CN112795829B - Fine-grain hard alloy and preparation method thereof - Google Patents
Fine-grain hard alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides a fine-grain hard alloy which is prepared from the following components in percentage by weight: 0.9-1.2% of grain growth inhibitor, 10-14% of cobalt powder and the balance of tungsten carbide, wherein the sum of the weight percentages of the components is 100%. The invention also provides a preparation method of the fine-grain hard alloy. The fine-grain hard alloy provided by the invention uses the grain growth inhibitor with better effect, thereby having stronger mechanical property.
Description
Technical Field
The invention relates to a hard alloy, in particular to a fine-grain hard alloy and a preparation method thereof.
Background
The fine-grained cemented carbide was developed on the basis of the WC-Co alloy strength-cobalt phase mean free path relationship model of Gurland. Keeping the mean free path at a certain optimum value, the strength and toughness of the WC crystal grains are obviously increased under the action of tensile stress by thinning the WC crystal grains. According to this model, the increase in the number of carbide phase grain contacts due to the decrease in the grain size of WC is eliminated by the highly uniformly distributed cobalt, and the hardness is increased, whereby a high-performance alloy can be obtained.
In WC-Co hard alloy, with the refinement of original WC and Co powder particles, WC crystal grains grow excessively in the sintering process, so that discontinuous and large WC crystal grains are formed in a sintered product, and the discontinuous WC crystal grains can obviously reduce the mechanical and mechanical properties of the hard alloy. Therefore, grain growth inhibitors are often added to sinter ultra-fine grain cemented carbides to inhibit the rapid growth of WC grains, to minimize or eliminate the formation of such non-continuously grown WC large grains.
At present, the commonly used inhibitors for controlling the growth of WC crystal grains are VC and Cr3C2、TiC、ZrC、NbC、Mo2C. HfC, TaC and the like. When the inhibitor is saturated in the liquid binder phase, the grain refining effect is optimal, and carbides with low chemical stability show a high saturation state in the binder phase. However, the addition of too much inhibitor affects the densification process of the alloy and lowers the strength of the alloy, and thus, the effect of too much inhibitor is not good.
Chinese patent application CN201110232592.6 discloses a fine grain WC-based hard alloy material and a preparation method thereof, the fine grain WC-based hard alloy material adopts fine grain WC as a matrix, Mo or Ni as a binder, one or more of TaC, VC and TiC as a grain growth inhibitor, and Cr is used as a grain growth inhibitor3C2C, SiC or rare earth metal is used as a toughening agent as a hardening agent, and the size of fine-grained WC is 0.8-1 μm. The invention has the following problems: the effect of the used grain growth inhibitor is not ideal, so the performance of the prepared fine-grain WC-based hard alloy material is not good.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fine-grain hard alloy which uses a grain growth inhibitor with better effect and has stronger mechanical property.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the fine-grain hard alloy is prepared from the following components in percentage by weight: 0.9-1.2% of grain growth inhibitor, 10-14% of cobalt powder and the balance of tungsten carbide, wherein the sum of the weight percentages of the components is 100%.
Further, the grain growth inhibitor is prepared by the following steps:
adding niobium oxalate into a DMF (dimethyl formamide) ethanol solution, uniformly mixing to obtain a solution A, adding chromium nitrate into the DMF ethanol solution, uniformly mixing to obtain a solution B, adding rhenium nitrate into the DMF ethanol solution, uniformly mixing to obtain a solution C, adding 3-phenylacetylacetone into the DMF ethanol solution, uniformly mixing to obtain a solution D, mixing the solution A, the solution B, the solution C and the solution D, ultrasonically stirring until the mixture is uniformly mixed to obtain a mixed solution, heating the mixed solution to 90 ℃, keeping the temperature for 8 hours, cooling to room temperature, standing for 12 hours to obtain a mixture, washing the mixture for 3 times by using deionized water and ethanol respectively, and drying in an oven at 90 ℃ until the weight is constant to obtain the crystal grain growth inhibitor.
Further, in the preparation step of the crystal grain growth inhibitor, a DMF ethanol solution is formed by mixing DMF and ethanol with equal volumes, the concentration of niobium oxalate in the A solution is 0.3mol/L, the concentration of chromium nitrate in the B solution is 0.2mol/L, the concentration of rhenium nitrate in the C solution is 0.04mol/L, the concentration of 3-phenylacetylacetone in the D solution is 0.5mol/L, and the volume ratio of the A solution, the B solution, the C solution and the D solution is 1:1:1: 1.
Furthermore, the average particle size of the cobalt powder is 1-1.5 μm.
Furthermore, the average particle size of the tungsten carbide is 0.2-0.5 μm.
Another technical problem to be solved by the present invention is to provide a method for preparing the above fine-grained cemented carbide.
In order to solve the technical problems, the technical scheme is as follows:
a preparation method of a fine-grained cemented carbide comprises the following steps:
s1, weighing the components in percentage by weight, mixing the components to obtain alloy powder, adding the alloy powder, a ball milling medium and a forming agent into a ball mill, and performing wet ball milling for 24-48 hours to obtain mixed slurry;
s2, spray drying the mixed slurry obtained in the step S1 to obtain a mixed material;
s3, heating the mixture obtained in the step S2 to remove the forming agent to obtain mixed powder, and pressing the mixed powder into a green body;
and S4, placing the green body obtained in the step S3 into a sintering furnace, sintering for 30-45 minutes in vacuum, and then sintering for 30-45 minutes in a pressurizing manner to obtain the fine-grain hard alloy.
Further, in the step S1, the ball-to-material ratio during wet ball milling is 5:1, the ball milling medium is polyoxyethylene octyl phenol ether-10, and the weight ratio of the polyoxyethylene octyl phenol ether-10 to the alloy powder is 1: 5; the forming agent is paraffin, and the weight ratio of the paraffin to the alloy powder is 1: 100.
Further, in step S2, the ambient atmosphere during spray drying is nitrogen, the inlet temperature of nitrogen is 200 ℃, and the outlet temperature is 110 ℃.
Further, in the step S3, the temperature for heating and removing the forming agent is 400 ℃ and the time is 30-60 minutes.
Further, in the step S4, the temperature during vacuum sintering is 1350 ℃ and the pressure is 150 pa; the temperature during pressure sintering is 1450 ℃, and the pressure is 5 MPa.
Compared with the prior art, the invention has the following beneficial effects:
1) the crystal grain growth inhibitor containing niobium, chromium and rhenium and having a metal-organic composite structure is prepared by taking 3-phenylacetylacetone as a ligand and reacting with niobium oxalate, chromium nitrate and rhenium nitrate, and can be uniformly distributed in a hard alloy system, so that the effect of refining the crystal grains is fully exerted, and the hardness and the bending strength of the fine-grain hard alloy can be effectively improved; in addition, rhenium in the grain growth inhibitor can also effectively improve the transverse rupture strength and the wear resistance of the fine-grained cemented carbide.
2) The ball milling medium used in the wet ball milling process is polyoxyethylene octyl phenol ether-10, which can effectively improve the dispersibility of each component in the wet ball milling process and greatly reduce agglomeration, thereby further improving the transverse rupture strength of the fine-grained hard alloy.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, and the exemplary embodiments and descriptions thereof herein are provided to explain the present invention but not to limit the present invention.
Example 1
The fine-grained hard alloy is prepared from the following components in percentage by weight: 1 percent of grain growth inhibitor, 12 percent of cobalt powder with the average granularity of 1-1.5 mu m, and the balance of tungsten carbide with the average granularity of 0.2-0.5 mu m, wherein the sum of the weight percentages of the components is 100 percent. Wherein, the grain growth inhibitor is prepared by the following steps:
adding niobium oxalate into a DMF ethanol solution, uniformly mixing to obtain a first solution with the concentration of 0.3mol/L, adding chromium nitrate into the DMF ethanol solution, uniformly mixing to obtain a second solution with the concentration of 0.2mol/L, adding rhenium nitrate into the DMF ethanol solution, uniformly mixing to obtain a third solution with the concentration of 0.04mol/L, adding 3-phenylacetacetone into the DMF ethanol solution, uniformly mixing to obtain a third solution with the concentration of 0.5mol/L, mixing the first solution, the second solution, the third solution and the third solution in a volume ratio of 1:1:1:1, ultrasonically stirring until the mixture is uniformly mixed to obtain a mixed solution, heating the mixed solution to 90 ℃, preserving heat for 8 hours, cooling to room temperature, standing for 12 hours to obtain a mixture, washing the mixture respectively with deionized water and ethanol for 3 times, drying in an oven at 90 ℃ until the weight is constant to obtain a crystal grain inhibitor, wherein, the DMF ethanol solution is prepared by mixing equal volumes of DMF and ethanol.
The preparation method of the fine-grained hard alloy comprises the following steps:
s1, weighing the components according to the weight percentage, mixing the components to obtain alloy powder, adding the alloy powder, polyoxyethylene octyl phenol ether-10 and paraffin into a ball mill, and performing wet ball milling for 36 hours to obtain mixed slurry, wherein the ball-to-material ratio during the wet ball milling is 5:1, the weight ratio of the polyoxyethylene octyl phenol ether-10 to the alloy powder is 1:5, and the weight ratio of the paraffin to the alloy powder is 1: 100;
s2, spray-drying the mixed slurry obtained in the step S1 to obtain a mixture, wherein the environment atmosphere during spray-drying is nitrogen, the inlet temperature of the nitrogen is 200 ℃, and the outlet temperature of the nitrogen is 110 ℃;
s3, heating the mixture obtained in the step S2 to remove the forming agent to obtain mixed powder, pressing the mixed powder into a green body, wherein the temperature for heating to remove the forming agent is 400 ℃, and the time is 45 minutes;
s4, placing the green body obtained in the step S3 into a sintering furnace, sintering for 35 minutes in vacuum at 1350 ℃ and under the pressure of 150pa, and then sintering for 40 minutes in a pressurized manner at 1450 ℃ and under the pressure of 5Mpa to obtain the fine-grain hard alloy.
Example 2
The fine-grained hard alloy is prepared from the following components in percentage by weight: 0.9 percent of grain growth inhibitor, 14 percent of cobalt powder with the average granularity of 1-1.5 mu m, and the balance of tungsten carbide with the average granularity of 0.2-0.5 mu m, wherein the sum of the weight percentages of the components is 100 percent. Wherein the procedure for preparing the grain growth inhibitor was the same as in example 1.
The preparation method of the fine-grained hard alloy comprises the following steps:
s1, weighing the components according to the weight percentage, mixing the components to obtain alloy powder, adding the alloy powder, polyoxyethylene octyl phenol ether-10 and paraffin into a ball mill, and performing wet ball milling for 24 hours to obtain mixed slurry, wherein the ball-to-material ratio during the wet ball milling is 5:1, the weight ratio of the polyoxyethylene octyl phenol ether-10 to the alloy powder is 1:5, and the weight ratio of the paraffin to the alloy powder is 1: 100;
s2, spray-drying the mixed slurry obtained in the step S1 to obtain a mixture, wherein the environment atmosphere during spray-drying is nitrogen, the inlet temperature of the nitrogen is 200 ℃, and the outlet temperature of the nitrogen is 110 ℃;
s3, heating the mixture obtained in the step S2 to remove the forming agent to obtain mixed powder, pressing the mixed powder into a green body, wherein the temperature for heating to remove the forming agent is 400 ℃, and the time is 30 minutes;
s4, placing the green body obtained in the step S3 into a sintering furnace, sintering for 30 minutes in vacuum at 1350 ℃ and under the pressure of 150pa, and then sintering for 45 minutes under the pressure of 1450 ℃ and under the pressure of 5Mpa to obtain the fine-grain hard alloy.
Example 3
The fine-grained hard alloy is prepared from the following components in percentage by weight: 1.2 percent of grain growth inhibitor, 10 percent of cobalt powder with the average granularity of 1-1.5 mu m, and the balance of tungsten carbide with the average granularity of 0.2-0.5 mu m, wherein the sum of the weight percentages of the components is 100 percent. Wherein the procedure for preparing the grain growth inhibitor was the same as in example 1.
The preparation method of the fine-grained hard alloy comprises the following steps:
s1, weighing the components according to the weight percentage, mixing the components to obtain alloy powder, adding the alloy powder, polyoxyethylene octyl phenol ether-10 and paraffin into a ball mill, and performing wet ball milling for 48 hours to obtain mixed slurry, wherein the ball-to-material ratio during the wet ball milling is 5:1, the weight ratio of the polyoxyethylene octyl phenol ether-10 to the alloy powder is 1:5, and the weight ratio of the paraffin to the alloy powder is 1: 100;
s2, spray-drying the mixed slurry obtained in the step S1 to obtain a mixture, wherein the environment atmosphere during spray-drying is nitrogen, the inlet temperature of the nitrogen is 200 ℃, and the outlet temperature of the nitrogen is 110 ℃;
s3, heating the mixture obtained in the step S2 to remove the forming agent to obtain mixed powder, pressing the mixed powder into a green body, wherein the temperature for heating to remove the forming agent is 400 ℃, and the time is 60 minutes;
s4, placing the green body obtained in the step S3 into a sintering furnace, sintering for 45 minutes in vacuum at 1350 ℃ and under the pressure of 150pa, and then sintering for 30 minutes under the pressure of 1450 ℃ and under the pressure of 5Mpa to obtain the fine-grain hard alloy.
Example 4
The fine-grained hard alloy is prepared from the following components in percentage by weight: 1.1 percent of grain growth inhibitor, 13 percent of cobalt powder with the average granularity of 1-1.5 mu m, and the balance of tungsten carbide with the average granularity of 0.2-0.5 mu m, wherein the sum of the weight percentages of the components is 100 percent. Wherein the procedure for preparing the grain growth inhibitor was the same as in example 1.
The preparation method of the fine-grained hard alloy comprises the following steps:
s1, weighing the components according to the weight percentage, mixing the components to obtain alloy powder, adding the alloy powder, polyoxyethylene octyl phenol ether-10 and paraffin into a ball mill, and performing wet ball milling for 40 hours to obtain mixed slurry, wherein the ball-to-material ratio during the wet ball milling is 5:1, the weight ratio of the polyoxyethylene octyl phenol ether-10 to the alloy powder is 1:5, and the weight ratio of the paraffin to the alloy powder is 1: 100;
s2, spray-drying the mixed slurry obtained in the step S1 to obtain a mixture, wherein the environment atmosphere during spray-drying is nitrogen, the inlet temperature of the nitrogen is 200 ℃, and the outlet temperature of the nitrogen is 110 ℃;
s3, heating the mixture obtained in the step S2 to remove the forming agent to obtain mixed powder, pressing the mixed powder into a green body, wherein the temperature for heating to remove the forming agent is 400 ℃, and the time is 50 minutes;
s4, placing the green body obtained in the step S3 into a sintering furnace, sintering for 40 minutes in vacuum at 1350 ℃ and under the pressure of 150pa, and then sintering for 35 minutes under the pressure of 1450 ℃ and under the pressure of 5Mpa to obtain the fine-grain hard alloy.
Reference example 1:
the difference from example 1 is that: the grain growth inhibitor in the components is replaced by niobium carbide, and the preparation step of the grain growth inhibitor is omitted.
Reference example 2:
the difference from example 1 is that: the crystal growth inhibitor is prepared without rhenium nitrate and solution, i.e. rhenium is absent in the crystal growth inhibitor.
Reference example 3:
the difference from example 1 is that: in step S1, polyoxyethylene octylphenol ether-10 was not used in the wet ball milling. Comparative example: embodiment one of chinese patent application No. CN 201110232592.6.
The first test example: bending strength test
The test method comprises the following steps: the flexural strength of examples 1 to 4, reference examples 1 to 3 and comparative example were measured by a three-point bending test using a universal tester, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the bending strengths of inventive examples 1-4 are all higher than those of comparative examples, indicating that the inventive compositions have higher bending strengths. The differences between the components or preparation steps of reference examples 1-3 and example 1 indicate that the grain growth inhibitor prepared by the present invention has a better effect of improving the flexural strength of cemented carbide than the conventional niobium carbide, because the flexural strength of reference example 1 is reduced.
Test example two: hardness test
The test method comprises the following steps: the rockwell hardness of examples 1 to 4, reference examples 1 to 3 and comparative example were measured using a rockwell hardness tester, respectively, and the test results are shown in table 2:
| rockwell Hardness (HRA) | |
| Example 1 | 95.8 |
| Example 2 | 95.7 |
| Example 3 | 95.5 |
| Example 4 | 95.6 |
| Reference example 1 | 92.3 |
| Reference example 2 | 95.7 |
| Reference example 3 | 95.8 |
| Comparative example | 93 |
TABLE 2
As can be seen from Table 2, the Rockwell hardness of examples 1 to 4 of the present invention is higher than that of the comparative example, indicating that the present invention has a higher hardness. The differences between the components or preparation steps of reference examples 1-3 and example 1 indicate that the grain growth inhibitor prepared by the present invention has a better effect of increasing the hardness of cemented carbide than conventional niobium carbide, because the Rockwell hardness of reference example 1 is reduced.
Test example three: transverse rupture Strength test
The test method comprises the following steps: the transverse rupture strength of examples 1-4, reference examples 1-3 and comparative example were determined with reference to GB/T3851-2015, and the test results are shown in Table 3:
| transverse rupture Strength (Mpa) | |
| Example 1 | 1793 |
| Example 2 | 1782 |
| Example 3 | 1787 |
| Example 4 | 1790 |
| Reference example 1 | 1728 |
| Reference example 2 | 1726 |
| Reference example 3 | 1759 |
| Comparative example | 1701 |
TABLE 3
As can be seen from Table 3, the transverse rupture strengths of inventive examples 1 to 4 are all higher than those of comparative example, indicating that the inventive examples have higher transverse rupture strengths. The parts of the components or the preparation steps of the reference examples 1-3 are different from those of the reference example 1, the transverse rupture strength of the reference examples 1 and 2 is obviously reduced, and the rhenium in the grain growth inhibitor prepared by the invention is a main factor for improving the transverse rupture strength of the fine-grained cemented carbide; the transverse rupture strength of reference example 3 is also reduced, indicating that the polyoxyethylene octylphenol ether-10 used in the present invention is also effective in improving the transverse rupture strength of fine grained cemented carbide.
Test example four: abrasion resistance test
The test method comprises the following steps: the abrasion resistance parameters of examples 1 to 4, reference examples 1 to 3 and comparative example were measured using a friction abrasion tester, respectively, the grinding medium was a mixture of alumina and water, a load was applied to 196N, a rotation speed of a grinding wheel was 100rpm, and the abrasion resistance parameters were calculated from the mass loss of the sample after 1000 revolutions according to the following formula:
S＝D/(m1-m2)
wherein S is a wear resistance parameter, cm-3(ii) a D is the density of the sample, g/cm3(ii) a m1 is the weight of the sample before the test, g; m2 is the weight of the sample after the test, g.
The larger the wear resistance parameter, the better the wear resistance, and the test results are shown in table 4:
| abrasion resistance parameter (cm)-3) | |
| Example 1 | 4.069 |
| Example 2 | 4.028 |
| Example 3 | 4.045 |
| Example 4 | 4.051 |
| Reference example 1 | 3.237 |
| Reference example 2 | 3.234 |
| Reference example 3 | 4.068 |
| Comparative example | 3.154 |
TABLE 4
As can be seen from Table 4, the wear resistance parameters of examples 1-4 of the present invention are all significantly greater than those of the comparative examples, indicating that the present invention has better wear resistance. The parts of the components or the preparation steps of the reference examples 1-3 are different from those of the reference example 1, the wear-resisting parameters of the reference examples 1 and 2 are obviously reduced, and the rhenium in the grain growth inhibitor prepared by the invention is a main factor for improving the wear resistance of the fine-grained cemented carbide.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. A fine grained cemented carbide characterized by: the paint is prepared from the following components in percentage by weight: 0.9-1.2% of grain growth inhibitor, 10-14% of cobalt powder and the balance of tungsten carbide, wherein the sum of the weight percentages of the components is 100%;
the grain growth inhibitor is prepared by the following steps:
adding niobium oxalate into a DMF (dimethyl formamide) ethanol solution, uniformly mixing to obtain a solution A, adding chromium nitrate into the DMF ethanol solution, uniformly mixing to obtain a solution B, adding rhenium nitrate into the DMF ethanol solution, uniformly mixing to obtain a solution C, adding 3-phenylacetylacetone into the DMF ethanol solution, uniformly mixing to obtain a solution D, mixing the solution A, the solution B, the solution C and the solution D, ultrasonically stirring until the mixture is uniformly mixed to obtain a mixed solution, heating the mixed solution to 90 ℃, keeping the temperature for 8 hours, cooling to room temperature, standing for 12 hours to obtain a mixture, washing the mixture for 3 times by using deionized water and ethanol respectively, and drying in an oven at 90 ℃ until the weight is constant to obtain the crystal grain growth inhibitor.
2. The fine-grained cemented carbide of claim 1, wherein: in the preparation step of the crystal grain growth inhibitor, a DMF ethanol solution is formed by mixing DMF and ethanol with equal volumes, the concentration of niobium oxalate in the solution A is 0.3mol/L, the concentration of chromium nitrate in the solution B is 0.2mol/L, the concentration of rhenium nitrate in the solution C is 0.04mol/L, the concentration of 3-phenylacetylacetone in the solution D is 0.5mol/L, and the volume ratio of the solution A to the solution B to the solution C to the solution D is 1:1:1: 1.
3. The fine-grained cemented carbide of claim 1, wherein: the average particle size of the cobalt powder is 1-1.5 mu m.
4. The fine-grained cemented carbide of claim 1, wherein: the average particle size of the tungsten carbide is 0.2-0.5 mu m.
5. A method of producing a fine grained cemented carbide according to any one of claims 1 to 4 wherein: the method comprises the following steps:
s1, weighing the components according to the weight percentage, mixing the components to obtain alloy powder, adding the alloy powder, a ball milling medium and a forming agent into a ball mill, and performing wet ball milling for 24-48 hours to obtain mixed slurry, wherein the ball-material ratio during the wet ball milling is 5:1, the ball milling medium is polyoxyethylene octyl phenol ether-10, and the weight ratio of the polyoxyethylene octyl phenol ether-10 to the alloy powder is 1: 5; the forming agent is paraffin, and the weight ratio of the paraffin to the alloy powder is 1: 100;
s2, spray drying the mixed slurry obtained in the step S1 to obtain a mixed material;
s3, heating the mixture obtained in the step S2 to remove the forming agent to obtain mixed powder, and pressing the mixed powder into a green body;
and S4, placing the green body obtained in the step S3 into a sintering furnace, sintering for 30-45 minutes in vacuum, and then sintering for 30-45 minutes in a pressurizing manner to obtain the fine-grain hard alloy.
6. The method of making a fine grained cemented carbide as claimed in claim 5 wherein: in step S2, the ambient atmosphere during spray drying is nitrogen, the inlet temperature of nitrogen is 200 ℃, and the outlet temperature is 110 ℃.
7. The method of making a fine grained cemented carbide as claimed in claim 5 wherein: in the step S3, the temperature for heating and removing the forming agent is 400 ℃, and the time is 30-60 minutes.
8. The method of making a fine grained cemented carbide as claimed in claim 5 wherein: in the step S4, the temperature during vacuum sintering is 1350 ℃ and the pressure is 150 Pa; the temperature during pressure sintering is 1450 ℃, and the pressure is 5 MPa.
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| CN111363963A (en) * | 2020-04-07 | 2020-07-03 | 广东正信硬质材料技术研发有限公司 | Double-layer structure hard alloy with surface layer rich in cubic phase and preparation method thereof |
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