CN114318040A - Rare earth-added hard alloy and preparation method thereof - Google Patents
Rare earth-added hard alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 79
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000002699 waste material Substances 0.000 claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 238000005261 decarburization Methods 0.000 claims description 3
- 238000011534 incubation Methods 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- 241000276425 Xiphophorus maculatus Species 0.000 description 5
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- 238000007373 indentation Methods 0.000 description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000007550 Rockwell hardness test Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
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- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a preparation method of rare earth-added hard alloy, which comprises the following preparation steps: (1) calcining the waste high-cobalt coarse-grain hard alloy to obtain eta-phase-containing waste hard alloy; (2) crushing and sieving the eta-phase-containing waste hard alloy to obtain waste hard alloy powder; (3) carrying out ball milling mixing, granulating, pressing and sintering on the waste hard alloy powder, the rare earth element salt solution, the C powder and the WC powder to obtain rare earth-added hard alloy; the eta-phase-containing waste hard alloy contains 50 to 80 wt% of eta phase. The method provided by the invention comprises the steps of calcining the waste high-cobalt coarse-grain hard alloy, sintering the calcined waste high-cobalt coarse-grain hard alloy with rare earth elements and WC powder together to obtain WC crystal grains with plate-shaped structures, and simultaneously improving the hardness and toughness of the hard alloy.
Description
Technical Field
The invention relates to the technical field of hard alloy, in particular to rare earth-added hard alloy and a preparation method thereof.
Background
Cemented carbide has high strength, high hardness, high wear resistance, and high red hardness, and is widely used as cutting tools, mining tools, wear-resistant parts, and the like. The hard alloy material mainly comprises hard phase WC and binder phase Co metal, wherein the hard phase WC mainly provides the wear resistance and hardness of the material, and the binder phase Co mainly provides the fracture toughness of the material. The introduction of plate-like WC grains into the cemented carbide can improve the morphology of hard phase grains and realize the 'double height' of the hardness and toughness of the cemented carbide. When the plate-shaped WC crystal grains exist in the hard alloy and the content (mass fraction) of the plate-shaped WC crystal grains is higher than 20%, the alloy can show a series of excellent mechanical properties such as high hardness, high toughness, good high-temperature creep property, high-temperature fatigue strength and the like. The existing main methods for preparing the hard alloy containing the platy WC crystal grains comprise the following three methods:
(1) adopting a WC powder raw material with nano-scale granularity, heating the liquid-phase sintering temperature to be higher than the critical temperature, and realizing the preparation of platy WC crystal grains by dissolving and separating out the WC crystal grains; the method requires that the size of the WC raw material reaches the nanometer level, the activity is high, and the control difficulty of the organization structure is high in the production process.
(2) WC forms plate-like WC grains by nucleation and growth in a solid or liquid binder phase, wherein the formation of WC grains mainly results from the decomposition of η -phase powder. Such as by adding a small amount of eta-phase powder (mainly Co) to WC-10Co powder3W3C and Co6W6C) And C powder required for decomposition, and can be prepared into hard alloy containing tabular WC grains by adopting the traditional powder metallurgy processAnd (4) a heavy alloy. This method is used for CoxWyCzThe quality requirement of the powder is high, and Co is prepared in advancexWyCzPowder; in addition, the eta-phase decomposition rate is slow during sintering, and W is easily formed2C brittle phase, which adversely affects the alloy properties;
(3) by adding plate-shaped WC crystal grain forming elements such as TiC, the method requires that the WC raw material is in a superfine nanometer level, and introduces plate-shaped WC crystal grain inducing elements, which are unfavorable for the fracture toughness of the alloy.
Especially for coarse grain hard alloy, because of using coarse grain WC raw material, the activity is low, the tabular WC crystal grain is not easy to form in the sintering process. The coarse eta-phase powder is used as the raw material, so that incomplete eta-phase decomposition and W formation are easy to occur2C brittle phase.
In conclusion, the prior hard alloy preparation has the problems of difficult formation of platy WC crystal grains, high preparation process requirement and difficult control of the comprehensive performance of the alloy.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a rare earth-added hard alloy, the preparation method recycles the waste high-cobalt coarse-grain hard alloy, and the prepared hard alloy contains WC grains with a plate-shaped structure and simultaneously improves the hardness and toughness of the material. The invention also provides the hard alloy added with the rare earth.
The invention provides a preparation method of rare earth-added hard alloy, which comprises the following preparation steps:
(1) calcining the waste high-cobalt coarse-grain hard alloy to obtain eta-phase-containing waste hard alloy;
(2) crushing and sieving the eta-phase-containing waste hard alloy to obtain waste hard alloy powder;
(3) carrying out ball milling mixing, granulating, pressing and sintering on the waste hard alloy powder, the rare earth element salt solution, the C powder and the WC powder to obtain rare earth-added hard alloy;
the eta-phase-containing waste hard alloy contains 50 to 80 wt% of eta phase.
According to some embodiments of the invention, the eta-phase-containing waste cemented carbide contains 50 to 80% by weight of eta-phase, for example, 55 to 75% by weight of eta-phase, 60 to 70% by weight of eta-phase, and 65% by weight of eta-phase. In the present invention, a specific content of η phase can be obtained by adjusting the calcination process, mainly the calcination time. In the eta phase range of 50-80 wt%, the subsequent steps are facilitated, and the hard alloy containing WC crystal grains with plate-shaped structures can be prepared, and meanwhile, the hardness and the toughness of the material can be improved.
According to some embodiments of the invention, the spent high cobalt macrocrystalline cemented carbide has a Co binder phase content of 20-25 wt%.
According to some embodiments of the invention, the spent high cobalt macrocrystalline cemented carbide has a Co binder phase content of 23 wt%.
According to some embodiments of the invention, the particle size of the waste cemented carbide powder is 4-8 μm.
According to some embodiments of the invention, the particle size of the waste cemented carbide powder is 6-8 μm.
According to some embodiments of the invention, the particle size of the waste cemented carbide powder is 5-8 μm.
According to some embodiments of the invention, the particle size of the scrap cemented carbide powder is 4.5 μm.
According to some embodiments of the invention, the WC powder has a particle size of 4-8 μm.
According to some embodiments of the invention, the WC powder has a particle size of 6-8 μm.
According to some embodiments of the invention, the WC powder has a particle size of 5-8 μm.
According to some embodiments of the invention, the WC powder has a particle size of 4.5-8 μm.
According to some embodiments of the invention, the WC powder is added in an amount of 25-52 wt% of the rare earth-doped cemented carbide.
According to some embodiments of the invention, the scrap cemented carbide powder is added in an amount of 48-75 wt% of the rare earth cemented carbide.
According to some embodiments of the present invention, in the sintering stage in step (3), the heat preservation is performed at 1250-.
According to some embodiments of the invention, in the sintering phase in step (3), the incubation is performed at 1300 ℃ in the solid phase.
According to some embodiments of the invention, the incubation time is 3-5 hours.
According to some embodiments of the present invention, the sintering temperature is 1410-1500 ℃.
According to some embodiments of the invention, the rare earth element is one or more of Ce, Y, Sm, Nd, La.
According to some embodiments of the invention, the rare earth element is Ce.
According to some embodiments of the invention, the rare earth element salt solution is a rare earth element nitrate solution.
According to some embodiments of the present invention, the concentration of the rare earth element in the rare earth element salt solution is 150 to 200 g/l.
According to some embodiments of the invention, the rare earth element is added in an amount of 0.1 to 0.5 wt% of the total amount of cemented carbide powder.
According to some embodiments of the invention, the rare earth element is added in an amount of 0.3 wt%.
According to some embodiments of the invention, the ball-to-feed ratio of the ball mill in step (3) is 3 to 6.
According to some embodiments of the invention, the ball milling time is from 24 to 36 hours.
According to some embodiments of the invention, the calcination in step (1) is performed in a decarbonation protective atmosphere.
According to some embodiments of the present invention, the decarburization atmosphere may be selected from an inert gas atmosphere or a hydrogen gas atmosphere.
According to some embodiments of the present invention, the temperature of the calcination is 1480-.
The addition amount of the C powder is calculated according to the WC content in the hard alloy which is required to be prepared. For example, in the case of a WC-20 wt% Co cemented carbide, because the eta phase is decarburized (for example, 20 wt% of waste high cobalt macrocrystalline cemented carbide is used as a raw material, the carbon content is generally less than 4.50 wt%), in order to make the eta phase decompose and the alloy phase region in the sintered alloy be in a two-phase region (the third phase, namely, the carburized phase and the decarburized phase, does not occur), C powder must be added so that the carbon content in the alloy reaches 4.82 to 5.01 wt%, that is, 0.32 to 0.51 wt% of C powder must be added. The addition amount of the C powder can be performed according to the conventional operation in the field, and is not described in detail herein.
In a second aspect, the invention provides a rare earth-doped cemented carbide prepared by the method of the first aspect.
According to some embodiments of the invention, the rare earth-added cemented carbide comprises plate-like structure WC grains.
According to some embodiments of the invention, the content of the plate-like structure WC grains is 50-80 wt%.
According to some embodiments of the invention, the rare earth-doped cemented carbide has a binder phase content of 12-15 wt%.
According to some embodiments of the invention, the binder phase content of the rare earth-doped cemented carbide is 13.5 wt%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the rare earth-added hard alloy provided by the invention realizes the efficient utilization of the waste high-cobalt coarse-grain hard alloy, obtains the eta-phase powder containing 50-80 wt%, and is beneficial to the control of the quantity of the plate-shaped WC crystal grains of the subsequent hard alloy;
(2) the rare earth-added hard alloy provided by the invention has good fracture toughness and strong wear resistance;
(3) the preparation method of the rare earth-added hard alloy provided by the invention has unexpected fast decomposition of eta phase and avoids forming W2C brittle phase, enabling sufficient formation of tabular WC grains;
(4) in the waste hard alloy powder, WC and Co exist in a prealloy form, Co, WC phases and eta phases are in close contact, C can be better transmitted in the sintering process, WC grains can quickly grow into plate-shaped grains, and the eta phases can be promoted to decompose to form the plate-shaped grains;
(5) the rare earth elements are added in the form of salt solution, especially nitrate solution, which is helpful for the rare earth elements to be dispersed uniformly and achieve the purpose of uniform molecular mixing.
Drawings
FIG. 1 is a flow chart of the preparation of rare earth-doped cemented carbide according to example 1 of the present invention;
FIG. 2 is a structural view of a microstructure of a rare earth-doped cemented carbide according to example 1 of the present invention;
fig. 3 is a view showing a microstructure of a cemented carbide according to comparative example 1 of the present invention.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The test method and the equipment used in the test are as follows:
the method for measuring the content of the binding phase and the eta phase comprises the following steps: x-ray diffraction method, i.e. the percentage content of eta phase in the alloy can be calculated according to the intensity of eta phase diffraction peak.
In the present invention, the spent high cobalt macrocrystalline cemented carbide comes from cemented carbide dies and rolls, and the specific cemented carbide grade is commercially available tungsten carbide cemented carbide, such as YG20, YG20C, YG25 and YG 25C.
Example 1
And preparing the rare earth-added hard alloy. The preparation process is shown in figure 1, and the specific preparation method comprises the following steps:
(1) calcining the waste high-cobalt coarse-grained hard alloy with the content of the Co binder phase of 20 weight percent for 1h at the temperature of 1480 ℃ in a decarburization protective atmosphere to obtain the waste hard alloy with the content of eta phase of 50 weight percent and the content of carbon of 4.5 weight percent;
(2) crushing and sieving the waste hard alloy containing eta phase calcined in the step (1) to obtain waste hard alloy powder containing eta phase with the granularity of 4 mu m;
(3) and (3) performing ball milling mixing, granulating, pressing and sintering on 60 wt% of eta-phase-containing waste hard alloy powder, 0.248 wt% of C powder, 0.1 wt% of Ce rare earth element nitrate solution (in the solution, the concentration of Ce is 150 g/L) and 39.652 wt% of WC powder (carbon content is 6.13 wt%) with the particle size of 4 mu m in the step (2), and performing heat preservation at 1250 ℃ in a solid phase stage for 3 hours to obtain the rare earth-added hard alloy with the binder phase content of 12 wt%, wherein the carbon content in the alloy is 5.4 wt%.
(wherein the adding amount of the C powder is calculated according to the following steps of 60% by 4.5% to 2.7% of waste high-cobalt coarse-grain cemented carbide with 20 wt% of Co binder phase, 40% by 6.13% to 2.452% of WC powder, 2.7% by 2.452% of total carbon and 5.152% of carbon to be supplemented, and 5.4% to 5.152% by 0.248% of carbon to be supplemented)
Examples 2 to 17
And preparing the rare earth-added hard alloy. The preparation method is the same as that of example 1, except that the preparation parameters are different, and the specific preparation parameters are shown in table 1.
Comparative example 1
WC powder with the grain size of 4 mu m, Co powder and nitric acid solution containing 0.1 wt% Ce rare earth element (in the solution, the concentration of Ce is 150 g/L) are subjected to ball milling mixing, granulation, pressing and sintering, and heat preservation is carried out for 3 hours at the solid phase stage 1250 ℃, so that the hard alloy with the binding phase content of 12 wt% is obtained.
Comparative examples 2 to 3
And preparing the rare earth-added hard alloy. The preparation method is the same as that of example 1, except that the preparation parameters are different, and the specific preparation parameters are shown in table 1.
Test example 1
And testing the content of the plate-shaped WC crystal grains.
(1) The hard alloys obtained in example 1 and comparative example 1 were examined metallographically using a Leica DMI5000M optical microscope, Leica, Germany, and the microstructure diagrams are shown in FIG. 2 and FIG. 3, respectively.
As can be seen from fig. 2 and 3, the rare earth addition cemented carbide according to the present invention formed more plate-like WC grains than the cemented carbide according to comparative example 1.
(2) The cemented carbides prepared in example 1 and comparative example 1 were subjected to a content test of plate-like WC grains: the WC grain shape was measured by using WC grain statistical analysis software Image J, as plate-like WC grains having an aspect ratio of more than 3.
According to the measurement results, the plate-like WC grain content of example 1 is more than 50%; and the content of the tabular WC grains of comparative example 1 is less than 10%, which shows that the rare earth-added cemented carbide provided by the present invention promotes the formation of the tabular WC grains.
Test example 2
The cemented carbides of examples 1-17 and comparative examples 1-3 were subjected to performance tests and the results are shown in table 2. The test method comprises the following steps:
fracture toughness: cemented carbide is a brittle material, the fracture of which is typically a brittle fracture. The rupture toughness of the alloy is measured by adopting a Palmqvist indentation method. According to the international standard ISO28079-2009 for fracture toughness of cemented carbides. Before testing, the sample is made into a metallographic sample, and then a pyramid-shaped pressure head is pressed into the surface of the hard alloy sample to be tested under the pressure of 30kgf (294N) to obtain an indentation. And crack lengths L1, L2, L3 and L4 at the corners of the indentation of the sample were measured. The fracture toughness of each sample was measured at three points and averaged.
Hardness: according to GBT 3849.1-2015 Rockwell hardness test (Scale A) part 1 test method. The Rockwell Hardness (HRA) of the alloy was determined using a double Rockwell hardness tester (Wilson 574T). Before testing, the surface of the hard alloy sample is ground to a thickness of more than 0.2mm, the surface roughness is not less than R alpha 1.25 mu m, and the sample has a thickness of more than 3 x 3mm2The bottom surface of the sample and the working surface are ground to be flat and parallel. Three points were tested for rockwell hardness of each sample and the average was taken.
Table 2 table of performance test results
According to the test results shown in table 2, the content of the plate-shaped grains of examples 1 to 17 is high, the plate-shaped grains do not appear in comparative example 1, and the fracture toughness and hardness of examples 1 to 17 are higher than those of comparative example 1, which shows that the rare earth-added cemented carbide provided by the invention promotes the formation of the plate-shaped grains and improves the fracture toughness and hardness of the cemented carbide. The content of platy crystals, the fracture toughness and the hardness of the example 1 are all superior to those of the comparative examples 2 and 3, which shows that the prepared hard alloy forms more platy crystals and improves the fracture toughness and the hardness of the hard alloy by controlling the eta phase content of the waste hard alloy.
In conclusion, the preparation method of the rare earth-added hard alloy provided by the invention enables the plate-shaped WC crystal grains to be fully formed, improves the hardness and toughness of the hard alloy, and prolongs the service life of the hard alloy.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (10)
1. The preparation method of the rare earth-added hard alloy is characterized by comprising the following preparation steps:
(1) calcining the waste high-cobalt coarse-grain hard alloy to obtain eta-phase-containing waste hard alloy;
(2) crushing and sieving the eta-phase-containing waste hard alloy to obtain waste hard alloy powder;
(3) carrying out ball milling mixing, granulating, pressing and sintering on the waste hard alloy powder, the rare earth element salt solution, the C powder and the WC powder to obtain rare earth-added hard alloy;
the eta-phase-containing waste hard alloy contains 50 to 80 wt% of eta phase.
2. The method according to claim 1, wherein the spent high cobalt macrocrystalline cemented carbide has a Co binder phase content of 20-25 wt-%.
3. The method according to claim 1 or 2, wherein the particle size of the scrap cemented carbide powder is 4-8 μ ι η;
preferably, the WC powder has a particle size of 4-8 μm;
preferably, the addition amount of the WC powder is 25-52 wt% of the rare earth-doped cemented carbide;
preferably, the amount of the waste cemented carbide powder added is 48-75 wt% of the rare earth-doped cemented carbide.
4. The method as claimed in any one of claims 1 to 3, wherein the sintering stage in step (3) is performed at 1250 ℃.;
preferably, the incubation time is 3-5 hours.
5. The process according to any one of claims 1 to 4, wherein the rare earth element is one or more of Ce, Y, Sm, Nd, La, preferably Ce;
preferably, the rare earth element salt solution is a rare earth element nitrate solution;
preferably, the concentration of the rare earth element in the salt solution of the rare earth element is 150-200 g/l.
6. The method according to any one of claims 1 to 5, wherein the rare earth element is added in an amount of 0.1 to 0.5 wt% based on the total amount of the cemented carbide powder.
7. The method according to any one of claims 1 to 6, wherein the calcination in step (1) is carried out in a decarburization atmosphere.
8. The method as claimed in any one of claims 1 to 7, wherein the calcination temperature is 1480-1550 ℃ and the calcination time is 1 to 10 hours.
9. A rare earth-doped cemented carbide produced by the method of any one of claims 1 to 8.
10. The rare earth cemented carbide of claim 9, wherein the rare earth-added cemented carbide comprises plate-like structure WC grains;
preferably, the content of the plate-like structure WC crystal grains is 50-80 wt%;
preferably, the binder phase content of the rare earth-doped cemented carbide is 12 to 15 wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114752801A (en) * | 2022-05-12 | 2022-07-15 | 崇义章源钨业股份有限公司 | Plate-shaped crystal reinforced net-shaped structure hard alloy and preparation method thereof |
| CN115305400A (en) * | 2022-08-16 | 2022-11-08 | 江西理工大学 | WC-Co-Al hard alloy added with rare earth and preparation method thereof |
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| CN115305400A (en) * | 2022-08-16 | 2022-11-08 | 江西理工大学 | WC-Co-Al hard alloy added with rare earth and preparation method thereof |
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