CN111996432B - Preparation method of ultra-coarse hard alloy material - Google Patents
Preparation method of ultra-coarse hard alloy material Download PDFInfo
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
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- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Abstract
The invention discloses a preparation method of an ultra-coarse hard alloy, which is characterized by comprising the steps of carrying out surface roughening treatment on ultra-coarse WC powder, introducing a Cu element (and a small amount of a P element) into the WC powder by utilizing a chemical reaction, carrying out heat preservation at 700-710 ℃ for 1h to form a Cu-P solid solution in the WC powder, mixing the Cu-P solid solution with Co powder, carrying out low-parameter ball milling to realize uniform mixing of WC and Co and reduce the crushing degree of WC, carrying out sintering after compression molding, filling Ar gas at 700 ℃ to inhibit Cu volatilization, finally carrying out sintering at 1370-1380 ℃, and rapidly cooling to below 700 ℃ at the average cooling speed of 100-110 ℃/min after sintering is finished to avoid Cu3P、Co2P brittle phase is precipitated at WC/Co interface. The invention overcomes the problems that the prior ultra-coarse hard alloy is wide in grain size distribution and abnormally large due to high sintering temperature, and densification is difficult to realize due to low sintering temperature. The ultra-coarse hard alloy with the WC grain size of 6-10 mu m is prepared at a low sintering temperature, the structure is uniform, abnormal growth is avoided, the grain distribution dispersion is low, and the strength is good.
Description
Technical Field
The invention relates to a preparation method of a hard alloy material, in particular to a preparation method of an ultra-coarse hard alloy, and belongs to the field of hard alloys.
Background
The ultra-coarse hard alloy is hard alloy with average grain size over 6 μm, has excellent heat conduction performance, thermal shock resistance and thermal fatigue resistance, is an ideal tool material for ground and mine engineering, and is one of the development directions of hard alloy materials.
CN103866172B discloses a method for preparing ultra-coarse hard alloy with narrow particle size distribution, which comprises crushing ultra-coarse hard aggregate of tungsten carbide powder, grading the particle size of the tungsten carbide powder, coating cobalt on the tungsten carbide powder by magnetron sputtering, wet mixing, drying, pressing and sintering. The prepared ultra-coarse WC-Co hard alloy has the advantages of uniform structure, large average grain size of WC hard phase and narrow grain distribution. CN111069619A discloses a preparation method of an extra-coarse grain hard alloy mixture, which comprises the following steps: mechanically mixing materials: stirring and drying the base liquid and the solid raw material at the rotation speed of 1-200r/min, the vacuum degree of-0.05-0.99 MPa and the temperature of 25-120 ℃, and sieving to obtain mixed powder; wherein the solid raw material comprises a cobalt salt, an additive and WC powder. And calcining and reducing the mixed powder to obtain the extra-coarse grain hard alloy mixture. The invention adopts a mechanical method to uniformly mix the cobalt salt and the WC powder, avoids the WC powder from being crushed, keeps the integrity of crystal grains, and can obtain the extra-coarse grain hard alloy with the WC average grain size larger than 6 mu m after the prepared extra-coarse grain hard alloy mixture is pressed, formed and sintered.
In the preparation process of the ultra-coarse tungsten carbide powder, the ultra-coarse tungsten carbide powder is easy to crush during ball milling, the WC particle size is reduced, and the WC and Co cannot be uniformly mixed by reducing the ball milling parameters; in order to obtain the ultra-coarse WC grain size, a higher temperature is adopted in the sintering process, but WC is abnormally grown, and the mechanical property of the ultra-coarse hard alloy is influenced. Therefore, how to obtain ultra-coarse grain size. Narrow grain size distribution and uniform microstructure are key issues in the preparation of ultra-coarse hard alloys.
Disclosure of Invention
Aiming at the problems that WC grains grow abnormally while growing normally due to the adoption of low ball milling parameters and high sintering temperature in the existing preparation process of preparing the ultra-coarse hard alloy, so that the grain size distribution is wider and the material performance is reduced, the invention provides the method for preparing the ultra-coarse hard alloy by introducing a Cu element into WC powder, and realizing densification by utilizing a Co-Cu solid solution formed in the sintering process and a liquid phase at a lower sintering temperature, so that the problems are avoided. The method firstly coarsens the ultra-coarse WC, and then utilizes chemical reaction to form WC powderCu (and P) is introduced into the powder, the Cu and the Co powder are mixed and ball-milled and then are pressed and formed, Cu and Co form a solid solution at a middle temperature in the sintering process, P and Co form an eutectic phase, and finally densification is realized at a lower sintering temperature. The uniform mixing of WC and Co and the reduction of WC crushing degree are realized by carrying out low-parameter planetary ball milling on the Co powder mixture, argon is filled in the medium-temperature stage in the sintering process to avoid evaporation loss and hole formation after the Cu liquid phase appears, the vacuum is restored in the final stage of high-temperature stage sintering, and the argon is filled again for quick cooling, so that Co is prevented from being rapidly cooled2The P brittle phase is separated out at a WC/Co interface, and the ultra-coarse hard alloy with uniform microstructure, no abnormal growth of WC grains and WC grain size larger than 6 mu m is prepared at low sintering temperature.
The preparation method of the ultra-coarse hard alloy material is characterized by sequentially comprising the following steps of:
(1) coarsening WC powder: weighing ultra-coarse WC powder with a Fisher particle size of 25-50 mu m, and adding the ultra-coarse WC powder into absolute ethyl alcohol to prepare a mixed solution A, wherein the concentration of WC in the mixed solution A is 150-250 g/L; then adding HF into the mixed solution A to enable the concentration of the HF to be 30-50 ml/L, and preserving the temperature of the mixed solution A at 50-60 ℃ for 12-24 h to finish WC coarsening treatment; after the coarsening treatment is finished, cleaning the mixed solution A for more than 5 times by adopting absolute ethyl alcohol, and preserving heat at 90 ℃ for 1h to finish drying;
(2) introducing Cu element into the ultra-coarse WC powder: weighing the WC powder subjected to roughening treatment and drying, adding the WC powder into deionized water to form a mixed solution B, controlling the concentration of WC in the mixed solution B to be (40 + 0.4X powder Fisher size value) g/L so that a mixed solution D formed after the WC is added into the mixed solution C is kept stable, then adding Tween 60 into the mixed solution B so that the concentration of the Tween is 1-2 g/L, and performing ultrasonic dispersion treatment for 30 min; weighing copper sulfate, nickel sulfate, sodium hypophosphite, boric acid and sodium citrate, adding the weighed copper sulfate, nickel sulfate, sodium hypophosphite, boric acid and sodium citrate into deionized water to prepare a mixed solution C, wherein the formula of the mixed solution C is 35-45 g/L of copper sulfate, 1-2 g/L of nickel sulfate, 20-35 g/L of sodium hypophosphite, 30-40 ml/L of boric acid and 15-20 g/L of sodium citrate; mixing the mixed solution B and the mixed solution C together according to the volume ratio of 1:1 to form a mixed solution D, adjusting the pH value of the mixed solution D to be 8-10 to control the content of P, keeping the temperature at 50-75 ℃ for 60-90 min, continuously stirring during the heat preservation period to keep WC suspended, and reducing copper sulfate by sodium hypophosphite to deposit Cu and P elements on the surfaces of the ultra-coarse WC particles; finally, cleaning the mixed solution D for more than 5 times by adopting absolute ethyl alcohol, and preserving heat for 1h at 90 ℃ to finish drying to obtain ultra-coarse WC powder introduced with Cu element and a small amount of P element;
(3) solution treatment of ultra-coarse WC powder: heating the super-coarse WC powder containing Cu and a small amount of P element to 700-710 ℃ in a vacuum sintering furnace, and preserving heat for 1h to make P solid dissolved in Cu to form super-coarse WC powder containing a Cu-P solid solution;
(4) preparing an ultra-coarse hard alloy mixture: weighing super-coarse WC powder containing a Cu-P solid solution and Co powder with a Fisher size of 1.0-1.5 mu m to prepare a WC-Co super-coarse hard alloy, wherein the adding amount of the Co powder is 6-15 wt.%; ball-milling the mixed powder for 18-24 h at the rotating speed of 56r/min, adopting WC-6Co superfine hard alloy grinding balls with the diameter of 6mm, wherein the weight ratio of the grinding balls to the hard alloy mixed powder is (0.5-1): 1, and filtering, drying and sieving the mixed powder after the ball-milling is finished to prepare a superfine hard alloy mixture;
(5) forming and sintering the ultra-coarse hard alloy: pressing the ultra-coarse hard alloy mixture into a green body under the pressure of 250-350 MPa; sintering the green body in an atmosphere sintering furnace, heating to 300-450 ℃, and keeping the temperature for 2h to remove the forming agent; after the temperature is raised to 700 ℃, a vacuum pump is closed, argon gas with pressure of 0.1-0.15 MPa is filled in the vacuum pump, and partial pressure treatment is carried out to inhibit Cu volatilization; continuously heating to form a Cu-P and Co-P eutectic liquid phase, and finally preserving heat at 1370-1380 ℃ for 1.5h to finish sintering; quickly vacuumizing to 10-20 Pa 2-5 min before sintering; immediately introducing Ar gas with the flow rate of 55-65L/h after sintering, and rapidly cooling to below 700 ℃, wherein the average cooling speed is 90-100 ℃/min; and then cooling along with the furnace, wherein the density of the prepared ultra-coarse hard alloy is more than 99.5 percent, the average grain size D50 of WC is 6-10 mu m, the grain size distribution of WC is narrow, the dispersion of the grain distribution (D90-D10)/D50= 1.4-1.5, the microstructure is uniform, no grains grow up abnormally, and the phase interface of WC and Co does not contain Cu3P、Co2P phase is generated, and the bending strength is not less than 1800 MPa.
The preparation method of the ultra-coarse hard alloy material is further characterized by comprising the following steps:
(1) adopting absolute ethyl alcohol to clean the mixed solution A, and enabling the mixed solution to be neutral;
(2) the mixed solution D is subjected to ultrasonic stirring when the temperature is kept at 50-75 ℃, and the ultrasonic frequency is 4 x 104Hz, power 100W; adopting absolute ethyl alcohol to clean the mixed solution D, and enabling the mixed solution to be neutral;
(3) during the solution treatment of the ultra-coarse WC powder, the heating rate is 5 ℃/min, the vacuum degree is 10-15 Pa, and after the heat preservation is finished, the ultra-coarse WC powder is cooled along with a furnace;
(4) the ball milling medium of the ball milling of the WC-Co mixed powder is absolute ethyl alcohol, the addition amount of the absolute ethyl alcohol is 15-20% of the total weight of the hard alloy mixed powder, and PEG4000 with the weight being 2% of the total weight of the hard alloy mixed powder is added to serve as a forming agent; filtering by using a 400-mesh screen after the ball milling is finished, drying at 90-95 ℃, and sieving by using a 100-mesh sieve;
(5) the temperature rise speed during sintering of the hard alloy is 10 ℃/min, and the vacuum degree before 700 ℃ is 5-10 Pa.
The invention has the advantages that: (1) the Cu element is introduced into coarse-grain WC raw material powder by a chemical method, and the Cu-P, Co-P eutectic with low eutectic temperature is formed, so that the sintering temperature is reduced, the densification is realized at a lower temperature, and the prepared ultra-coarse hard alloy has no abnormal growth of grains. The traditional ultra-coarse hard alloy has high sintering temperature, abnormal WC growth, wide grain size distribution and difficult realization of densification due to low sintering temperature. (2) Harmful substances such as formaldehyde and the like are not used in the process of introducing the Cu element; the process is simple, and special means such as vapor deposition and the like are not used; (3) controlling the loading of WC to keep the mixed solution of the introduced Cu stable, and controlling the pH value to obtain low P content; (4) the Cu-containing WC powder forms a Cu-P solid solution after heat treatment, and can avoid the formation of Co at a WC/Co interface in the subsequent sintering process2P causes increased brittleness. (5) The P element and the Cu element are introduced into the raw material powder of the coarse WC particles, which is beneficial to improving the uniform distribution of WC-Co, so that parameters such as low ball-to-material ratio, ball-milling time and the like are adopted in the ball-milling process, and the crushing degree of the coarse WC particles in the ball-milling process can be reduced by adopting fine grinding balls; (6) after sintering, Ar gas is adopted for forced cooling, thereby avoiding Co in the cooling process2P、Cu3The P phase precipitates at the WC/Co interface, resulting in increased brittleness.
Drawings
FIG. 1 is a schematic view of a process for preparing an ultra-coarse hard alloy by the method of the present invention
Detailed Description
Example 1: the ultra-coarse hard alloy material is prepared by the following steps:
(1) coarsening WC powder: weighing extra-coarse WC powder with a Fisher particle size of 25 mu m, and adding the extra-coarse WC powder into absolute ethyl alcohol to prepare a mixed solution A, wherein the concentration of WC in the mixed solution A is 190 g/L; then adding HF into the mixed solution A to enable the concentration of the HF to be 32ml/L, and preserving the temperature of the mixed solution A at 55 ℃ for 16h to finish WC coarsening treatment; after the coarsening treatment is finished, cleaning the mixed solution A for more than 5 times to be neutral by adopting absolute ethyl alcohol, and preserving heat for 1h at 90 ℃ to finish drying;
(2) introducing Cu element into the ultra-coarse WC powder: weighing the WC powder subjected to roughening treatment and drying, adding the WC powder into deionized water to form a mixed solution B, controlling the concentration of WC in the mixed solution B to be 50g/L so that the mixed solution D formed after the WC is added into the mixed solution C is kept stable, then adding Tween 60 into the mixed solution B so that the concentration of the Tween 60 is 1g/L, and performing ultrasonic dispersion treatment for 30 min; weighing copper sulfate, nickel sulfate, sodium hypophosphite, boric acid and sodium citrate, adding the weighed copper sulfate, nickel sulfate, sodium hypophosphite, boric acid and sodium citrate into deionized water to prepare a mixed solution C, wherein the formula of the mixed solution C is 35g/L of copper sulfate, 1g/L of nickel sulfate, 23g/L of sodium hypophosphite, 32ml/L of boric acid and 16g/L of sodium citrate; mixing the mixed solution B and C at a volume ratio of 1:1 to form a mixed solution D, adjusting the pH value of the mixed solution D to 9 to control the content of P, keeping the temperature at 55 ℃ for 65min, and continuously carrying out ultrasonic stirring during the heat preservation period to keep WC suspended, wherein the ultrasonic frequency is 4 x 104Hz, the power is 100W, and copper sulfate is reduced by sodium hypophosphite to ensure that Cu and P elements are deposited on the surfaces of the ultra-coarse WC particles; finally, cleaning the mixed solution D for more than 5 times by using absolute ethyl alcohol until the mixed solution D is neutral, and preserving heat for 1h at 90 ℃ to finish drying to obtain ultra-coarse WC powder introduced with Cu element and a small amount of P element;
(3) solution treatment of ultra-coarse WC powder: heating ultra-coarse WC powder containing Cu and a small amount of P elements to 700 ℃ in a vacuum sintering furnace, preserving heat for 1h to enable P to be dissolved in Cu in a solid solution mode, wherein the temperature rise speed of the ultra-coarse WC powder in the solid solution treatment is 5 ℃/min, the vacuum degree is 10Pa, and cooling along with the furnace after the heat preservation is finished to form the ultra-coarse WC powder containing the Cu-P solid solution;
(4) preparing an ultra-coarse hard alloy mixture: weighing super-coarse WC powder containing a Cu-P solid solution and Co powder with the Fisher size of 1.4 mu m to prepare WC-Co super-coarse hard alloy, wherein the adding amount of the Co powder is 12 wt.%; ball-milling the mixed powder for 20h at the rotating speed of 56r/min, adopting WC-6Co superfine hard alloy grinding balls with the diameter of 6mm, wherein the weight ratio of the grinding balls to the hard alloy mixed powder is 0.6:1, the ball-milling medium is absolute ethyl alcohol, the addition amount of the absolute ethyl alcohol is 16 percent of the total weight of the hard alloy mixed powder, and PEG4000 with the weight of 2 percent of the total weight of the hard alloy mixed powder is added as a forming agent; filtering by using a 400-mesh screen after the ball milling is finished, drying at 90 ℃, and sieving by using a 100-mesh sieve to prepare an ultra-coarse hard alloy mixture;
(5) forming and sintering the ultra-coarse hard alloy: pressing the ultra-coarse hard alloy mixture into a green body under the pressure of 250 MPa; sintering the green body in an atmosphere sintering furnace, heating to 350 ℃, and keeping the temperature for 2h to remove the forming agent; the heating rate in the sintering process is 10 ℃/min, and the vacuum degree before 700 ℃ is 6 Pa; after the temperature is raised to 700 ℃, a vacuum pump is closed, and argon gas with the pressure of 0.1MPa is filled for partial pressure treatment so as to inhibit Cu volatilization; continuously heating to form a Cu-P and Co-P eutectic liquid phase, and finally preserving heat at 1375 ℃ for 1.5h to finish sintering; 2min before sintering, quickly vacuumizing to 12 Pa; after sintering, Ar gas with the flow rate of 60L/h is immediately fed in and is rapidly cooled to below 700 ℃, and the average cooling speed is 95 ℃/min; then cooling along with the furnace, the density of the prepared ultra-coarse hard alloy is 99.7 percent, the average grain size D50 of WC is 6 μm, the grain size distribution of WC is narrow, the dispersion of the grain distribution (D90-D10)/D50=1.4, the microstructure is uniform, no grains grow up abnormally, and the phase interface of WC and Co has no Cu3P、Co2P phase is generated, and the bending strength is 1820 MPa.
Example 2: the ultra-coarse hard alloy material is prepared by the following steps:
(1) coarsening WC powder: weighing extra-coarse WC powder with Fisher granularity of 45 μm, and adding into anhydrous ethanol to obtain mixed solution A, wherein the concentration of WC in the mixed solution A is 220 g/L; then adding HF into the mixed solution A to enable the concentration of the HF to be 45ml/L, and preserving the temperature of the mixed solution A at 60 ℃ for 22h to finish WC coarsening treatment; after the coarsening treatment is finished, cleaning the mixed solution A for more than 5 times to be neutral by adopting absolute ethyl alcohol, and preserving heat for 1h at 90 ℃ to finish drying;
(2) introducing Cu element into the ultra-coarse WC powder: weighing WC powder which is subjected to roughening treatment and drying, adding the WC powder into deionized water to form a mixed solution B, controlling the concentration of WC in the mixed solution B to be 58g/L so that the mixed solution D formed after the WC is added into the mixed solution C is kept stable, then adding Tween 60 into the mixed solution B so that the concentration of the Tween 60 is 1.5g/L, and performing ultrasonic dispersion treatment for 30 min; weighing copper sulfate, nickel sulfate, sodium hypophosphite, boric acid and sodium citrate, adding into deionized water to prepare a mixed solution C, wherein the formula of the mixed solution C comprises 40g/L of copper sulfate, 2g/L of nickel sulfate, 30g/L of sodium hypophosphite, 35ml/L of boric acid and 20g/L of sodium citrate; mixing the mixed solution B and C together according to a volume ratio of 1:1 to form a mixed solution D, adjusting the pH value of the mixed solution D to 10 to control the content of P, keeping the temperature at 70 ℃ for 90min, continuously carrying out ultrasonic stirring during the heat preservation period to keep WC suspended, wherein the ultrasonic frequency is 4 x 104Hz, the power is 100W, and copper sulfate is reduced by sodium hypophosphite to ensure that Cu and P elements are deposited on the surfaces of the ultra-coarse WC particles; finally, cleaning the mixed solution D for more than 5 times by using absolute ethyl alcohol until the mixed solution D is neutral, and preserving heat for 1h at 90 ℃ to finish drying to obtain ultra-coarse WC powder introduced with Cu element and a small amount of P element;
(3) solution treatment of ultra-coarse WC powder: heating ultra-coarse WC powder containing Cu and a small amount of P elements to 710 ℃ in a vacuum sintering furnace, preserving heat for 1h to enable P to be dissolved in Cu in a solid solution mode, wherein the temperature rise speed of the ultra-coarse WC powder in the solid solution treatment is 5 ℃/min, the vacuum degree is 15Pa, and after the heat preservation is finished, cooling the ultra-coarse WC powder along with the furnace to form the ultra-coarse WC powder containing the Cu-P solid solution;
(4) preparing an ultra-coarse hard alloy mixture: weighing super-coarse WC powder containing a Cu-P solid solution and Co powder with the Fisher size of 1.5 mu m to prepare WC-Co super-coarse hard alloy, wherein the adding amount of the Co powder is 6 wt.%; ball-milling the mixed powder for 18h at the rotating speed of 56r/min, adopting WC-6Co superfine hard alloy grinding balls with the diameter of 6mm, wherein the weight ratio of the grinding balls to the hard alloy mixed powder is 1:1, the ball-milling medium is absolute ethyl alcohol, the addition amount of the absolute ethyl alcohol is 18 percent of the total weight of the hard alloy mixed powder, and PEG4000 with the weight percent of 2 percent of the total weight of the hard alloy mixed powder is added as a forming agent; filtering by using a 400-mesh screen after the ball milling is finished, drying at 95 ℃, and sieving by using a 100-mesh sieve to prepare an ultra-coarse hard alloy mixture;
(5) forming and sintering the ultra-coarse hard alloy: pressing the ultra-coarse hard alloy mixture into a green body under the pressure of 300 MPa; sintering the green body in an atmosphere sintering furnace, heating to 400 ℃, and keeping the temperature for 2h to remove the forming agent; the heating rate in the sintering process is 10 ℃/min, and the vacuum degree before 700 ℃ is 8 Pa; after the temperature is raised to 700 ℃, a vacuum pump is closed, and argon gas with the pressure of 0.15MPa is filled for partial pressure treatment so as to inhibit Cu volatilization; continuously heating to form a Cu-P and Co-P eutectic liquid phase, and finally preserving heat at 1370 ℃ for 1.5h to finish sintering; 3min before sintering, quickly vacuumizing to 15 Pa; after sintering, Ar gas with the flow rate of 55L/h is immediately fed in and is rapidly cooled to below 700 ℃, and the average cooling speed is 90 ℃/min; then cooling along with the furnace, the density of the prepared ultra-coarse hard alloy is 99.7 percent, the average grain size D50 of WC is 8 μm, the grain size distribution of WC is narrow, the dispersion of the grain distribution (D90-D10)/D50=1.46, the microstructure is uniform, no grains grow up abnormally, and the phase interface of WC and Co has no Cu3P、Co2P phase is formed, and the bending strength is 1920 MPa.
Claims (2)
1. The preparation method of the ultra-coarse hard alloy material is characterized by sequentially comprising the following steps of:
(1) coarsening WC powder: weighing ultra-coarse WC powder with a Fisher particle size of 25-50 mu m, and adding the ultra-coarse WC powder into absolute ethyl alcohol to prepare a mixed solution A, wherein the concentration of WC in the mixed solution A is 150-250 g/L; then adding HF into the mixed solution A to enable the concentration of the HF to be 30-50 ml/L, and preserving the temperature of the mixed solution A at 50-60 ℃ for 12-24 h to finish WC coarsening treatment; after the coarsening treatment is finished, cleaning the mixed solution A for more than 5 times by adopting absolute ethyl alcohol, and preserving heat at 90 ℃ for 1h to finish drying;
(2) introducing Cu element into the ultra-coarse WC powder: weighing the WC powder subjected to roughening treatment and drying, adding the WC powder into deionized water to form a mixed solution B, controlling the concentration of WC in the mixed solution B to be (40 + 0.4X powder Fisher size value) g/L so that a mixed solution D formed after the WC is added into the mixed solution C is kept stable, then adding Tween 60 into the mixed solution B so that the concentration of the Tween is 1-2 g/L, and performing ultrasonic dispersion treatment for 30 min; weighing copper sulfate, nickel sulfate, sodium hypophosphite, boric acid and sodium citrate, adding the weighed copper sulfate, nickel sulfate, sodium hypophosphite, boric acid and sodium citrate into deionized water to prepare a mixed solution C, wherein the formula of the mixed solution C is 35-45 g/L of copper sulfate, 1-2 g/L of nickel sulfate, 20-35 g/L of sodium hypophosphite, 30-40 ml/L of boric acid and 15-20 g/L of sodium citrate; mixing the mixed solution B and the mixed solution C together according to the volume ratio of 1:1 to form a mixed solution D, adjusting the pH value of the mixed solution D to be 8-10 to control the content of P, keeping the temperature at 50-75 ℃ for 60-90 min, continuously stirring during the heat preservation period to keep WC suspended, and reducing copper sulfate by sodium hypophosphite to deposit Cu and P elements on the surfaces of the ultra-coarse WC particles; finally, cleaning the mixed solution D for more than 5 times by adopting absolute ethyl alcohol, and preserving heat for 1h at 90 ℃ to finish drying to obtain ultra-coarse WC powder introduced with Cu element and a small amount of P element;
(3) solution treatment of ultra-coarse WC powder: heating the super-coarse WC powder containing Cu and a small amount of P element to 700-710 ℃ in a vacuum sintering furnace, and preserving heat for 1h to make P solid dissolved in Cu to form super-coarse WC powder containing a Cu-P solid solution;
(4) preparing an ultra-coarse hard alloy mixture: weighing super-coarse WC powder containing a Cu-P solid solution and Co powder with a Fisher size of 1.0-1.5 mu m to prepare a WC-Co super-coarse hard alloy, wherein the adding amount of the Co powder is 6-15 wt.%; ball-milling the mixed powder for 18-24 h at the rotating speed of 56r/min, adopting WC-6Co superfine hard alloy grinding balls with the diameter of 6mm, wherein the weight ratio of the grinding balls to the hard alloy mixed powder is (0.5-1): 1, and filtering, drying and sieving the mixed powder after the ball-milling is finished to prepare a superfine hard alloy mixture;
(5) forming and sintering the ultra-coarse hard alloy: pressing the ultra-coarse hard alloy mixture into a green body under the pressure of 250-350 MPa; sintering the green body in an atmosphere sintering furnace, heating to 300-450 ℃, and keeping the temperature for 2h to remove the forming agent; after the temperature is raised to 700 ℃, a vacuum pump is closed, argon gas with pressure of 0.1-0.15 MPa is filled in the vacuum pump, and partial pressure treatment is carried out to inhibit Cu volatilization; continuously heating to form a Cu-P and Co-P eutectic liquid phase, and finally preserving heat at 1370-1380 ℃ for 1.5h to finish sintering; quickly vacuumizing to 10-20 Pa 2-5 min before sintering; immediately introducing Ar gas with the flow rate of 55-65L/h after sintering, and rapidly cooling to below 700 ℃, wherein the average cooling speed is 90-100 ℃/min; and then cooling along with the furnace, wherein the density of the prepared ultra-coarse hard alloy is more than 99.5 percent, the WC average grain size D50 is 6-10 mu m, the WC grain size distribution is narrow, the grain distribution dispersion (D90-D10)/D50= 1.4-1.5, and the microstructures are all uniformUniform and no abnormal growth of crystal grains, no Cu in the phase interface of WC and Co3P、Co2P phase is generated, and the bending strength is not less than 1800 MPa.
2. The method of preparing an extra coarse hard alloy material according to claim 1, further characterized by:
(1) adopting absolute ethyl alcohol to clean the mixed solution A, and enabling the mixed solution to be neutral;
(2) the mixed solution D is subjected to ultrasonic stirring when the temperature is kept at 50-75 ℃, and the ultrasonic frequency is 4 x 104Hz, power 100W; adopting absolute ethyl alcohol to clean the mixed solution D, and enabling the mixed solution to be neutral;
(3) during the solution treatment of the ultra-coarse WC powder, the heating rate is 5 ℃/min, the vacuum degree is 10-15 Pa, and after the heat preservation is finished, the ultra-coarse WC powder is cooled along with a furnace;
(4) the ball milling medium of the ball milling of the WC-Co mixed powder is absolute ethyl alcohol, the addition amount of the absolute ethyl alcohol is 15-20% of the total weight of the hard alloy mixed powder, and PEG4000 with the weight being 2% of the total weight of the hard alloy mixed powder is added to serve as a forming agent; filtering by using a 400-mesh screen after the ball milling is finished, drying at 90-95 ℃, and sieving by using a 100-mesh sieve;
(5) the temperature rise speed during sintering of the hard alloy is 10 ℃/min, and the vacuum degree before 700 ℃ is 5-10 Pa.
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