosage of the paraffin to the total amount of the raw materials is 0-2%. (carbon black, glucose and paraffin are three forms of carbon sources, wherein carbon elements are mainly added in two forms of pure carbon black and glucose, and paraffin is only used for adjusting the carbon content of the alloy).
Preferably, the average particle size of W powder is below 0.8 μm, the average particle size of Co powder is below 1.0 μm, and the purity of carbon black is above 99%.
Compared with the existing hard alloy material preparation method, the invention is characterized in that:
(1) in the existing method, W and C are firstly reacted to generate WC powder, then Co powder is added for ball milling, granulation and sintering to prepare the hard alloy. In the invention, W, Co and C (pure carbon black or carbon black and glucose) are ball-milled and mixed, and then paraffin is added in a solution form to finely adjust the carbon content of the powder, so that the C can be uniformly distributed in the powder, the diffusion path of the C during W powder carbonization is reduced, the carbonization time is shortened, and the growth of WC grains is effectively inhibited;
(2) the added glucose can be decomposed to form cracking C with higher activity in the subsequent reaction sintering process, so that W is more easily carbonized to generate WC; meanwhile, the water-soluble glucose can also improve the dispersion degree of the C element in the ball-milling mixed powder, reduce the diffusion path of the C in the carbonization process and promote the carbonization;
(3) in-situ synthesis is carried out on the mixed powder by adopting a discharge plasma technology to prepare the superfine hard alloy, the high-pressure rapid sintering characteristic of SPS is fully utilized, the temperature is respectively preserved for 10-30min at the temperature of 900 ℃ with 800 ℃ and 10-30min at the temperature of 1100 ℃ with 1000 ℃ with the addition of temperature, the decomposition of glucose and paraffin is promoted to form activated carbon, and the carbonization of W powder is promoted;
(4) the spark plasma sintering technology has the characteristics that rapid temperature rise and sintering and pressing can be carried out synchronously, when the spark plasma sintering technology is used for sintering and preparing hard alloy, sintering can be controlled to be carried out at a lower temperature, and at the moment, powder is subjected to solid-phase sintering or liquid phase appears in a short time to inhibit the growth of WC grains;
(5) the elements in the W, Co and C mixed powder are uniformly distributed, and the promotion effect of Co on W powder carbonization is utilized, so that W can be completely carbonized at the temperature lower than the conventional carbonization temperature, and the growth condition of WC grains is effectively reduced;
(6) the invention shortens the W powder carbonization and hard alloy sintering process into one step, the prepared hard alloy material is compact fine grain hard alloy material with the relative density of more than 98.5 percent, the preparation process route has less steps and low energy consumption, WC crystal grains in the prepared alloy are uniformly distributed and have excellent mechanical property, and important technical support is provided for the batch production of the ultrafine grain hard alloy material.
Drawings
FIG. 1 is a scanning electron microscope image of the ultra-fine W-Co-C mixed powder after ball milling in example 3;
fig. 2 is a scanning electron microscope image of the ultra-fine grain tungsten carbide-cobalt cemented carbide material prepared in example 3.
Detailed Description
The following examples further illustrate the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Respectively weighing 176.4g of W powder with the average particle size of 0.8 mu m, 12g of Co powder with the average particle size of 1.0 mu m and 11.6g of carbon black with the average particle size of 0.6 mu m and the purity of 99% according to the proportion of WC-6% Co, putting the W powder and the carbon black into a lining hard alloy ball milling tank, adding 1000g of hard alloy balls with the diameter of 10mm according to the ball-to-material ratio of 5:1, ball milling the mixture for 48 hours by using absolute ethyl alcohol as a ball milling medium, then putting the powder into a vacuum drying oven for drying, and sieving the mixture to obtain superfine tungsten-cobalt-carbon mixed powder;
adding 300mL of absolute ethyl alcohol into a beaker, heating the beaker to 80 ℃ in a water bath, weighing 2g of paraffin, pouring the paraffin into the beaker, continuously stirring the paraffin, pouring the superfine crystal tungsten-cobalt-carbon mixed powder prepared by ball milling into the beaker, and continuously heating and stirring the mixture in the water bath until the absolute ethyl alcohol is evaporated to be viscous; drying in a vacuum drying oven, and sieving in a vacuum glove box to obtain mixed powder of tungsten, cobalt and carbon;
loading the tungsten-cobalt-carbon mixed powder into a high-strength graphite mould, and putting the high-strength graphite mould into discharge plasma sintering equipment for in-situ reaction synthesis densification sintering, wherein the sintering process parameters are as follows: sintering pressure is 50MPa, heating rate is 60 ℃/min, heat preservation is carried out for 30min at 800 ℃, heat preservation is carried out for 30min at 1100 ℃, then heating is carried out to 1250 ℃, heat preservation is carried out for 5min, heating is stopped after heat preservation is finished, furnace cooling is carried out to room temperature, and the superfine crystal tungsten carbide-cobalt hard alloy material with the relative density of 98.5% is prepared, and the mechanical property is shown in table 1.
Example 2
According to the proportion of WC-13% Co, 81.7g of W powder with the average particle size of 0.6 mu m, 13g of Co powder with the average particle size of 0.8 mu m, 2.7g of carbon black with the average particle size of 0.3 mu m and the purity of 99.9% and 6.7g of analytically pure glucose are respectively weighed, the W powder and the Co powder are put into a lining hard alloy ball milling tank, 1000g of hard alloy balls with the diameter of 10mm are added according to the ball-to-material ratio of 10:1, the ball milling medium is absolute ethyl alcohol, ball milling is carried out for 24 hours, then the powder is put into a vacuum drying oven to be dried and sieved to prepare ultrafine crystal tungsten-cobalt-carbon mixed powder;
placing the ultra-fine grain tungsten-cobalt-carbon mixed powder into a high-strength graphite die, and placing the high-strength graphite die into discharge plasma sintering equipment for in-situ reaction synthesis densification sintering, wherein the sintering process parameters are as follows: sintering at 60MPa, heating rate of 100 ℃/min, maintaining at 900 ℃ for 10min, maintaining at 1050 ℃ for 10min, heating to 1250 ℃ for 10min, stopping heating after the temperature is maintained, and cooling to room temperature along with the furnace to obtain the ultrafine grain tungsten carbide-cobalt hard alloy material with the relative density of 99.2%, wherein the mechanical properties are shown in Table 1.
Example 3
Respectively weighing 168.9g of W powder with the average particle size of 0.1 micrometer and 20g of Co powder with the average particle size of 0.1 micrometer according to the proportion of WC-10% Co, 5.55g of carbon black with the average particle size of 0.1 micrometer and the purity of 99.99% and 13.89g of analytically pure glucose, putting the powder into a lining hard alloy ball milling tank, adding 600g of hard alloy small balls with the diameter of 10mm according to the ball-to-material ratio of 3:1, ball milling the mixture for 96 hours by using absolute ethyl alcohol as a ball milling medium, then putting the powder into a vacuum drying oven for drying, and sieving the powder to prepare ultrafine crystal tungsten-cobalt-carbon mixed powder, wherein a scanning electron microscope picture of the powder is shown in figure 1, the powder after ball milling has good dispersibility, the W can be contacted with the C, and the subsequent reaction sintering can be favorably carried;
adding 400mL of absolute ethyl alcohol into a beaker, heating the beaker to 60 ℃ in a water bath, weighing 4g of paraffin, pouring the paraffin into the beaker, continuously stirring the paraffin, pouring the superfine crystal tungsten-cobalt-carbon mixed powder prepared by ball milling into the beaker, and continuously heating and stirring the mixture in the water bath until the absolute ethyl alcohol is evaporated to be viscous; drying in a vacuum drying oven, and sieving in a vacuum glove box to obtain mixed powder of tungsten, cobalt and carbon;
loading the tungsten-cobalt-carbon mixed powder into a high-strength graphite mould, and putting the high-strength graphite mould into discharge plasma sintering equipment for in-situ reaction synthesis densification sintering, wherein the sintering process parameters are as follows: sintering pressure is 100MPa, heating rate is 20 ℃/min, heat preservation is carried out for 20min at 850 ℃, heat preservation is carried out for 20min at 1000 ℃, then heating is carried out for 20min when temperature preservation is finished, heating is stopped after heat preservation, furnace cooling is carried out to room temperature, and the superfine crystal tungsten carbide-cobalt hard alloy material with the relative density of 99.2% is prepared, wherein a scanning electron microscope picture of the material is shown in figure 2, WC crystal grains are uniform in size, the average grain size is about 0.52 mu m calculated by adopting an intercept method, and the mechanical properties are shown in Table 1.
TABLE 1 Properties of ultra-fine grained tungsten carbide-cobalt cemented carbide materials prepared in examples 1-3
Comparing the detection data in table 1 with the existing literature, it can be seen that the performance of the alloy prepared by the present invention is similar to that of the alloy prepared by the traditional process, but the process of the present invention is shorter than that of the traditional preparation process, the sintering temperature is lower, and the energy consumption for preparing the hard alloy can be effectively reduced.
Claims (5)
1. A preparation method of a tungsten carbide-cobalt hard alloy material comprises the following steps:
(1) weighing W powder, Co powder, carbon black and glucose, mixing and ball-milling, and vacuum drying and sieving the ball-milled mixed powder to obtain ultrafine-grained tungsten-cobalt-carbon mixed powder;
(2) adding paraffin into absolute ethyl alcohol, heating in water bath and continuously stirring until the paraffin is dissolved, pouring the superfine crystal tungsten-cobalt-carbon mixed powder prepared in the step (1), and continuously heating in water bath and stirring until the solvent is evaporated to form viscous slurry; vacuum drying and sieving the slurry to obtain tungsten-cobalt-carbon mixed powder;
(3) filling the tungsten-cobalt-carbon mixed powder prepared in the step (2) into a high-strength graphite mould, and putting the high-strength graphite mould into discharge plasma sintering equipment for in-situ synthesis densification sintering to prepare a tungsten carbide-cobalt hard alloy material;
the sintering process parameters in the step (3) are as follows: the sintering pressure is 40-100MPa, the heating rate is 20-100 ℃/min, the temperature is increased from room temperature to 800-.
2. The preparation method according to claim 1, wherein the W powder accounts for 81.7-89.2% by mass of the total amount of the raw materials; the Co powder accounts for 5-13% of the total weight of the raw materials; the total mass of carbon elements contained in the carbon black and the glucose accounts for 5.3-5.8% of the total mass of the raw materials, wherein the molar ratio of the carbon black to the C element in the glucose is 1:0-1: 1; the mass percentage of the dosage of the paraffin and the total amount of the raw materials is 0-2%; wherein the total amount of the raw materials = W powder mass + Co powder mass + total mass of carbon black and carbon element contained in glucose.
3. The production method according to claim 1 or 2, wherein the average particle size of the W powder is 0.8 μm or less, the average particle size of the Co powder is 1.0 μm or less, and the purity of the carbon black is 99% or more.
4. The method according to claim 1, wherein the ball milling process parameters in step (1): the ball-material ratio is 3:1-10:1, the ball milling time is 24-96h, the ball milling medium is absolute ethyl alcohol, and the ball milling tank and the milling balls are made of hard alloy materials.
5. The method according to claim 1, wherein the water bath in the step (2) is heated to 60 to 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810526357.1A CN108486398B (en) | 2018-05-29 | 2018-05-29 | Preparation method of tungsten carbide-cobalt hard alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810526357.1A CN108486398B (en) | 2018-05-29 | 2018-05-29 | Preparation method of tungsten carbide-cobalt hard alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108486398A CN108486398A (en) | 2018-09-04 |
| CN108486398B true CN108486398B (en) | 2020-04-07 |
Family
ID=63352339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810526357.1A Active CN108486398B (en) | 2018-05-29 | 2018-05-29 | Preparation method of tungsten carbide-cobalt hard alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108486398B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266940B (en) * | 2018-10-26 | 2021-04-09 | 南方科技大学 | Carbon-tungsten-cobalt composite material and preparation method and application thereof |
| CN109355522A (en) * | 2018-10-30 | 2019-02-19 | 湖南工业大学 | A kind of novel hard alloy and preparation method thereof |
| CN109226741A (en) * | 2018-10-30 | 2019-01-18 | 湖南工业大学 | A kind of hard alloy and preparation method thereof |
| CN109234595A (en) * | 2018-10-30 | 2019-01-18 | 湖南工业大学 | A kind of nonmagnetic hard alloy and preparation method thereof |
| CN109504868A (en) * | 2018-10-30 | 2019-03-22 | 湖南工业大学 | A kind of mine tool hard alloy and preparation method thereof |
| CN109234596A (en) * | 2018-10-30 | 2019-01-18 | 湖南工业大学 | A kind of hard alloy and its preparation method and application |
| CN109317680A (en) * | 2018-10-30 | 2019-02-12 | 湖南工业大学 | A kind of hard alloy and preparation method thereof suitable for Gear Processing |
| CN111940742B (en) * | 2020-08-08 | 2022-07-05 | 邹爱忠 | Preparation method of gradient hard alloy |
| CN114029497A (en) * | 2021-11-09 | 2022-02-11 | 北京工业大学 | Preparation of high-specific gravity tungsten nickel cobalt nano powder and alloy with uniform element distribution and small particle size |
| CN114836642B (en) * | 2022-05-10 | 2023-05-12 | 岭南师范学院 | Double-form hard alloy and preparation method thereof |
| CN115110077A (en) * | 2022-06-29 | 2022-09-27 | 潜江市江汉钻具有限公司 | Preparation method of high-performance PDC drilling tool ball teeth |
| CN115820043A (en) * | 2022-11-25 | 2023-03-21 | 浙江恒成硬质合金有限公司 | Coating for sintering hard alloy blade and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103695685B (en) * | 2013-12-26 | 2016-02-24 | 昆明理工大学 | A kind of microwave sintering reaction prepares the method for WC-Co hard alloy |
-
2018
- 2018-05-29 CN CN201810526357.1A patent/CN108486398B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108486398A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108486398B (en) | Preparation method of tungsten carbide-cobalt hard alloy | |
| CN107739950B (en) | WC-Co-cBN composite hard alloy and preparation method thereof | |
| CN109252081A (en) | A kind of high-entropy alloy Binder Phase ultrafine tungsten carbide hard alloy and preparation method thereof | |
| CN104451322B (en) | A kind of tungsten carbide base carbide alloy and preparation method thereof | |
| WO2015161732A1 (en) | Method for preparing cobalt-coated nanometer wc crystal composite powder and ultra-fine grain cemented carbide | |
| CN113817947B (en) | Coarse WC (wolfram carbide) grain reinforced superfine hard alloy and preparation method thereof | |
| CN109943739B (en) | Method for preparing ultrafine-grained WC-Co hard alloy by plasma ball milling | |
| CN110964965A (en) | High-entropy alloy binding phase tungsten carbide hard alloy for water jet cutter and preparation method thereof | |
| CN112921227B (en) | Tungsten carbide-cobalt hard alloy and preparation method thereof | |
| CN113106281B (en) | Preparation method of yttrium oxide doped tungsten-based nano composite powder and alloy thereof | |
| CN114538929A (en) | Preparation method of high-density boron carbide ceramic | |
| CN113004052B (en) | Multi-walled carbon nanotube toughened boron carbide-based ceramic material and preparation method and application thereof | |
| CN109665848B (en) | Ultrahigh-temperature SiC-HfB2Composite ceramic and preparation method and application thereof | |
| CN112941352B (en) | Hard alloy and preparation method thereof | |
| CN110699617B (en) | Preparation method of graphene and aluminum oxide whisker co-reinforced copper-based composite material and product thereof | |
| CN111204721A (en) | MnAlCxNn-1-xMethod for preparing phase powder | |
| CN110616344B (en) | Method for preparing superfine hard alloy by adopting nano-scale crystal grain inhibitor vanadium carbide | |
| CN114318163B (en) | Superfine multi-element prealloy powder for diamond tool and preparation method thereof | |
| CN115259859A (en) | Boron carbide bulletproof ceramic material and preparation method thereof | |
| CN112063871B (en) | Preparation method of coarse-particle hard alloy | |
| CN112921198A (en) | Preparation method of ultra-coarse grain hard alloy | |
| KR100636798B1 (en) | Method for manufacturing b4c sintered body having low density | |
| KR102345328B1 (en) | Manufacturing method for titanium parts using granule and titanium part manufactured using the same | |
| CN115287487B (en) | Preparation method of nano hard alloy | |
| CN111718196B (en) | Preparation method of tungsten aluminum carbide-titanium carbide hard material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |