CN114561564B - Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio - Google Patents

Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio Download PDF

Info

Publication number
CN114561564B
CN114561564B CN202210190319.XA CN202210190319A CN114561564B CN 114561564 B CN114561564 B CN 114561564B CN 202210190319 A CN202210190319 A CN 202210190319A CN 114561564 B CN114561564 B CN 114561564B
Authority
CN
China
Prior art keywords
powder
lath
hard alloy
ball milling
carbon black
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
Application number
CN202210190319.XA
Other languages
Chinese (zh)
Other versions
CN114561564A (en
Inventor
宋晓艳
徐毛宝
刘雪梅
赵冲
吕皓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN202210190319.XA priority Critical patent/CN114561564B/en
Publication of CN114561564A publication Critical patent/CN114561564A/en
Application granted granted Critical
Publication of CN114561564B publication Critical patent/CN114561564B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

A preparation method of a hard alloy with lath-shaped WC with high proportion and large length-diameter ratio belongs to the field of hard alloy material preparation. The method comprises the following steps: ball milling cobalt powder, tungsten powder and carbon black as raw materials, and then carrying out chemical reaction in a vacuum furnace to prepare Co 2 W 4 C single phase of Co 2 W 4 C, single phase, carbon black and ball milling and spark plasma sintering. The hard alloy with lath WC with high proportion and large length-diameter ratio, which is obtained by the method, has the advantages that the content of lath WC crystal grains (area fraction on a two-dimensional section) is not lower than 90 percent, the average length-diameter ratio of the WC crystal grains on the two-dimensional section is 2.5-3.9, and the hard alloy has good comprehensive mechanical property.

Description

Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio
Technical Field
The invention belongs to the field of hard alloy material preparation, and particularly relates to a preparation method of a lath-shaped WC hard alloy with high proportion and large length-diameter ratio.
Background
The WC-Co hard alloy has high hardness, wear resistance, high elastic modulus, low expansion coefficient, high hardness and high strength at high temperature and other excellent performances, and may find its wide application in metal machining tool, mine excavation, petroleum drilling, national defense and military industry and other fields. In the WC-Co hard alloy, a WC hard phase is taken as a matrix and is a main source of the properties of high hardness, high wear resistance and the like of the hard alloy. In the prior method, WC-Co composite powder or WC and Co mixed powder is directly sintered to prepare a hard alloy block material, WC crystal grains in the sintered block do not have the characteristic of preferred orientation, the orientation of the WC crystal grains in the prepared hard alloy is randomly distributed, and the shape of the crystal grains is close to an equiaxial shape (the length-diameter ratio is slightly larger than 1, and the length-diameter ratio refers to the ratio of the long axis size to the short axis size of the WC crystal grains on a two-dimensional section). For WC crystals with a close-packed hexagonal structure, c/a is 0.98, the mechanical properties in the different crystal planes are anisotropic, e.g. with a hardness of 2100HV in the WC (0001) plane 30 While the hardness on the WC (10-10) surface is only 1080HV 30 . If the growth process of WC crystal grains can be regulated and controlled to obtain the orientation distribution of special crystal planes in the alloy, hard phase crystals can be regulated and controlledThe grain shape provides a new effective way for obtaining high-performance hard alloy, and has important significance for developing hard alloy materials applied in special environments.
Utilizing WC in the process of WC crystal grain growth<0001>Crystal orientation and in
Figure BDA0003524591250000011
The growth rate of the crystal orientation is inconsistent, and
Figure BDA0003524591250000012
crystal orientation growth rate is greater than<0001>The crystal orientation is expected to obtain the hard alloy material with WC in a strip shape with a larger length-diameter ratio. The methods for preparing lath-shaped WC grains are currently very limited. There are three main types: firstly, the addition of the compound inhibits WC<10-10>Directionally growing additives (such as TiC); and secondly, flattening the W by high-energy ball milling, reacting with the C, and carbonizing and sintering at high temperature to obtain the plate-shaped WC. The alloy prepared by the method has low lath WC content, and the length-diameter ratio of WC crystal grains is difficult to control. Alternatively, there are methods involving ternary compounds (e.g. Co) x W y C z ) Adding carbon, and sintering to prepare lath-shaped WC, but the method is characterized in that Co is used x W y C z The phase is complex, the grain structure obtained is usually not uniform, and it is difficult to ensure that a higher proportion of lath-shaped WC with a large aspect ratio is obtained.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hard alloy which can obtain high lath WC content, large WC grain length-diameter ratio and uniform grain structure distribution, and has good comprehensive mechanical properties, and the invention comprises the following steps:
(1) Cobalt powder, tungsten powder and carbon black are used as raw materials, wherein the particle size of the cobalt powder is 200-500 nm, the particle size of the tungsten powder is 100-500 nm, the particle size of the carbon black is 100-300 nm, and the weight ratio of cobalt: tungsten: carbon =2:4: (1.66-1.70) preparing Co-W-C powder according to the stoichiometric ratio; adding Co-W-C powder, hard alloy grinding balls and absolute ethyl alcohol into a hard alloy ball milling tank, and uniformly mixing, wherein the ball material ratio is (3-5): 1, ball milling time is 10-20 h, ball milling rotating speed is 80-120 r/min, stopping once every 1.5-2.5 h in the ball milling process, and stopping time is 30-50 min;
(2) Placing the prepared Co-W-C mixed powder into a vacuum furnace for chemical reaction, wherein the reaction temperature is 1275-1325 ℃, and the heat preservation time is 2.0-3.0 h; when the reaction temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the partial pressure of the argon is 120-180 mbar; obtaining Co through the reaction 2 W 4 A single phase C having an average particle size in the range of 300 to 500nm;
(3) Co obtained by the reaction 2 W 4 Mixing the single-phase powder C with carbon black uniformly, wherein the carbon black is added in Co 2 W 4 3.7-4.1% of the powder C, and the ball material ratio is (3-5): 1, ball milling time is 10-20 h, ball milling rotating speed is 80-120 r/min, stopping is carried out every 1.5-2.5 h in the ball milling process, and stopping time is 30-50 min;
(4) Mixing Co 2 W 4 C and carbon black are put into a discharge plasma sintering device for sintering, the sintering temperature is 1100-1200 ℃, the sintering pressure is 30-100 MPa, the heat preservation time is 3-5 min, and finally the WC-Co hard alloy block material with high proportion and large length-diameter ratio lath WC is obtained.
The content of the lath-shaped WC crystal grains (area fraction on a two-dimensional section) is not less than 90 percent, and the average length-diameter ratio of the WC crystal grains on the two-dimensional section is 2.5 to 3.9. The area fraction content of lath-shaped WC crystal grains on a two-dimensional section is increased by increasing the addition amount of carbon black and Co 2 W 4 Ratio of C powder mass, increasing Co 2 W 4 The grain size of the C powder is further improved by increasing the sintering temperature and reducing the sintering pressure. Carbon black addition amount and Co 2 W 4 The smaller the mass ratio of the C powder, the lower the sintering temperature and the higher the sintering pressure, the larger the average aspect ratio of lath-shaped WC grains.
The invention has the technical advantages and effects that:
(1) The invention prepares pure Co by determining the component proportion and the process parameters and utilizing the synthesis reaction for the first time 2 W 4 C single phase, thereby ensuring Co is formed in the subsequent heating sintering process 2 W 4 C carbonWhen WC is generated, the nucleation and growth of WC have no impurity blocking effect, and a key foundation is laid for preparing lath-shaped WC with characteristic orientation.
(2) Compared with the method for preparing the lath-shaped WC by prefabricating the flattened W through long-time high-energy ball milling and then carbonizing the flattened W, the method adopts Co 2 W 4 The mixed powder of C and carbon black is sintered, so that the problem of impurity introduction in the ball milling process is effectively avoided, and the defect density and stress concentration of high-energy ball milling in W are greatly reduced, so that the prepared WC crystal grain with characteristic orientation has good performance.
(3) The invention can regulate and control the distribution ratio and the length-diameter ratio of anisotropic WC grains by adjusting the carbon black and Co 2 W 4 Ratio of C powder, co 2 W 4 The grain size of the C powder, the sintering temperature and the sintering pressure are used for regulating and controlling the area fraction and the average length-diameter ratio of lath-shaped WC grains on the two-dimensional section.
(4) The lath-shaped WC prepared by the method has a larger length-diameter ratio (the average length-diameter ratio is up to 2.5-3.9) than that of the conventional method, and the proportion of lath-shaped WC grains in the hard alloy block is higher (the area fraction of the lath-shaped WC grains on a two-dimensional section is not less than 90 percent), so that the effect of an anisotropic WC matrix on the mechanical property of the hard alloy can be exerted, and the requirement on the hard alloy material under special application conditions can be met.
(5) The method is fundamentally different from the conventional preparation methods such as controlling the growth of crystal grains to prefer orientation by adding special compounds (such as TiC and the like) or obtaining the oriented growth of WC crystal grain structures in the vertical direction of load by directional pressurization in the sintering process. The method does not introduce any additive in component design, and the oriented and grown grain structure does not depend on the oriented sintering pressure, so that the method has more convenient feasibility and wider applicability.
Drawings
FIG. 1 shows an X-ray diffraction pattern and a scanning electron microscope profile of cobalt powder, tungsten powder and carbon black, wherein (a) shows the X-ray diffraction pattern and the scanning electron microscope profile of cobalt powder, (b) shows the X-ray diffraction pattern and the scanning electron microscope profile of tungsten powder, and (c) shows the X-ray diffraction pattern and the scanning electron microscope profile of carbon black.
FIG. 2 shows the Co prepared by the present invention 2 W 4 X-ray diffraction pattern of C single phase, wherein (a) is Co prepared in example 1 2 W 4 X-ray diffraction pattern of C single phase, (b) Co prepared in example 2 2 W 4 X-ray diffraction pattern of C single phase (C) Co prepared in example 3 2 W 4 X-ray diffraction pattern of C single phase.
Fig. 3 is an X-ray diffraction pattern of the WC-Co cemented carbide prepared according to the present invention, wherein (a) is the X-ray diffraction pattern of the cemented carbide prepared in example 1, (b) is the X-ray diffraction pattern of the cemented carbide prepared in example 2, and (c) is the X-ray diffraction pattern of the cemented carbide prepared in example 3.
Fig. 4 is a scanning electron microscope of the WC-Co cemented carbide prepared in the present invention, wherein (a) is the scanning electron microscope of the grain structure of the cemented carbide prepared in example 1, (b) is the scanning electron microscope of the grain structure of the cemented carbide prepared in example 2, and (c) is the scanning electron microscope of the grain structure of the cemented carbide prepared in example 3.
Figure 5 is a statistical representation of the aspect ratios of the WC grains in the WC-Co cemented carbide made according to the present invention, where (a) is the aspect ratio statistics of the WC in the cemented carbide made in example 1, (b) is the aspect ratio statistics of the WC in the cemented carbide made in example 2, and (c) is the aspect ratio statistics of the WC in the cemented carbide made in example 3.
Table 1 shows the hardness and fracture toughness measurements of WC-Co cemented carbides prepared in three examples of the present invention.
Detailed Description
The following examples further illustrate the present invention, but the present invention is not limited to the following examples. The following three examples illustrate the preparation of cemented carbide containing high aspect ratio lath-like WC, corresponding to cemented carbide materials with WC-13Co content.
Example 1
Cobalt powder, tungsten powder and carbon black are used as raw materials, wherein the particle size of the cobalt powder is 200nm, the particle size of the tungsten powder is 100nm, the particle size of the carbon black is 100nm, and the ratio of cobalt: tungsten: carbon =2:4:1.70 in a stoichiometric ratioCo-W-C powder; adding Co-W-C powder, hard alloy grinding balls and absolute ethyl alcohol into a hard alloy ball milling tank, and uniformly mixing, wherein the ball material ratio is 3:1, ball milling time is 20 hours, ball milling rotating speed is 80r/min, the ball milling process is stopped once every 2.5 hours, and the stopping time is 50min; placing the prepared Co-W-C mixed powder into a vacuum furnace for chemical reaction, wherein the reaction temperature is 1275 ℃, and the heat preservation time is 3.0h; when the reaction temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the pressure of the argon partial pressure is 180mbar; obtaining Co through the reaction 2 W 4 C, single phase; co obtained by reaction 2 W 4 C, uniformly mixing the single-phase powder and carbon black, wherein the addition amount of the carbon black is 4.1 percent of the total powder mass, and the ball material ratio is 3:1, ball milling time is 20 hours, ball milling rotating speed is 80r/min, stopping is carried out every 2.5 hours in the ball milling process, and stopping time is 50min; mixing Co 2 W 4 C, uniformly mixing the powder with carbon black, putting the powder into a discharge plasma sintering device for sintering, wherein the sintering temperature is 1200 ℃, the sintering pressure is 30MPa, and the heat preservation time is 3min; finally, the WC-Co hard alloy block material with the lath-shaped WC crystal grain content (area fraction on the two-dimensional section) of 95 percent and the average value of the WC length-diameter ratio of 2.92 is prepared. The morphology and phase analysis of the raw materials in the preparation process of this example are shown in FIG. 1, and the prepared Co 2 W 4 The X-ray diffraction analysis of the C phase is shown in figure 2, the phase analysis and the microstructure appearance of the prepared WC-Co hard alloy block material are respectively shown in figures 3 and 4, the length-diameter ratio statistical result of WC grains in the prepared WC-Co hard alloy is shown in figure 5, and the performance test result of the prepared WC-Co hard alloy block material is shown in table 1.
Example 2
Cobalt powder, tungsten powder and carbon black are used as raw materials, wherein the particle size of the cobalt powder is 350nm, the particle size of the tungsten powder is 300nm, the particle size of the carbon black is 200nm, and the ratio of cobalt: tungsten: carbon =2:4:1.68 into Co-W-C powder; adding Co-W-C powder, hard alloy grinding balls and absolute ethyl alcohol into a hard alloy ball milling tank, and uniformly mixing, wherein the ball material ratio is 4:1, ball milling time is 15h, ball milling rotating speed is 100r/min, stopping is carried out every 2.0h in the ball milling process, and stopping time is 40min; placing the prepared Co-W-C mixed powder into a vacuum furnace for chemical reactionThe reaction temperature is 1300 ℃, and the heat preservation time is 2.5h; when the reaction temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the partial pressure of argon is 150mbar; obtaining Co through the reaction 2 W 4 C, single phase; co obtained by reaction 2 W 4 C, uniformly mixing the single-phase powder and carbon black, wherein the addition amount of the carbon black is 3.9 percent of the total powder mass, and the ball material ratio is 4:1, ball milling time is 15h, ball milling rotating speed is 100r/min, stopping is carried out every 2.0h in the ball milling process, and stopping time is 40min; mixing Co 2 W 4 C, uniformly mixing the powder with carbon black, putting the powder into a discharge plasma sintering device for sintering, wherein the sintering temperature is 1150 ℃, the sintering pressure is 70MPa, and the heat preservation time is 4min; finally, the WC-Co hard alloy block material with the lath-shaped WC crystal grain content (area fraction on the two-dimensional section) of 92 percent and the average value of the WC length-diameter ratio of 3.25 is prepared. The morphology and phase analysis of the raw materials in the preparation process of this example are shown in FIG. 1, and the prepared Co 2 W 4 The X-ray diffraction analysis of the C phase is shown in figure 2, the phase analysis and the microstructure morphology of the prepared WC-Co hard alloy block material are respectively shown in figures 3 and 4, the statistical result of the length-diameter ratio of WC grains in the prepared WC-Co hard alloy is shown in figure 5, and the performance test result of the prepared WC-Co hard alloy block material is shown in table 1.
Example 3
Cobalt powder, tungsten powder and carbon black are used as raw materials, wherein the particle size of the cobalt powder is 500nm, the particle size of the tungsten powder is 500nm, the particle size of the carbon black is 300nm, and the ratio of cobalt: tungsten: carbon =2:4:1.66 into Co-W-C powder; adding Co-W-C powder, hard alloy grinding balls and absolute ethyl alcohol into a hard alloy ball milling tank, and uniformly mixing, wherein the ball material ratio is 5:1, ball milling time is 10 hours, ball milling rotating speed is 120r/min, stopping is carried out once every 1.5 hours in the ball milling process, and stopping time is 30min; placing the prepared Co-W-C mixed powder into a vacuum furnace for chemical reaction, wherein the reaction temperature is 1325 ℃, and the heat preservation time is 2.0h; when the reaction temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the partial pressure of argon is 120mbar; obtaining Co through the reaction 2 W 4 C, single phase; co obtained by reaction 2 W 4 Mixing the powder C and carbon black uniformly, wherein the carbon black is added3.7 percent of the total powder mass, and the ball-material ratio is 5:1, ball milling time is 10 hours, ball milling rotating speed is 120r/min, stopping is carried out once every 1.5 hours in the ball milling process, and stopping time is 30min; mixing Co 2 W 4 C, uniformly mixing the powder with carbon black, putting the powder into a discharge plasma sintering device for sintering, wherein the sintering temperature is 1100 ℃, the sintering pressure is 100MPa, and the heat preservation time is 5min; finally, the WC-Co hard alloy block material with the lath-shaped WC crystal grain content (area fraction on the two-dimensional section) of 90 percent and the average value of the WC length-diameter ratio of 3.80 is prepared. The morphology and phase analysis of the raw materials in the preparation process of this example are shown in FIG. 1, and the prepared Co 2 W 4 The X-ray diffraction analysis of the C phase is shown in figure 2, the phase analysis and the microstructure appearance of the prepared WC-Co hard alloy block material are respectively shown in figures 3 and 4, the length-diameter ratio statistical result of WC grains in the prepared WC-Co hard alloy is shown in figure 5, and the performance test result of the prepared WC-Co hard alloy block material is shown in table 1.
TABLE 1 Properties of WC-13Co cemented carbide bulk materials prepared in the examples
Figure BDA0003524591250000061
/>

Claims (3)

1. A preparation method of a hard alloy with high-proportion and large length-diameter ratio lath-shaped WC is characterized by comprising the following steps:
(1) Cobalt powder, tungsten powder and carbon black are used as raw materials, wherein the particle size of the cobalt powder is 200-500 nm, the particle size of the tungsten powder is 100-500 nm, the particle size of the carbon black is 100-300 nm, and the weight ratio of cobalt: tungsten: carbon =2:4: (1.66-1.70) preparing Co-W-C powder according to the stoichiometric ratio; adding Co-W-C powder, hard alloy grinding balls and absolute ethyl alcohol into a hard alloy ball milling tank, and uniformly mixing, wherein the ball material ratio is (3-5): 1, ball milling time is 10-20 h, ball milling rotating speed is 80-120 r/min, stopping is carried out every 1.5-2.5 h in the ball milling process, and stopping time is 30-50 min;
(2) Placing the prepared Co-W-C mixed powder into a vacuum furnace for chemical reaction, wherein the reaction temperature is 1275-1325 ℃, and the heat preservation time is 2.0-3.0 h; when the reaction temperature is highWhen the temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the partial pressure of the argon is 120-180 mbar; obtaining Co through the reaction 2 W 4 C single phase with average particle size of 300-500 nm;
(3) Co obtained by the reaction 2 W 4 Mixing the single-phase powder C with carbon black uniformly, wherein the addition amount of the carbon black is Co 2 W 4 3.7-4.1% of the powder C, and the ball material ratio is (3-5): 1, ball milling time is 10-20 h, ball milling rotating speed is 80-120 r/min, stopping once every 1.5-2.5 h in the ball milling process, and stopping time is 30-50 min;
(4) Mixing Co 2 W 4 C and carbon black are evenly mixed, and the mixture is put into a spark plasma sintering device for sintering, wherein the sintering temperature is 1100-1200 ℃, the sintering pressure is 30-100 MPa, and the heat preservation time is 3-5 min;
the hard alloy with high proportion and large length-diameter ratio lath-shaped WC refers to that: the integral number on the two-dimensional section of the content of the lathy WC crystal grains is not less than 90 percent, and the average length-diameter ratio of the WC crystal grains on the two-dimensional section is 2.5 to 3.9.
2. The method for producing a cemented carbide having a high ratio of length to diameter of lath-shaped WC according to claim 1, wherein the area fraction of the lath-shaped WC grains in the two-dimensional cross section is increased by increasing the amount of carbon black and the Co content 2 W 4 Mass ratio of C powder, increasing Co 2 W 4 C, increasing the particle size of the powder, increasing the sintering temperature and reducing the sintering pressure, thereby further improving the sintering temperature; carbon black addition amount and Co 2 W 4 The smaller the mass ratio of the C powder, the lower the sintering temperature and the higher the sintering pressure, the larger the average aspect ratio of lath-shaped WC grains.
3. A cemented carbide having a high proportion of lath WC with a large length to diameter ratio, produced by a method according to any of claims 1-2.
CN202210190319.XA 2022-02-28 2022-02-28 Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio Active CN114561564B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210190319.XA CN114561564B (en) 2022-02-28 2022-02-28 Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210190319.XA CN114561564B (en) 2022-02-28 2022-02-28 Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio

Publications (2)

Publication Number Publication Date
CN114561564A CN114561564A (en) 2022-05-31
CN114561564B true CN114561564B (en) 2023-04-07

Family

ID=81715157

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210190319.XA Active CN114561564B (en) 2022-02-28 2022-02-28 Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio

Country Status (1)

Country Link
CN (1) CN114561564B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59185702A (en) * 1983-04-06 1984-10-22 Mitsubishi Metal Corp Composite raw material powder for producing sintered hard alloy and its production
WO2009001929A1 (en) * 2007-06-27 2008-12-31 Kyocera Corporation Cemented carbide, cutting tool, and cutting device
JP5393004B2 (en) * 2007-06-27 2014-01-22 京セラ株式会社 Cemented carbide small diameter rod and cutting tool and miniature drill
CN105154703B (en) * 2015-08-11 2017-04-19 北京工业大学 Preparing method for pure single-phase ternary carbide Co6W6C
CN109175387B (en) * 2018-10-23 2021-05-25 北京工业大学 Method for preparing nanocrystalline WC-Co hard alloy by amorphous crystallization

Also Published As

Publication number Publication date
CN114561564A (en) 2022-05-31

Similar Documents

Publication Publication Date Title
Cheng et al. Texture formation in titanium nitride films prepared by chemical vapor deposition
CN109576547B (en) Ternary boride reinforced Ti (C, N) -based metal ceramic material and preparation method thereof
Yang et al. Effect of carbon content on microstructure and mechanical properties of WC-10Co cemented carbides with plate-like WC grain
Lao et al. Mutual promotion effect of crystal growth in TiN∕ SiC nanomultilayers
US10961606B2 (en) Preparation method of a WC cemented carbide with adjustable alignment of plate-shape grains
CN109778050B (en) WVTaTiZr refractory high-entropy alloy and preparation method thereof
US20140178139A1 (en) Method of manufacturing super hard alloy containing carbon nanotubes, super hard alloy manufactured using same, and cutting tool comprising super hard alloy
CN111809073A (en) Gradient hard alloy square block and preparation method thereof
CN114561564B (en) Preparation method of hard alloy with lath-shaped WC (wolfram carbide) with high proportion and large length-diameter ratio
CN113087533B (en) In-situ synthesis of Ti on SiC fiber surface by using SiC nano crystal particles 3 SiC 2 Method for preparing interface phase
US5326732A (en) Carbon-silicon carbide composite material and method for the preparation thereof
CN112723888B (en) High-entropy ceramic material and preparation method thereof
Zhang et al. Effect of holding time and pressure on the densification, microstructure and mechanical properties of hot pressed Al2O3-CA6-ZrO2/Ni multi-phase composites
CN113548891A (en) Two-phase cobalt tantalate ceramic block and preparation method thereof
CN1721367A (en) A kind of with aluminium sesquioxide dispersion-strengthened Ti2AlN ceramic composite and preparation method thereof
Kinoshita et al. Mechanisms for formation of highly oriented plate-like triangular prismatic WC grains in WC-Co base cemented carbides prepared from W and C instead of WC
CN114262229B (en) Preparation method and application of high-strength and high-toughness diboride-carbide complex-phase high-entropy ceramic
CN112313354A (en) Cemented carbide with alternative binder
JPH07278719A (en) Particulate plate crystal cemented carbide containing wc and its production
CN110512132B (en) Gradient hard alloy with long rod-shaped crystal grains as surface layer WC and no cubic phase and preparation method thereof
CN109175387B (en) Method for preparing nanocrystalline WC-Co hard alloy by amorphous crystallization
CN109180209B (en) Method for preparing silicon carbide nanowire reinforced graphite-silicon carbide composite material by adopting in-situ self-generation method
CN113403517A (en) Heterostructure CrCoNi-Al2O3Nano composite material and preparation method thereof
Shul’zhenko et al. New Diamond-Based Superhard Materials. Production and Properties. Review
CN113462944A (en) Boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, cermet and preparation method

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