CN107964620B - Tungsten-nickel-based enhanced hard alloy and preparation method thereof - Google Patents
Tungsten-nickel-based enhanced hard alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of hard alloy materials, and discloses tungsten-nickel-based enhanced hard alloy and a preparation method thereof. The enhanced hard alloy based on tungsten and nickel is prepared from the following components in percentage by weight: 0.1 to 0.3% Cr3C20.02-1% of AlN, 9% of Ni powder and the balance of WC powder. In order to improve the high-temperature oxidation resistance and the thermal conductivity of the WC-9Ni tungsten-nickel alloy, the invention prepares the high-oxidation-resistance hard alloy by creatively introducing chromium carbide and trace aluminum nitride into a tungsten-nickel hard alloy mixture preparation process, and carrying out drying, glue mixing, forming and sintering processes after wet grinding of the mixture. The preparation method is simple in preparation process, and the prepared alloy is excellent in performance and convenient for industrial production and application.
Description
Technical Field
The invention relates to the technical field of hard alloy materials, in particular to tungsten-nickel-based enhanced hard alloy based on WC-9Ni and a preparation method thereof.
Background
Cemented carbide is an alloy material made from a hard compound of refractory metals and a binder metal by a powder metallurgy process. The hard alloy has a series of excellent performances of high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, particularly high hardness and wear resistance, basically keeps unchanged even at the temperature of 500 ℃, and still has high hardness at the temperature of 1000 ℃. Cemented carbide is widely used as a tool material, such as turning tools, milling cutters, planing tools, drill bits, boring tools and the like, for cutting cast iron, nonferrous metals, plastics, chemical fibers, graphite, glass, stone and common steel, and also for cutting refractory steel, stainless steel, high manganese steel, tool steel and other materials which are difficult to process.
With the development of modern industry, many instruments work under harsh environmental conditions, such as acid-base corrosion, material abrasion, high pressure sealing, etc., and under severe use conditions, the choice of materials for exploring tools is particularly important. The hard alloy has the advantages of high hardness, high Young's modulus, heat resistance, corrosion resistance and the like, is not only an ideal material for manufacturing dies, cutters and mining wear-resistant parts, but also can be used as sliding friction pair parts, seabed dynamic pressure sealing parts, shaft sealing materials and the like.
When the application range of the hard alloy is continuously expanded, the hard alloy has higher requirements on the corrosion resistance and the high-temperature oxidation resistance of the hard alloy besides the hardness and the strength, and some hard alloys can be corroded and oxidized in certain severe environments, so that the application of some fields is limited to a certain extent.
In the design of hard alloy, the tungsten-nickel alloy is often designed to be corrosion-resistant hard alloy, and the corrosiveness of the tungsten-nickel alloy comprises chemical corrosion and high-temperature oxidation corrosion, but the existing tungsten-nickel alloy has low oxidation corrosion resistance at high temperature and low thermal conductivity. According to the invention, chromium carbide and aluminum nitride are introduced to the WC-9Ni tungsten-nickel alloy to improve the high-temperature oxidation resistance and the thermal conductivity of the alloy, and the high-temperature oxidation corrosion resistance of the tungsten-nickel alloy can be realized by adding chromium carbide.
Disclosure of Invention
Aiming at the defects in the prior art, in order to further improve the high-temperature oxidation resistance and the thermal conductivity of the tungsten-nickel alloy, the invention introduces chromium carbide and aluminum nitride to improve the high-temperature oxidation resistance and the thermal conductivity of the WC-9Ni tungsten-nickel alloy, and provides the tungsten-nickel-based enhanced hard alloy based on WC-9 Ni.
The invention also provides a preparation method of the enhanced hard alloy based on tungsten nickel.
The purpose of the invention is realized by the following technical scheme:
provides a tungsten-nickel based reinforced hard alloy, which is based on WC-9Ni and added with Cr3C2And AlN, wherein the mixture ratio is carried out according to the following components in percentage by weight:
the invention mainly surrounds the WC-9Ni tungsten-nickel alloy, and aims to improve the resistance of the WC-9Ni tungsten-nickel alloyHigh-temperature oxidation performance and thermal conductivity, and AlN and Cr are introduced3C2The mechanism is that the solid solution strengthening of chromium carbide to nickel is utilized, and AlN is added into the alloy to improve the high-temperature oxidation resistance and the thermal conductivity of the alloy.
Preferably, the reinforced cemented carbide based on tungsten and nickel is prepared by mixing the following components in percentage by weight:
the invention also provides a preparation method of the tungsten-nickel-based enhanced hard alloy, which comprises the following steps:
s1, preparing materials according to the proportion of the enhanced hard alloy based on tungsten nickel, carrying out wet grinding, and obtaining slurry after the wet grinding is finished;
and S2, drying the slurry, carrying out glue blending and granulation on the dried material powder, then carrying out compression molding, and carrying out degumming and sintering to finally obtain the tungsten-nickel-based reinforced hard alloy with the required shape.
Preferably, in step S1, the WC powder ficoll size is 2um, and the Ni powder ficoll size is 2 um.
Preferably, the wet milling medium for the wet milling in step S1 is industrial alcohol having a water content of 5 wt%.
Preferably, the wet grinding time in the step S1 is 20-40 h.
Preferably, the wet milling ball to feed ratio in step S1 is 3: 1.
Preferably, the sintering temperature in step S2 is 1400-1600, and the sintering time is 1-3 h.
Compared with the prior art, the invention has the following beneficial effects:
in order to improve the high-temperature oxidation resistance and the thermal conductivity of the WC-9Ni tungsten-nickel alloy, the invention creatively introduces chromium carbide and trace aluminum nitride in the preparation process of the tungsten-nickel hard alloy mixture, and the hard alloy with high oxidation resistance is prepared after the wet grinding of the mixture is finished and the processes of drying, glue mixing, forming and sintering are carried out. The preparation method is simple in preparation process, and the prepared alloy is excellent in performance and convenient for industrial production and application.
Drawings
Figure 1 example 1 cemented carbide high temperature oxidation surface.
Figure 2 example 2 cemented carbide high temperature oxidation surface.
Figure 3 example 3 cemented carbide high temperature oxidation surface.
Figure 4 comparative example 1 cemented carbide high temperature oxidation surface.
Detailed Description
The invention is developed based on WC-9Ni alloy, provides tungsten-nickel-based enhanced hard alloy, and is prepared from the following components in percentage by weight:
the invention mainly surrounds WC-9Ni tungsten-nickel alloy, and AlN and Cr are introduced to improve the high-temperature oxidation resistance and the heat conductivity of the WC-9Ni tungsten-nickel alloy3C2The mechanism is that the solid solution strengthening of chromium carbide to nickel is utilized, and AlN is added into the alloy to improve the high-temperature oxidation resistance and the thermal conductivity of the alloy.
Preferably, when the enhanced cemented carbide based on tungsten and nickel is mixed according to the following components by weight percentage, the enhanced cemented carbide based on tungsten and nickel has the best high-temperature oxidation resistance and thermal conductivity, and specifically comprises the following components:
the invention also provides a preparation method of the tungsten-nickel-based enhanced hard alloy, which comprises the following steps:
s1, preparing materials according to the proportion of the enhanced hard alloy based on tungsten nickel, and carrying out wet grinding, wherein a wet grinding medium is industrial alcohol with the water content of 5wt%, the time is 20-40 h, and slurry is obtained after the wet grinding is finished, wherein the Fisher particle size of WC powder is 2um, and the Fisher particle size of Ni powder is 2 um;
s2, drying the slurry, carrying out glue blending and granulation on the dried material powder, then carrying out compression molding, carrying out degumming and sintering, wherein the sintering temperature is 1400-1600 ℃, and the heat preservation time is 1-3 h, and finally obtaining the tungsten-nickel-based reinforced hard alloy with the required shape.
After the alloy prepared by the process is subjected to air oxidation at 850 ℃ for 30min, the surface change of the alloy is observed, the weight loss is calculated, the oxidation degree and the weight loss of the alloy added with the chromium carbide and the aluminum nitride are lower than those of the alloy not added, and the thermal conductivity of the alloy added with the chromium carbide and the aluminum nitride is higher than that of the alloy not added through a thermal conductivity test.
The invention is further illustrated by the following specific examples. The following examples are illustrative only and are not to be construed as unduly limiting the invention which may be embodied in many different forms as defined and covered by the summary of the invention. Reagents, compounds and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment provides a preparation method of a tungsten-nickel-based reinforced hard alloy, which comprises the following steps:
s1, adding 0.3 percent of Cr according to weight percentage3C20.02% of AlN, 9% of Ni powder and 90.68% of WC powder are mixed to obtain 1Kg of mixture, the Fisher particle size of the WC powder in the mixture is 2um, the Fisher particle size of the Ni powder is 2um, 1Kg of mixture is added into a ball milling cylinder with the volume of 2L, 3Kg of hard alloy grinding rod is added, a wet milling medium is industrial alcohol with the water content of 5wt%, the wet milling time is 30h, and slurry is obtained after wet milling;
s2, drying the slurry, carrying out glue blending granulation on the dried material powder, then pressing into a test sample strip, carrying out degumming and sintering, keeping the temperature for 1h at the final sintering temperature of 1440 ℃, and preparing the enhanced hard alloy test sample strip based on tungsten-nickel, wherein the specification of the enhanced hard alloy test sample strip is 5.25mm x 6.5mm x 20 mm.
Example 2
The embodiment provides a preparation method of a tungsten-nickel-based reinforced hard alloy, which comprises the following steps:
S10.2% by weight of Cr3C20.05 percent of AlN, 9 percent of Ni powder and 90.68 percent of WC powder are mixed to obtain 1Kg of mixture, the Fisher particle size of the WC powder in the mixture is 2um, the Fisher particle size of the Ni powder is 2um, 1Kg of mixture is added into a ball milling cylinder with the volume of 2L, 3Kg of hard alloy grinding rod is added, the wet milling medium is industrial alcohol with the water content of 5 weight percent, the wet milling time is 30 hours, and slurry is obtained after wet milling;
s2, drying the slurry, carrying out glue blending granulation on the dried material powder, then pressing into a test sample strip, carrying out degumming and sintering, keeping the temperature for 1h at the final sintering temperature of 1440 ℃, and preparing the enhanced hard alloy test sample strip based on tungsten-nickel, wherein the specification of the enhanced hard alloy test sample strip is 5.25mm x 6.5mm x 20 mm.
Example 3
The embodiment provides a preparation method of a tungsten-nickel-based reinforced hard alloy, which comprises the following steps:
s1, mixing 0.1 percent of Cr according to weight percentage3C20.1% of AlN, 9% of Ni powder and 90.68% of WC powder are mixed to obtain 1Kg of mixture, the Fisher particle size of the WC powder in the mixture is 2um, the Fisher particle size of the Ni powder is 2um, 1Kg of mixture is added into a ball milling cylinder with the volume of 2L, 3Kg of hard alloy grinding rod is added, a wet milling medium is industrial alcohol with the water content of 5wt%, the wet milling time is 30h, and slurry is obtained after wet milling;
s2, drying the slurry, carrying out glue blending granulation on the dried material powder, then pressing into a test sample strip, carrying out degumming and sintering, keeping the temperature for 1h at the final sintering temperature of 1440 ℃, and preparing the enhanced hard alloy test sample strip based on tungsten-nickel, wherein the specification of the enhanced hard alloy test sample strip is 5.25mm x 6.5mm x 20 mm.
Comparative example 1
The comparative example provides a method for preparing WC-9Ni tungsten-nickel hard alloy, comprising the following steps:
s1, mixing 9% of Ni powder and 90% of WC powder according to weight percentage to obtain 1Kg of mixture, wherein the Fisher particle size of the WC powder in the mixture is 2um, the Fisher particle size of the Ni powder is 2um, adding 1Kg of mixture into a ball milling cylinder with the volume of 2L, adding 3Kg of hard alloy grinding rod, wet milling medium is industrial alcohol with the water content of 5wt%, wet milling time is 30h, and wet milling to obtain slurry;
s2, drying the slurry, carrying out glue blending granulation on the dried material powder, then pressing into a test sample strip, carrying out degumming and sintering, keeping the temperature for 1h at the final sintering temperature of 1440 ℃, and preparing the WC-9Ni alloy test sample strip with the specification of 5.25mm 6.5mm 20 mm.
As is apparent from fig. 4, the high temperature oxidation surface of the cemented carbide had many spots.
Comparative example 2
This comparative example is substantially the same as example 1 except that AlN is not added and the balance is replaced with WC powder.
Comparative example 3
This comparative example is substantially the same as example 1 except that Cr is not added3C2And the balance is replaced by WC powder.
Performance testing and characterization
Alloy test specimens prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to high-temperature oxidation at 850 ℃ for 30min, the high-temperature oxidation surfaces of which are shown in fig. 1 to 4, and performance tests were carried out, specifically shown in table 1.
TABLE 1
Through surface observation and data analysis in table 1, it can be obtained from examples 1 to 3 that the oxidation degree and weight loss of the alloy with chromium carbide and aluminum nitride added into WC-9Ni are lower than those of the alloy without the chromium carbide and aluminum nitride (comparative example 1), and through a thermal conductivity test, the thermal conductivity of the alloy with the chromium carbide and the aluminum nitride is higher than that of the alloy without the chromium carbide and the aluminum nitride (comparative example 1).
According to comparative examples 2 to 3, it can be seen that when only Cr is added3C2When the alloy is oxidized to a lower degree, the thermal conductivity is not effectively improved because of Cr3C2Effectively strengthening the nickel binding phase by solid solution, and forming a compact anti-oxidation layer on the surface of the alloy in time in the oxidation process of the alloy to prevent the alloy from further oxidation. When only AlN is added, the thermal conductivity of the alloy is significantly increased, but the oxidation degree of the alloy is not effectively reduced, because AlN is a high thermal conductivityAfter the compound is added into the mixture, AlN is dispersed and distributed among hard phase grains in the processes of uniform wet grinding and sintering of the mixture, so that a good heat-conducting bridge is formed, and the heat conductivity of the alloy is improved.
In conclusion, Cr is added3C2And AlN is added into the alloy at the same time, so that the method is an effective way for improving the oxidation resistance and the heat conductivity of the alloy. From the analysis of examples 1, 2 and 3, example 2 is Cr in the present application3C2And the optimum amount of AlN to be added.
Claims (9)
1. The tungsten-nickel based reinforced hard alloy is characterized in that the WC-9Ni is taken as the base, and Cr for enhancing the high-temperature oxidation resistance is added3C2And AlN for enhancing the thermal conductivity, and the mixture ratio is carried out according to the following components by weight percentage:
Cr3C20.1～0.2%,
AlN 0.02～1%,
9 percent of Ni powder,
the balance of WC powder.
2. The tungsten-nickel based reinforced hard alloy according to claim 1, wherein the mixture ratio is as follows:
Cr3C20.2%,
AlN 0.05%,
9 percent of Ni powder,
90.75 percent of WC powder.
3. The preparation method of the enhanced hard alloy based on tungsten nickel is characterized by comprising the following steps:
s1, preparing materials according to the proportion of the enhanced tungsten-nickel-based hard alloy in any one of claims 1-2, carrying out wet grinding, and obtaining slurry after the wet grinding is finished;
and S2, drying the slurry, carrying out glue blending and granulation on the dried material powder, then carrying out compression molding, and carrying out degumming and sintering to finally obtain the tungsten-nickel-based reinforced hard alloy with the required shape.
4. The method for preparing the enhanced tungsten-nickel-based cemented carbide according to claim 3, wherein the Fisher size of the WC powder in step S1 is 2 μm.
5. The method for preparing the enhanced tungsten-nickel-based hard alloy according to the claim 4, wherein the Fisher size of the Ni powder in the step S1 is 2 μm.
6. The enhanced tungsten-nickel based cemented carbide manufacturing method as claimed in claim 4, wherein the wet milling medium for the wet milling in step S1 is industrial alcohol with 5wt% water content.
7. The method for preparing the enhanced tungsten-nickel-based hard alloy according to claim 4, wherein the wet grinding time in the step S1 is 20-40 h.
8. The method for preparing the enhanced tungsten-nickel based cemented carbide according to claim 4, wherein the wet grinding in step S1 has a ball-to-feed ratio of 3: 1.
9. The method for preparing the enhanced tungsten-nickel-based hard alloy according to claim 4, wherein in the step S2, the sintering temperature is 1400-1600 ℃ and the sintering time is 1-3 h.
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| CN102433488A (en) * | 2011-12-29 | 2012-05-02 | 株洲硬质合金集团有限公司 | WC-Co-Ni-Al-B hard alloy, roll collar prepared from hard alloy and preparation method of roll collar |
| CN102766796A (en) * | 2012-07-23 | 2012-11-07 | 自贡硬质合金有限责任公司 | Hard alloy and preparation method thereof |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| JP6162311B1 (en) * | 2016-11-21 | 2017-07-12 | 冨士ダイス株式会社 | Manufacturing method of powder metallurgy sintered body by additive manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433488A (en) * | 2011-12-29 | 2012-05-02 | 株洲硬质合金集团有限公司 | WC-Co-Ni-Al-B hard alloy, roll collar prepared from hard alloy and preparation method of roll collar |
| CN102766796A (en) * | 2012-07-23 | 2012-11-07 | 自贡硬质合金有限责任公司 | Hard alloy and preparation method thereof |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| JP6162311B1 (en) * | 2016-11-21 | 2017-07-12 | 冨士ダイス株式会社 | Manufacturing method of powder metallurgy sintered body by additive manufacturing method |
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