Summary of the invention
The objective of the invention is to overcome the shortcoming and the weak point of above-mentioned prior art, a kind of preparation method of WC-Co Wimet is provided, it adopts the carburizing sintering close-coupled process, can improve production cycle in the Wimet preparation process long, process is loaded down with trivial details, energy consumption is high and make impurity introduce shortcomings such as chance increasing owing to process is loaded down with trivial details.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of WC-Co Wimet, and it adopts the incorporate method of carburizing sintering, specifically may further comprise the steps:
(1) adopts dielectric barrier discharge plasma auxiliary high-energy ball milling method that W, C, Co raw material and benefit carbon are carried out ball milling by dielectric barrier discharge plasma auxiliary high-energy ball mill, obtain W, C, Co mixed powder;
(2) with described W, C, Co mixed powder press forming, obtain green compact;
(3) described green compact are put into thermal source environment sintering and prepared the WC-Co Wimet.
For realizing the present invention better, the described W of step (1), each raw material of C, Co carry out proportioning according to WC-XCo, and wherein, the span of X is 3≤X≤20, and the mass ratio of described benefit carbon and C raw material is 4%~10%.
Described dielectric barrier discharge plasma auxiliary high-energy ball mill, comprise base, abrading-ball, spring, motor, the elasticity shaft coupling, the exciting piece, frame, ball grinder, vacuum valve, front shroud, Wimet jar liner, outer jar of ball grinder, back shroud, electrode bar and plasma electrical source, described ball grinder is installed on the frame, the inside of ball grinder is placed with abrading-ball, frame is installed on the base by spring, its arranged outside has the exciting piece, drive-motor is installed on the base, and by the elasticity shaft coupling respectively with frame, the exciting piece connects, described plasma electrical source links to each other with any one bolt and the electrode bar of front shroud respectively, described Wimet jar liner is the WC-XCo Wimet, and the span of described X should be 3≤X≤20 mutually.
The described dielectric barrier discharge plasma auxiliary high-energy of step (1) ball milling method may further comprise the steps:
(1.1) install the front shroud and the electrode bar of ball grinder, and front shroud is linked to each other with the positive and negative two-stage of plasma electrical source respectively with electrode bar, wherein, electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(1.2) in ball grinder, pack into abrading-ball and W, C, Co raw material and mend carbon, when electrode bar and abrading-ball all with after W, C, Co raw material contact, build the back shroud of ball grinder;
(1.3) by vacuum valve airtight ball grinder is vacuumized, feed the discharge gas medium by vacuum valve again, the pressure in this ball grinder is 0.01~0.30MPa;
(1.4) connect plasma electrical source, regulate discharge parameter according to discharge gas medium and pressure thereof, plasma electrical source voltage is 3~30KV, discharge frequency is corresponding with voltage of supply, realize dielectric barrier discharge, and start drive-motor and drive the exciting piece, make frame and the ball grinder that is fixed on the frame vibrates simultaneously, thereby change the relative position of abrading-ball in electrode bar and the ball grinder, carry out dielectric barrier discharge plasma auxiliary high-energy ball milling.
In the above-mentioned dielectric barrier discharge plasma auxiliary high-energy ball milling method, described abrading-ball cumulative volume accounts for ball grinder volume 70~75%, wherein the abrading-ball of diameter 20~22mm accounts for total abrading-ball quantity 10~15%, the abrading-ball of diameter 15~18mm accounts for total abrading-ball quantity 75~80%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co powder pine volume accounts for 30%~130% of space between the abrading-ball.
The ball powder ratio of ball milling is 10: 1~200: 1.
Described discharge gas medium is argon gas, nitrogen, ammonia or methane.
Described exciting piece adopts double-amplitude 5mm~10mm, motor speed 930~1400r/min; The ball milling time is 1~9h.
The mode of the press forming described in the step (2) is a die forming, and the unit pressing force is 50MPa~1000MPa.
The temperature of the thermal source environment described in the step (3) is 1320~1480 ℃; The atmosphere of thermal source environment is vacuum, argon gas or nitrogen, and atmosphere pressures is 1Pa~10MPa; The agglomerating mode is that vacuum sintering or vacuum sintering are in conjunction with hot pressed sintering (pressure is less than the vacuum sintering that is of 0.1MPa).
The present invention compares with conventional art, has following advantage and characteristic:
(1) implementing process is simple, and is with short production cycle, and it is little that impurity is introduced chance.Replace in the traditional technology technology that adds the binder granulation, dries, is pressed into green compact with the technology generation that directly pressed by powder behind the ball milling is become green compact, this technology has been simplified the preparation technology of Wimet greatly, shorten the production cycle, reduced the chance that impurity is introduced in the traditional technology.
(2) energy consumption is low.Directly the green compact that W, C, Co powder mix are pressed into are made WC, Co powder mix the technology that green sintering is shaped with elder generation in the incorporate technology replacement of the carburizing sintering traditional technology again with the carbonization of W powder.The present invention only exists once from room temperature to pyritous heat-processed, and traditional technology needs when carbonization of W powder and green sintering each experience once from room temperature to pyritous heat-processed, thereby can cut down the consumption of energy greatly.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Adopt the preparation method of this WC-Co Wimet to prepare the WC-10Co Wimet, as shown in Figure 1, 2, adopt dielectric barrier discharge plasma auxiliary high-energy ball mill, it comprises base 1, abrading-ball 2, spring 3, motor 4, elasticity shaft coupling 5, exciting piece 6, frame 7, ball grinder 8, vacuum valve 8-1, front shroud 8-2, Wimet jar liner 8-3, ball grinder outer jar 8-4, back shroud 8-5, electrode bar 9, plasma electrical source 10.Ball grinder 8 is installed on the frame 7, and its inside is placed with abrading-ball 2, and frame 7 is installed on the base 1 by spring 3, and its arranged outside has exciting piece 6, and drive-motor 4 is installed on the base 1, and is connected with frame 7, exciting piece 6 respectively by elasticity shaft coupling 5.Plasma electrical source 10 links to each other with any one bolt 8-6 and the electrode bar 9 of front shroud 8-2 respectively.
In the ball grinder 8, select for use stainless steel as body material as outer jar of 8-4 of ball grinder, its Wimet jar liner 8-3 is a WC-10Co type Wimet.
As shown in Figure 3, adopt the preparation method of this WC-Co Wimet to prepare the WC-10Co Wimet, it adopts the incorporate method of carburizing sintering, specifically may further comprise the steps:
(1) adopt dielectric barrier discharge plasma auxiliary high-energy ball milling method that W, C, Co raw material and benefit carbon are carried out ball milling by the plasma auxiliary high-energy ball mill, obtain W, C, Co mixed powder, wherein, described W, C, each raw material of Co carry out proportioning according to WC-10Co, and the mass ratio of described benefit carbon and C raw material is 7.5%;
Wherein, as shown in Figure 1, 2, the step of dielectric barrier discharge plasma auxiliary high-energy ball milling method is:
(1.1) install the front shroud and the electrode bar of ball grinder, and front shroud is linked to each other with the positive and negative two-stage of plasma electrical source respectively with electrode bar, wherein, electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(1.2) in ball grinder, pack into abrading-ball and W, C, Co raw material and mend carbon, when electrode bar and abrading-ball all with after W, C, Co raw material contact, build the back shroud of ball grinder;
(1.3) by vacuum valve airtight ball grinder is vacuumized, feed the discharge gas medium by vacuum valve again, the pressure in this ball grinder is 0.12MPa;
(1.4) connect plasma electrical source, regulate discharge parameter according to discharge gas medium and pressure thereof, plasma electrical source voltage is 28KV, discharge frequency is corresponding with voltage of supply, is 60KHz, realizes dielectric barrier discharge, and the startup drive-motor drives the exciting piece, the ball grinder that makes frame and be fixed on the frame vibrates simultaneously, thereby changes the relative position of abrading-ball in electrode bar and the ball grinder, carries out dielectric barrier discharge plasma auxiliary high-energy ball milling.
In the above-mentioned dielectric barrier discharge plasma auxiliary high-energy ball milling method, described abrading-ball cumulative volume accounts for ball grinder volume 70~75%, wherein the abrading-ball of diameter 20~22mm accounts for total abrading-ball quantity 10~15%, the abrading-ball of diameter 15~18mm accounts for total abrading-ball quantity 75~80%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co powder pine volume accounts for 30%~130% of space between the abrading-ball; The ball powder ratio of ball milling is 80: 1; Described discharge gas medium is argon gas, nitrogen, ammonia or methane; Described exciting piece adopts double-amplitude 5mm~10mm, motor speed 930~1400r/min; The ball milling time is 3h.
(2) described W, C, Co mixed powder are packed into mould, press forming, unit pressure is 250MPa, and the dwell time is 3min, and the demoulding subsequently obtains green compact;
(3) described green compact are put into thermal source environment sintering and prepared the WC-Co Wimet.
(3) adopt vacuum sintering in conjunction with pressing methods, the green compact that step (2) is made are heated to 1340 ℃ and be incubated 15min with the speed of 10 ℃/min under the condition of 1Pa, speed with 2.5bar/min charges into argon gas to 5MPa subsequently, and continuation insulation 35min, be cooled to room temperature then, make the WC-10Co Wimet.
The WC-10Co Wimet Rockwell hardness HRA that makes is 90.2, and bending strength (TRS) is 3471MPa.
Embodiment 2
Adopt the preparation method of this WC-Co Wimet to prepare the WC-10Co Wimet, its step (1) is substantially the same manner as Example 1, and different is that ball powder ratio is 16: 1, and the ball milling time is 6h;
Step (2) is identical with embodiment 1;
Step (3): adopt the method for vacuum sintering, the green compact that step (2) is made are heated to 1380 ℃ and be incubated 60min with the speed of 10 ℃/min under the condition of 1Pa, be cooled to room temperature subsequently, make the WC-10Co Wimet.
The WC-10Co Wimet Rockwell hardness HRA that makes is 90.4, and bending strength (TRS) is 2305MPa.Its XRD spectra is seen Fig. 4, and its SEM figure sees Fig. 5.
Embodiment 3
Adopt the preparation method of this WC-Co Wimet to prepare the WC-10Co Wimet, its step (1), (2) and embodiment 1 are identical; Step (3) is identical with embodiment 2.
The WC-10Co Wimet Rockwell hardness HRA that makes is 90.1, and bending strength (TRS) is 1520MPa.
Embodiment 4
Adopt the preparation method of this WC-Co Wimet to prepare the WC-3Co Wimet, step (1) is substantially the same manner as Example 1, and difference is: described Wimet jar liner is the WC-3Co Wimet; W, C, Co press the WC-3Co proportioning, and mend carbon 4%; Ball powder ratio is 100: 1, and the ball milling time is 9h; Plasma electrical source voltage is 30KV, and the ball grinder internal pressure is 0.01MPa;
Step (2): with the mould of packing into of the powder behind the ball milling, press forming, unit pressure is 1000MPa, and the dwell time is 2min, and the demoulding subsequently obtains green compact;
Step (3): adopt the method for vacuum sintering, the green compact that step (2) is made are heated to 1480 ℃ and be incubated 60min with the speed of 10 ℃/min under the condition of 0.02Mpa argon gas, be cooled to room temperature subsequently, make the WC-3Co Wimet.
Embodiment 5
Adopt the preparation method of this WC-Co Wimet to prepare the WC-6Co Wimet, step (1) is substantially the same manner as Example 1, and difference is: described Wimet jar liner is the WC-6Co Wimet; W, C, Co press the WC-6Co proportioning, and mend carbon 6%; Ball powder ratio is 150: 1, and the ball milling time is 2h; Plasma electrical source voltage is 22KV, and the ball grinder internal pressure is 0.18MPa;
Step (2): with the mould of packing into of the powder behind the ball milling, press forming, unit pressure is 750MPa, and the dwell time is 90s, and the demoulding subsequently obtains green compact;
Step (3): adopt vacuum sintering in conjunction with pressing methods, the green compact that step (2) is made are heated to 1440 ℃ and be incubated 15min with the speed of 10 ℃/min under the condition of 1Pa, speed with 3bar/min charges into nitrogen to 8MPa subsequently, continue insulation 45min, be cooled to room temperature then, make the WC-6Co Wimet.
Embodiment 6
Adopt the preparation method of this WC-Co Wimet to prepare the WC-13Co Wimet, step (1) is substantially the same manner as Example 1, and difference is: described Wimet jar liner is the WC-16Co Wimet; W, C, Co press the WC-13Co proportioning, and mend carbon 8%; Ball powder ratio is 200: 1, and the ball milling time is 1h; Plasma electrical source voltage is 3KV, and the ball grinder internal pressure is 0.30MPa;
Step (2): with the mould of packing into of the powder behind the ball milling, press forming, unit pressure is 500MPa, and the dwell time is 2min, and the demoulding subsequently obtains green compact;
Step (3): adopt vacuum sintering in conjunction with pressing methods, the green compact that step (2) is made are heated to 1400 ℃ and be incubated 15min with the speed of 10 ℃/min under the condition of 1Pa, speed with 5bar/min charges into argon gas to 10MPa subsequently, continue insulation 45min, be cooled to room temperature subsequently, make the WC-13Co Wimet.
Embodiment 7
Adopt the preparation method of this WC-Co Wimet to prepare the WC-17Co Wimet, step (1) is substantially the same manner as Example 1, and difference is: described Wimet jar liner is the WC-17Co Wimet; W, C, Co press the WC-17Co proportioning, and mend carbon 9.5%; Ball powder ratio is 50: 1, and the ball milling time is 4.5h; Plasma electrical source voltage is 8KV, and the ball grinder internal pressure is 0.28MPa;
Step (2): with the mould of packing into of the powder behind the ball milling, press forming, unit pressure is 100MPa, and the dwell time is 150s, and the demoulding subsequently obtains green compact;
Step (3): adopt the method for vacuum sintering, the green compact that step (2) is made are heated to 1320 ℃ and be incubated 90min with the speed of 10 ℃/min under the condition of 1Pa, be cooled to room temperature subsequently, make the WC-17Co Wimet.
Embodiment 8
Adopt the preparation method of this WC-Co Wimet to prepare the WC-20Co Wimet, step (1) is substantially the same manner as Example 1, and difference is: described Wimet jar liner is the WC-20Co Wimet; W, C, Co press the WC-20Co proportioning, and mend carbon 10%; Ball powder ratio is 10: 1, and the ball milling time is 7h; Plasma electrical source voltage is 15KV, and the ball grinder internal pressure is 0.25MPa;
Step (2): with the mould of packing into of the powder behind the ball milling, press forming, unit pressure is 50MPa, and the dwell time is 4min, and the demoulding subsequently obtains green compact;
Step (3): adopt the method for vacuum sintering, the green compact that step (2) is made are heated to 1340 ℃ and be incubated 60min with the speed of 10 ℃/min under the condition of 0.01Mpa nitrogen, be cooled to room temperature subsequently, make the WC-20Co Wimet.
As mentioned above, just can realize the present invention preferably, the foregoing description is preferred embodiment of the present invention only, is not to be used for limiting practical range of the present invention; Be that all equalizations of doing according to content of the present invention change and modification, all contained by claim of the present invention scope required for protection.