CN113444953A - Hard alloy containing titanium and ruthenium and preparation method thereof - Google Patents

Hard alloy containing titanium and ruthenium and preparation method thereof Download PDF

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CN113444953A
CN113444953A CN202110737630.7A CN202110737630A CN113444953A CN 113444953 A CN113444953 A CN 113444953A CN 202110737630 A CN202110737630 A CN 202110737630A CN 113444953 A CN113444953 A CN 113444953A
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ruthenium
hard alloy
mixture
titanium
powder
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周新华
孟湘君
龙坚战
汪巍
管玉明
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Zhuzhou Cemented Carbide Group Co Ltd
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Zhuzhou Cemented Carbide Group Co Ltd
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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
    • C22C29/067—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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a titanium and ruthenium-containing hard alloy, which comprises 15-25% of (TI, W) C solid solution (TIC: WC: 4:6) with the granularity of 1.0-1.6 mu m, the balance of tungsten carbide with the granularity of 2.4-3.2 mu m, and 15.0-25.0% of cobalt and nickel. The preparation method of the hard alloy comprises the following steps: s1, carrying out ball milling pretreatment on ruthenium powder with the particle size of 1.5-2.0 mu m to obtain a first material; s2, ball-milling the first material and a (TI, W) C solid solution (TIC: WC: 4:6) with the granularity of 1.6-2.0 mu m to obtain a first mixture; s3, ball-milling the first mixture, tungsten carbide with the granularity of 20-25 mu m, cobalt powder and nickel powder to obtain a second mixture; and S4, drying, granulating, pressing and sintering the second mixture to obtain the bicrystal hard alloy. The addition of titanium and ruthenium simultaneously improves the wear resistance and fracture toughness of the alloy.

Description

Hard alloy containing titanium and ruthenium and preparation method thereof
Technical Field
The invention belongs to the technical field of hard alloy, and particularly relates to a hard alloy containing titanium and ruthenium and a preparation method thereof.
Background
In order to meet the requirements of mine tools, high-speed wire rollers, stamping dies and nonferrous metal processing and use and solve the contradiction between the toughness and the hardness of hard alloy, technologists have conducted a great deal of research and exploration in recent years, and the main approaches are bicrystal alloy, whisker toughening and addition of various carbides or intermetallic compounds such as Ni3 Al.
For example, chinese published patent, publication No. CN108441737A, published as 2018, 8 and 24, discloses a cemented carbide, and a preparation method and application thereof, including: 5-10 wt% of cobalt, 0.5-1.5 wt% of chromium carbide and the balance of tungsten carbide, wherein the tungsten carbide comprises non-flaky tungsten carbide grains and flaky crystal tungsten carbide, and the flaky crystal tungsten carbide accounts for 18-40 wt% of the total mass of the hard alloy. The hard alloy provided by the invention contains the appropriate amount of the flaky crystal tungsten carbide, can greatly improve the anti-adhesion abrasion performance of the alloy under the condition of considerable hardness, and can realize the 30% improvement of the rolling tonnage of the stainless steel wire by using the hard alloy as a roll collar for rolling the stainless steel wire.
The patent is characterized in that the tungsten carbide consists of non-flaked tungsten carbide grains and flaked tungsten carbide, wherein the flaked tungsten carbide accounts for 18-40 wt% of the alloy, and the alloy structure and performance can be improved, but it goes without saying that the flaked tungsten carbide is very difficult to obtain and the uniform mixing operation with the non-flaked tungsten carbide is also difficult.
Also, for example, chinese patent publication No. CN111187960A, published 2020, 5, 22, discloses a twinned cemented carbide and a method for preparing the same, which comprises tungsten carbide grains having a grain size of 1.6-2.0 μm and 5-10 μm. The content of tungsten carbide crystal grains with the granularity of 1.6-2.0 mu m is 60-80 wt% based on 100% of the total weight of the tungsten carbide crystal grains, and the balance is tungsten carbide crystal grains with the granularity of 5-10 mu m.
The preparation method of the patent bicrystal hard alloy comprises the following steps: s1, grinding first tungsten carbide powder with the particle size of 10-20 mu m to obtain a first material; s2, mixing the first material, second tungsten carbide powder with the granularity of 3-7 mu m and cobalt powder, and grinding to obtain a mixture; and S3, granulating, pressing and sintering the mixture to obtain the bicrystal hard alloy. The bicrystal hard alloy can meet the use requirements of machining, die manufacturing and the like, and solves the problem that the high fracture toughness and the high hardness of the macrocrystal WC-Co hard alloy are difficult to coexist.
The two tungsten carbides adopted by the patent are respectively 10-20 μm and 3-7 μm with the proportion of 4:1-3:2, the alloy crystal grains are respectively 5-10 μm and 1.6-2.0 μm, the hardness and the strength can be improved to a certain extent at the same time, but the problem of simultaneously and greatly improving the hardness and the strength cannot be fundamentally solved, and the preparation of the tungsten carbide with the granularity of 5-10 μm is very difficult.
Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and a method for preparing a cemented carbide containing titanium and ruthenium.
Disclosure of Invention
The invention aims to provide a titanium and ruthenium-containing hard alloy and a preparation method thereof aiming at the defects of the prior art, wherein the addition of titanium and ruthenium can greatly improve the hardness and the fracture toughness of WC-Co hard alloy, well solves the problem that the toughness and the hardness in the hard alloy production technology are both long-off and cannot be simultaneously improved, and well meets the requirements of mine tools, high-speed wire rollers, stamping dies and nonferrous metal processing and use.
According to one aspect of the present invention there is provided a cemented carbide containing titanium and ruthenium having a content of (TI, W) C solid solution (TIC: WC ═ 4:6) of 1.0 to 1.6 μm in size, calculated as 100% by total weight of carbide, of 17.6 to 33.3%, the balance being tungsten carbide of 2.4 to 3.2 μm in size, 15.0 to 25.0% cobalt and nickel, the raw materials being measured in fischer tropsch size and the alloy being made and then measured in grain size.
According to a preferred embodiment of the invention, the titanium content of the titanium and ruthenium containing cemented carbide is between 5% and 10%.
According to a preferred embodiment of the invention, the content of ruthenium in the titanium and ruthenium containing cemented carbide is 0.1-0.25%.
According to an aspect of the present invention, there is provided a method for preparing the above cemented carbide containing titanium and ruthenium, comprising the steps of:
s1, carrying out ball milling pretreatment on ruthenium powder with the particle size of 1.5-2.0 mu m for 2-4 hours to obtain a first material;
s2, ball-milling the first material and a (TI, W) C solid solution (TIC: WC: 4:6) with the granularity of 1.6-2.0 mu m for 10-12 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the granularity of 20-25 mu m, cobalt powder and nickel powder to obtain a second mixture;
and S4, drying, granulating, pressing and sintering the second mixture to obtain the bicrystal hard alloy.
According to a preferred embodiment of the present invention, the weight of the first carbide powder is 17.6 to 33.3% and the weight of the second carbide powder is 66.7 to 82.4% based on 100% of the sum of the weights of the first carbide powder and the second carbide powder.
According to a preferred embodiment of the invention, the sum of the contents of cobalt powder and nickel powder is 15.0-25.0%, based on 100% of the sum of the weights of all powders.
According to a preferred embodiment of the present invention, the ball milling pretreatment alcohol of the step S1 is added in an amount of 50 liters and ball milled for 2 to 4 hours.
According to a preferred embodiment of the present invention, the ball milling pretreatment alcohol of step S2 is added in an amount of 150 liters and ball milled for 10 to 12 hours.
Compared with the prior art, the invention has the beneficial effects that:
by applying the titanium and ruthenium-containing hard alloy in the hard alloy roller, the hardness and wear resistance of the alloy are greatly improved by adding titanium, the fracture toughness is greatly improved by adding ruthenium and a double-crystal structure, the wear resistance and the fracture toughness of the alloy are simultaneously improved, the titanium and ruthenium-containing hard alloy can be used for rolling special steel such as stainless steel, cord steel, welding wire steel and the like and rolling at low temperature, and the service life of a product is greatly prolonged and is very stable. The hardness and the fracture toughness of the titanium and ruthenium-containing hard alloy are obviously improved, the main contradiction between the hardness and the fracture toughness of the hard alloy is effectively solved, and the requirements of mine tools, high-speed wire rollers, stamping dies and nonferrous metal processing and use can be met.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is an SEM image of a twinned cemented carbide made according to example 1 of the present invention;
FIG. 2 is a graph comparing hardness of twinned cemented carbide made in accordance with example 1 of the present invention and cemented carbide having a binder phase content of 25% of the prior art;
FIG. 3 is a graph comparing hardness of twinned cemented carbide made in example 2 of the present invention and cemented carbide with a binder phase content of 20% according to the prior art;
FIG. 4 is a graph comparing hardness of twinned cemented carbide made in example 3 of the present invention and cemented carbide having a binder phase content of 15% of the prior art;
FIG. 5 is a comparison of transverse rupture strength of twinned cemented carbide made in accordance with example 4 of the present invention and cemented carbide having a binder phase content of 25% of the prior art;
FIG. 6 is a comparison of transverse rupture strength of twinned cemented carbide made in accordance with example 5 of the present invention and cemented carbide having a binder phase content of 20% of the prior art;
FIG. 7 is a comparison of transverse rupture strength of twinned cemented carbide made in accordance with example 6 of the present invention and cemented carbide having a 15% binder phase content according to the prior art;
FIG. 8 is a graph comparing fracture toughness for twinned cemented carbide made in example 3 of the present invention and cemented carbide with a binder phase content of 15% of the prior art;
FIG. 9 is a graph comparing the fracture toughness of twinned cemented carbide made in example 6 of the present invention and a prior art cemented carbide having a binder phase content of 15%.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are further described in detail below by way of examples with reference to the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of the embodiments of the present invention with reference to the accompanying drawings is intended to explain the general inventive concept of the present invention and should not be construed as limiting the invention.
Furthermore, in the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the disclosure. It may be evident, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are shown in schematic form in order to simplify the drawing.
Referring to fig. 1 to 9, according to one general technical concept of the present invention, hardness HRA of cemented carbide in examples of the present invention is measured using a rockwell hardness tester, and fracture toughness is measured using an indentation method using 100 kg pressure for 15% of cobalt powder and nickel powder.
The invention discloses a titanium and ruthenium-containing hard alloy which comprises a (Ti, W) C solid solution with the grain size of 1.0-1.6 mu m and tungsten carbide grains with the grain size of 2.4-3.2 mu m. Calculated by the total weight of 100 percent of carbide, the content of 1.6 to 2.0 mu m of solid solution is 17.6 to 33.3 percent, the balance is tungsten carbide crystal grains with the granularity of 2.4 to 3.2 mu m, and the content of 1.5 to 2.0 mu m of ruthenium is 0.1 to 0.25 percent. The preparation method of the titanium and ruthenium-containing hard alloy comprises the steps of carrying out ball milling pretreatment on ruthenium powder with the particle size of 1.5-2.0 micrometers for 2-4 hours, then adding a (TI, W) C solid solution (TIC: WC: 4:6) with the particle size of 1.6-2.0 micrometers, carrying out ball milling for 10-12 hours, then adding tungsten carbide, cobalt powder and nickel powder with the particle size of 20-25 micrometers, carrying out ball milling treatment, drying and granulating, then carrying out pressing and sintering, and finally obtaining the titanium and ruthenium-containing hard alloy.
The following is an illustration of specific embodiments of the present invention.
Example 1
S1, adding ruthenium powder with the particle size of 1.5 mu m, which accounts for 0.15 percent of the total mass of the hard alloy, into a ball mill, and then adding 50 liters of absolute alcohol to perform ball milling pretreatment for 2 hours to obtain a first material;
s2, ball-milling a first material, (TI, W) C solid solution (TIC: WC: 4:6) powder with the particle size of 1.6 mu m accounting for 30% of the total mass of the hard alloy and 150 liters of absolute alcohol for 10 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the particle size of 24.0 mu m accounting for 44.85 percent of the total mass of the alloy, cobalt powder and nickel powder accounting for 25 percent of the total mass of the hard alloy to obtain a second mixture;
and S4, drying, granulating, pressing and forming the second mixture, and finally sintering at 1450 ℃ and 6MPa to obtain the bicrystal hard alloy. The density of the obtained bicrystal hard alloy is 12.14g/cm3Hardness 82.5HRA and transverse rupture strength 2800 MPa.
Example 2
S1, adding ruthenium powder with the particle size of 1.5 mu m, which accounts for 0.10 percent of the total mass of the hard alloy, into a ball mill, and then adding 50 liters of absolute alcohol to perform ball milling pretreatment for 2 hours to obtain a first material;
s2, ball-milling a first material, 20% of (TI, W) C solid solution (TIC: WC: 4:6) powder with the particle size of 1.6 mu m and the total mass of the hard alloy and 150 liters of absolute alcohol for 10 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the particle size of 24.0 mu m accounting for 59.90 percent of the total mass of the hard alloy, cobalt powder and nickel powder accounting for 20 percent of the total mass of the hard alloy to obtain a second mixture;
and S4, drying, granulating and pressing the second mixture, and finally sintering at 1480 ℃ under the pressure of 6MPa to obtain the bicrystal hard alloy. The density of the obtained bicrystal hard alloy is 12.49g/cm3Hardness is 83.8HRA, and transverse rupture strength is 2860 MPa.
Example 3
S1, adding ruthenium powder with the particle size of 1.5 mu m, which accounts for 0.25 percent of the total mass of the hard alloy, into a ball mill, and then adding 50 liters of absolute alcohol to perform ball milling pretreatment for 2 hours to obtain a first material;
s2, ball-milling a first material, (TI, W) C solid solution (TIC: WC: 4:6) powder with the particle size of 1.6 mu m accounting for 15% of the total mass of the hard alloy and 150 liters of absolute alcohol for 10 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the particle size of 25.0 mu m accounting for 69.75 percent of the total mass of the hard alloy, cobalt powder and nickel powder accounting for 15 percent of the total mass of the hard alloy to obtain a second mixture;
and S4, drying, granulating, pressing and forming the second mixture, and finally sintering at 1520 ℃ and 10MPa to obtain the bicrystal hard alloy.The density of the obtained bicrystal hard alloy is 13.55g/cm3Hardness of 86.0HRA, transverse rupture strength of 2970MPa and rupture toughness of 21.5MPa/m1/2。
Example 4
S1, adding ruthenium powder with the particle size of 2.0 mu m accounting for 0.20 percent of the total mass of the hard alloy into a ball mill, and then adding 50 liters of absolute alcohol to perform ball milling pretreatment for 2 hours to obtain a first material;
s2, ball-milling a first material, (TI, W) C solid solution (TIC: WC: 4:6) powder with the particle size of 1.8 mu m accounting for 30% of the total mass of the hard alloy and 150 liters of absolute alcohol for 12 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the particle size of 21.5 mu m accounting for 44.80 percent of the total mass of the hard alloy, cobalt powder accounting for 25 percent of the total mass of the hard alloy and nickel powder to obtain a second mixture;
and S4, drying, granulating, pressing and forming the second mixture, and finally sintering at 1450 ℃ and 6MPa to obtain the bicrystal hard alloy. The density of the obtained bicrystal hard alloy is 12.15g/cm through measurement3Hardness of 82.7HRA and transverse rupture strength of 2820 MPa.
Example 5
S1, adding ruthenium powder with the particle size of 2.0 mu m accounting for 0.15 percent of the total mass of the hard alloy into a ball mill, and then adding 50 liters of absolute alcohol to perform ball milling pretreatment for 2 hours to obtain a first material;
s2, ball-milling a first material, 20% of (TI, W) C solid solution (TIC: WC: 4:6) powder with the particle size of 1.8 mu m and the total mass of the hard alloy and 150 liters of absolute alcohol for 12 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the particle size of 23.0 mu m accounting for 59.85% of the total mass of the hard alloy, cobalt powder and nickel powder accounting for 20% of the total mass of the hard alloy to obtain a second mixture;
and S4, drying, granulating and pressing the second mixture, and finally sintering at 1480 ℃ under the pressure of 10MPa to obtain the bicrystal hard alloy. The density of the obtained bicrystal hard alloy is 12.95g/cm3Hardness of 84.1HRA and transverse rupture strength of 2870 MPa.
Example 6
S1, adding ruthenium powder with the particle size of 2.0 mu m accounting for 0.25 percent of the total mass of the hard alloy into a ball mill, and then adding 50 liters of absolute alcohol to perform ball milling pretreatment for 2 hours to obtain a first material;
s2, ball-milling a first material, (TI, W) C solid solution (TIC: WC: 4:6) powder with the particle size of 2.0 mu m accounting for 15% of the total mass of the hard alloy and 150 liters of absolute alcohol for 12 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the particle size of 22.0 mu m accounting for 69.75 percent of the total mass of the hard alloy, cobalt powder and nickel powder accounting for 15 percent of the total mass of the hard alloy to obtain a second mixture;
and S4, drying, granulating, pressing and forming the second mixture, and finally sintering at 1520 ℃ and 6MPa to obtain the bicrystal hard alloy. The density of the obtained bicrystal hard alloy is 13.54g/cm3Hardness of 86.2HRA, transverse rupture strength of 2950MPa and rupture toughness of 21.3MPa/m1/2。
Representative data were selected from the measurements of the above examples to give the following table:
Figure BDA0003142136800000081
the above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A cemented carbide containing titanium and ruthenium characterised by a solid solution of C with a particle size of 1.0-1.6 μm and tungsten carbide grains of 2.4-3.2 μm, the cemented carbide containing titanium and ruthenium containing 15.0-25.0% cobalt and nickel.
2. The cemented carbide containing titanium and ruthenium according to claim 1, wherein the hardness of the cemented carbide is: 82-87 HRA;
the transverse rupture strength is: 2800 and 3000 MPa;
the density is: 12.1-13.6g/cm3；
Fracture toughness is more than or equal to 21.08MPa/m1/2。
3. The cemented carbide containing titanium and ruthenium according to claim 1, characterized in that the C solid solution content is 17.6-33.3% with the balance being tungsten carbide, calculated on the total weight of carbides as 100%.
4. A titanium and ruthenium containing cemented carbide according to claim 1 characterised in that the titanium content is 5-10%.
5. A cemented carbide containing titanium and ruthenium according to claim 1 characterised in that the ruthenium content is 0.1-0.25%.
6. A method for preparing titanium and ruthenium-containing hard alloy is characterized by comprising the following steps:
s1, carrying out ball milling pretreatment on ruthenium powder with the particle size of 1.5-2.0 mu m for 2-4 hours to obtain a first material;
s2, ball-milling the first material and the C solid solution with the granularity of 1.6-2.0 mu m for 10-12 hours to obtain a first mixture;
s3, ball-milling the first mixture, tungsten carbide with the granularity of 20-25 mu m, cobalt powder and nickel powder to obtain a second mixture;
and S4, drying, granulating, pressing and sintering the second mixture to obtain the titanium and ruthenium-containing hard alloy.
CN202110737630.7A 2021-06-30 2021-06-30 Hard alloy containing titanium and ruthenium and preparation method thereof Pending CN113444953A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1393116A (en) * 1971-05-28 1975-05-07 Int Nickel Ltd Hard metal articles and methods of treatment thereof
CN102433484A (en) * 2010-09-29 2012-05-02 成都邦普合金材料有限公司 Preparation method of hard alloy with double crystal structure
CN104404337A (en) * 2014-12-15 2015-03-11 株洲钻石切削刀具股份有限公司 Hard alloy and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1393116A (en) * 1971-05-28 1975-05-07 Int Nickel Ltd Hard metal articles and methods of treatment thereof
CN102433484A (en) * 2010-09-29 2012-05-02 成都邦普合金材料有限公司 Preparation method of hard alloy with double crystal structure
CN104404337A (en) * 2014-12-15 2015-03-11 株洲钻石切削刀具股份有限公司 Hard alloy and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HONG ZHANG ETAL: "Microstructure, mechanical properties, and cutting performances of WC-Co cemented carbides with Ru additions", 《CERAMICS INTERNATIONAL 47》 *
石丽秋等: "球磨时间对双晶结构的WC-TiC-Co/Ni硬质合金组织及性能的影响", 《硬质合金》 *

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Application publication date: 20210928

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