CN114561564A - 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

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CN114561564A
CN114561564A CN202210190319.XA CN202210190319A CN114561564A CN 114561564 A CN114561564 A CN 114561564A CN 202210190319 A CN202210190319 A CN 202210190319A CN 114561564 A CN114561564 A CN 114561564A
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宋晓艳
徐毛宝
刘雪梅
赵冲
吕皓
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Beijing University of Technology
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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 Co2W4C single phase of Co2W4C, 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 of the invention, has the lath WC crystal grain content (area fraction on the two-dimensional section) of not less than 90 percent and the two-dimensional sectionThe average length-diameter ratio of the upper WC crystal grains is 2.5-3.9, and the composite material has good comprehensive mechanical properties.

Description

Preparation method of lath-shaped WC hard alloy 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 crystal, it has close-packed hexagonal structure, c/a is 0.98, and its mechanical properties in different crystal planes are anisotropic, i.e. the hardness of WC (0001) plane is 2100HV30While the hardness on the WC (10-10) surface is only 1080HV30. If the growth process of WC crystal grains can be regulated and controlled to obtain the orientation distribution of a special crystal face in the alloy, a new effective way is provided for obtaining high-performance hard alloy from the angle of regulating the form of hard phase crystal grains, and the method has important significance for developing hard alloy materials applied under 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 not uniform, and
Figure BDA0003524591250000012
crystal orientation growth rate is greater than<0001>The crystal orientation of the alloy is expected to obtain the hard alloy material with WC in a lath 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 elongated additives (such as TiC); and secondly, flattening the W by high-energy ball milling, reacting with the C, and carrying out high-temperature carbonization and sintering to obtain the platy WC. The content of lath-shaped WC in the alloy prepared by the methodLower and the aspect ratio of the WC grains is difficult to control. In addition, there are methods of converting to ternary compounds (e.g., Co)xWyCz) Adding carbon, and sintering to prepare lath-shaped WC, but the method is characterized in that Co is usedxWyCzThe 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 proportion 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 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 reaction2W4A single phase C having an average particle diameter in the range of 300 to 500 nm;
(3) co obtained by reaction2W4Mixing the single-phase powder C with carbon black uniformly, wherein the addition amount of the carbon black is Co2W43.7-4.1% of the C powder by mass, and the ball-to-feed 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 Co2W4C and carbon black are put into a spark plasma sintering device for sintering,the sintering temperature is 1100-1200 ℃, the sintering pressure is 30-100 MPa, and the heat preservation time is 3-5 min, so that the WC-Co hard alloy block material with the lath WC and the high proportion and the large length-diameter ratio is obtained.
The content (area fraction on a two-dimensional section) of the lath-shaped WC crystal grains is not less than 90%, and the average length-diameter ratio of the WC crystal grains on the two-dimensional section is 2.5-3.9. 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 Co2W4Ratio of C powder mass, increasing Co2W4The grain size of the C powder is further improved by increasing the sintering temperature and reducing the sintering pressure. Carbon black addition amount and Co2W4The 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 the 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 time2W4C single phase, thereby ensuring Co is formed in the subsequent heating sintering process2W4When the C is carbonized to generate WC, the nucleation and growth of the WC have no impurity blocking effect, and a key foundation is laid for preparing the lath-shaped WC with the 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 Co2W4The 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 proportion and the length-diameter ratio of anisotropic WC grains by adjusting the carbon black and Co2W4Ratio of C powder, Co2W4The 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%), 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 a special application condition can be met.
(5) The method is essentially different from the prior preparation methods of controlling grain growth and preferred orientation by adding special compounds (such as TiC and the like) or obtaining the oriented growth WC grain structure 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 invention2W4X-ray diffraction pattern of C single phase, wherein (a) is Co prepared in example 12W4X-ray diffraction pattern of C single phase, (b) Co prepared in example 22W4X-ray diffraction pattern of C single phase (C) Co prepared in example 32W4X-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 a high proportion of lath-shaped WC with a large aspect ratio for 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 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 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 50 min; 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 3.0 h; when the reaction temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the pressure of the argon partial pressure is 180 mbar; obtaining Co through the reaction2W4C, single phase; co obtained by reaction2W4C, 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 50 min; mixing Co2W4C, 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 3 min; most preferablyThen the WC-Co hard alloy block material with the lath-shaped WC crystal grain content (area fraction on a 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 Co2W4The 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 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 40 min; placing the prepared Co-W-C mixed powder into a vacuum furnace for chemical reaction, wherein the reaction temperature is 1300 ℃, and the heat preservation time is 2.5 h; when the reaction temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the partial pressure of argon is 150 mbar; obtaining Co through the reaction2W4C, single phase; co obtained by reaction2W4C, 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 40 min; mixing Co2W4C, 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 4 min; 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 Co2W4The X-ray diffraction analysis of the C phase is shown in figure 2, and the WC-Co hard alloy block body is preparedThe phase analysis and the microstructure morphology of the material are respectively shown in fig. 3 and fig. 4, the length-diameter ratio statistical result of WC grains in the prepared WC-Co hard alloy is shown in fig. 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 to tungsten is calculated according to the following formula: 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, the ball milling process is stopped once every 1.5 hours, and the stopping time is 30 min; 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 2.0 h; when the reaction temperature is higher than 1100 ℃, argon is used as partial pressure gas, and the partial pressure of argon is 120 mbar; obtaining Co through the reaction2W4C, single phase; co obtained by reaction2W4And C, uniformly mixing the powder C and the carbon black, wherein the addition amount of the carbon black is 3.7 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 30 min; mixing Co2W4C, 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 5 min; 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 Co2W4The 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.
TABLE 1 Properties of WC-13Co cemented carbide bulk materials prepared in the examples
Figure BDA0003524591250000061

Claims (4)

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 proportion 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 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 reaction2W4A single phase C having an average particle diameter in the range of 300 to 500 nm;
(3) co obtained by reaction2W4Mixing the single-phase powder C with carbon black uniformly, wherein the addition amount of the carbon black is Co2W43.7-4.1% of the C powder by mass, and the ball-to-feed 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 Co2W4And C, uniformly mixing the powder with carbon black, putting the powder into a discharge plasma sintering device for sintering, wherein the sintering temperature is 1100-1200 ℃, the sintering pressure is 30-100 MPa, and the heat preservation time is 3-5 min.
2. The method for preparing a cemented carbide having a high proportion of lath-shaped WC having a large length to diameter ratio as claimed in claim 1, wherein the content of lath-shaped WC grains is not less than 90% by integral number on a two-dimensional section, and the average length to diameter ratio of the WC grains on the two-dimensional section is 2.5 to 3.9.
3. The method for producing a cemented carbide having a high ratio of length to diameter of lath-shaped WC according to claim 2, 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 addition2W4Ratio of C powder mass, increasing Co2W4C, 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 Co2W4The 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 the lath-shaped WC grains.
4. A cemented carbide having a high proportion of lath WC with a large length to diameter ratio, produced by a method according to any one of claims 1-3.
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