CN102181679A - Preparation method of inhibitor-containing W-C-Co powder and hard alloy thereof - Google Patents

Preparation method of inhibitor-containing W-C-Co powder and hard alloy thereof Download PDF

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CN102181679A
CN102181679A CN 201110100182 CN201110100182A CN102181679A CN 102181679 A CN102181679 A CN 102181679A CN 201110100182 CN201110100182 CN 201110100182 CN 201110100182 A CN201110100182 A CN 201110100182A CN 102181679 A CN102181679 A CN 102181679A
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ball
wimet
powder
abrading
inhibitor
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朱敏
施振华
曾美琴
李北
鲍贤勇
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention provides a preparation method of inhibitor-containing W-C-Co powder and hard alloy thereof. The method comprises the following steps of: performing ball milling on raw materials including W, C, Co and VC (or V2O5) and additional supplemented carbon by adopting a dielectric barrier discharge plasma aided high-energy ball milling method to obtain mixed powder; pressing the mixed powder to form a raw blank; and sintering the raw blank in a heat source environment to prepare the W-C-Co hard alloy. The raw materials are proportioned according to WC-XCo-YV2O5 or WC-XCo-YVC, wherein the numeric area of X is more than or equal to 3 and less than or equal to 20, the numeric area of Y is more than or equal to 0.09 and less than or equal to 2.4, and both X and Y are in a weight percentage form. The mass ratio of the additional supplemented carbon to the raw material C is 7.5 to 15 percent. By means of the method, the production period of the preparation process of the hard alloy can be shortened, the process is simplified, the energy consumption is reduced, the introduction probability of impurities is reduced, growth of WC crystal grains can be effectively inhibited, and the mechanical property of the hard alloy is improved.

Description

Contain the W-C-Co powder of inhibitor and the preparation method of Wimet thereof
Technical field
The present invention relates to the preparation of WC-Co Wimet, particularly contain the W-C-Co powder of inhibitor and the preparation method of Wimet thereof.
Background technology
The WC-Co Wimet is present industrial widely used worker, moulding stock, improves its mechanical property, simplifies the focus that preparation technology is Wimet research always.In the preparation process of Wimet, come crystal grain thinning by adding grain growth inhibitor usually, to improve the mechanical property of alloy.Traditional WC-Co Wimet preparation technology forms the tungsten powder carbonization wolfram varbide, the oxide form carbonization of inhibitor is formed carbide morphology; Then with the carbide morphology mixing wet-milling of wolfram varbide with cobalt powder and grain growth inhibitor; Add forming agent in the slurry after wet-milling, dry again, granulation; Press forming subsequently; Degreasing, sintering are carried out in last shove charge.On the one hand, form the back at WC and add inhibitor, make WC grain growth in forming process can not get effective inhibition, weakened the inhibition effect greatly; On the other hand, these steps are comparatively complicated, the energy consumption height, and have problem such as inhibitor skewness.Therefore, explore that step is simple, energy consumption is low, inhibitor is evenly distributed, suppress the WC grain effective hard alloy production process of growing up and become the certainty of social development.
Application number provides a kind of preparation method of WC-Co Wimet for the patent application document of CN200810028403.1, after it assists ball milling with W, C, Co powder by dielectric barrier discharge plasma, directly be pressed into green compact, handle under vacuum/low pressure sintering stove at last and obtain the WC-Co Wimet, its technology has advantages such as step is simple, energy consumption is low, pollution level is little.But under vacuum/low pressure sintering stove, the grain growth of WC can not get suppressing, and can not effectively improve the mechanical property of alloy to a certain extent.
Summary of the invention
Be the shortcoming and deficiency that overcomes above-mentioned prior art, the invention provides a kind of W-C-Co powder of inhibitor and preparation method of Wimet thereof of containing, it adopts the incorporate way of carburizing sintering, production cycle is long in improving the Wimet preparation process, process is loaded down with trivial details, energy consumption is high and owing to process is loaded down with trivial details impurity is introduced on the basis of shortcomings such as chance increasing, further, promptly in dielectric barrier discharge plasma auxiliary ball milling W, C, Co powder process, add grain growth inhibitor VC or V by before forming at WC 2O 5, with the remarkable action effect that improves inhibitor, and then the mechanical property of raising alloy.
Purpose of the present invention is achieved through the following technical solutions:
In the auxiliary mechanical milling process of dielectric barrier discharge plasma, add grain growth inhibitor VC or V 2O 5, prepare the W-C-Co Wimet by the incorporate way of carburizing sintering at last, specifically may further comprise the steps:
(1) adopts dielectric barrier discharge plasma auxiliary high-energy ball milling method, W, C, Co, grain growth inhibitor raw material and the mixed powder of additionally mending carbon are carried out ball milling, obtain containing the W-C-Co mixed powder of grain growth inhibitor;
(2) with described W-C-Co mixed powder press forming, obtain green compact;
(3) described green compact sintering in the thermal source environment is prepared the W-C-Co Wimet.
For realizing the present invention better, the described W of step (1), C, Co, VC or V 2O 5Each raw material is according to WC-XCo-YVC or WC-XCo-Y V 2O 5Carry out proportioning (interpolation of grain growth inhibitor oxide form according to its carbonization then form the required amount of corresponding carbide add), wherein, the span of X is 3≤X≤20, and the span of Y is 0.09≤Y≤2.4, and described X, Y all are weight percentage.
The amount of C also comprises extra benefit carbon amount in the mixed powder except that the needed theoretical carbon amount of W carbonization, and the mass ratio of itself and C raw material is 7.5%～15%.
The mode of described press forming is a single way stempressing, and unit pressure is 50MPa～1000 MPa.
Described thermal source environment is vacuum/low pressure sintering stove, and the temperature of thermal source environment is 1320 ℃～1480 ℃.
Described agglomerating mode is that vacuum sintering is in conjunction with hot pressed sintering or vacuum sintering.
Compare with conventional art, the present invention has the following advantages:
(1) the present invention is by adding grain growth inhibitor (VC or V in dielectric barrier discharge plasma ball milling W, C, Co process 2O 5), with in the traditional technology earlier with the W carbonization, again with grain growth inhibitor and WC, Co together ball milling compare, the present invention can increase the distributing homogeneity of grain growth inhibitor, and just can play the restraining effect that WC grain is grown up in the forming process of WC, and it is effective that the inhibition WC grain is grown up;
(2) the present invention is with oxide form V 2O 5Presoma as grain growth inhibitor has reduced cost, has improved mechanical property.The carbide morphology that directly adds in oxide form and the preparation of traditional Wimet is compared, and has not only reduced the step of high temperature cabonization, has reduced cost to a great extent;
(3) the present invention is in hard alloy sintering process, the oxide form V of selection 2O 5Can be at the better refinement WC of carbonation stage, WC has very big dispersivity in the prepared Wimet that goes out, and microstructure has high homogeneity, has excellent mechanical property.
Description of drawings
Fig. 1 is the structural representation of the dielectric barrier discharge plasma auxiliary high-energy ball mill of the present invention's employing;
Fig. 2 is the sectional view of dielectric barrier discharge plasma auxiliary high-energy ball mill shown in Figure 1;
Fig. 3 is preparation method's of the present invention process flow sheet;
Fig. 4 is the XRD spectra of the prepared Wimet of the embodiment of the invention 2;
Fig. 5 is the SEM spectrogram of the prepared Wimet of the embodiment of the invention 2;
Fig. 6 is the XRD spectra of the prepared Wimet of the embodiment of the invention 4.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The dielectric barrier discharge plasma auxiliary high-energy ball mill that the various embodiments of the present invention preparation is adopted, as depicted in figs. 1 and 2: comprise base 1, abrading-ball 2, spring 3, motor 4, elasticity shaft coupling 5, exciting piece 6, frame 7, ball grinder 8, motor rod 9, plasma electrical source 10; Cored 16 in the electrode bar, adopt PTFE medium layer 17; Ball grinder 8 comprises outer jar 14 of ball grinder, front shroud 12 and back shroud 15, in jar vacuum valve 11 is arranged, and outer jar is lined with Wimet jar liner 13.
Ball grinder 8 is installed on the frame 7, its inside is placed with abrading-ball 2, frame 7 is installed on the base 1 by spring 3, its arranged outside has exciting piece 6, drive-motor 4 is installed on the base 1, and be connected with frame 7, exciting piece 6 respectively by elasticity shaft coupling 5, plasma electrical source 10 links to each other with front shroud 12 and electrode bar 9 respectively.Ball grinder selects for use stainless steel as body material for outer jar 14, and Wimet jar liner 13 is a WC-10Co type Wimet.
As shown in Figure 1, 2, the step of dielectric barrier discharge plasma auxiliary high-energy ball milling method is:
(1) installs the front shroud and the electrode bar of ball grinder, and the iron core in front shroud and the electrode bar linked to each other with the positive and negative two-stage of plasma electrical source respectively, wherein, the iron core in the electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(2) pack in ball grinder abrading-ball and W, C, Co, VC raw material and the extra carbon amount of mending are built the back shroud of ball grinder;
(3) by vacuum valve ball grinder is vacuumized, charge into the discharge gas medium then, make the force value in the ball grinder reach 0.12MPa;
(4) connect plasma electrical source, it is 15KV that plasma electrical source voltage is set, and electric current is 1.5A, discharge frequency 60KHz, start drive-motor and drive the exciting piece, make frame and the ball grinder that is fixed on the frame vibrates simultaneously, 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, VC volume of powder account for 30%～130% of space between the abrading-ball; The ball powder ratio of ball milling is 30:1 ~ 100:1; Described discharge gas medium is any in helium, neon, argon gas, xenon, krypton gas or the nitrogen; Described exciting piece adopts double-amplitude 5mm～10mm, motor speed 930～1400r/min; The ball milling time is 0.5h ~ 9h.
Embodiment 1
As shown in Figure 3, adopt preparation method of the present invention to prepare the WC-10Co Wimet, the Wimet jar liner 13 that the ball grinder of dielectric barrier discharge plasma auxiliary high-energy ball mill is outer jar adopts the WC-10Co Wimet, and concrete preparation may further comprise the steps:
Step 1: W, C, each raw material of Co, VC are carried out proportioning according to WC-10Co-0.6VC, and the mass ratio of additionally mending carbon amount and theoretical carbon amount is 15%, adopts dielectric barrier discharge plasma auxiliary high-energy ball milling method that mixed powder is carried out ball milling; The abrading-ball cumulative volume accounts for ball grinder volume 70%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 15%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 80%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 3100% of space between the abrading-ball; The ball powder ratio of ball milling is 50:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 10mm, motor speed 1200r/min; The ball milling time is 3h;
Step 2: with the W behind the described ball milling, C, Co, the VC mixed powder mould of packing into, press forming, unit pressure is 300MPa, and the dwell time is 3min, and the demoulding subsequently obtains green compact;
Step 3: in vacuum/low pressure sintering stove, adopt the method for vacuum sintering in conjunction with pressure sintering, 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 4MPa subsequently, and continuation insulation 35min, speed with 10 ℃/min is cooled to room temperature then, makes the WC-10Co Wimet.
The WC-10Co-0.6VC Wimet Rockwell hardness HRA that makes is 91.8, and lateral cross section bending strength (TRS) is 3378MPa.
Embodiment 2
Preparation WC-10Co Wimet, concrete steps are:
Step 1: W, C, each raw material of Co, VC are carried out proportioning according to WC-10Co-0.9VC, and the mass ratio of additionally mending carbon amount and theoretical carbon amount is 15%, adopts dielectric barrier discharge plasma auxiliary high-energy ball milling method that mixed powder is carried out ball milling; The abrading-ball cumulative volume accounts for ball grinder volume 70%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 15%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 80%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 3100% of space between the abrading-ball; The ball powder ratio of ball milling is 50:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 10mm, motor speed 1200r/min; The ball milling time is 3h;
Step 2: with the W behind the described ball milling, C, Co, the VC mixed powder mould of packing into, press forming, unit pressure is 300MPa, and the dwell time is 3min, and the demoulding subsequently obtains green compact;
Step 3: in vacuum/low pressure sintering stove, adopt the method for vacuum sintering in conjunction with pressure sintering, 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 4MPa subsequently, and continuation insulation 35min, speed with 10 ℃/min is cooled to room temperature then, makes the WC-10Co-0.9VC Wimet.
The WC-10Co-0.9VC Wimet Rockwell hardness HRA that makes is 92.6, and bending strength (TRS) is 3628MPa, its XRD spectra see Fig. 4 (because of, its X-ray diffraction peak is invisible), its SEM figure sees Fig. 5.We can find from the XRD curve, only exist WC and Co mutually in the sample for preparing.Less because of the amount of VC, the peak is too low, can't manifest under the setting off at the peak of other phase.In SEM figure, color is divided into the WC phase than superficial part, and it is dark-coloured that Co phase color is, and is filled in the gap between the WC phase.
Embodiment 3
Preparation WC-10Co Wimet, concrete steps are:
Step 1: W, C, each raw material of Co, VC are carried out proportioning according to WC-10Co-1.2VC, and the mass ratio of additionally mending carbon amount and theoretical carbon amount is 15%, adopts dielectric barrier discharge plasma auxiliary high-energy ball milling method that mixed powder is carried out ball milling; The abrading-ball cumulative volume accounts for ball grinder volume 70%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 15%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 80%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 3100% of space between the abrading-ball; The ball powder ratio of ball milling is 50:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 10mm, motor speed 1200r/min; The ball milling time is 3h;
Step 2: with the W behind the described ball milling, C, Co, the VC mixed powder mould of packing into, press forming, unit pressure is 300MPa, and the dwell time is 3min, and the demoulding subsequently obtains green compact;
Step 3: in vacuum/low pressure sintering stove, adopt the method for vacuum sintering in conjunction with pressure sintering, 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 4MPa subsequently, and continuation insulation 35min, speed with 10 ℃/min is cooled to room temperature then, makes the WC-10Co-1.2VC Wimet.
The Wimet Rockwell hardness HRA that makes is 92.8, and bending strength (TRS) is 3062MPa.
Embodiment 4
Preparation WC-10Co Wimet, concrete steps are:
Step 1: with W, C, Co, V 2O 5Each raw material is according to WC-10Co-0.58V 2O 5Carry out proportioning, the mass ratio of additionally mending carbon amount and theoretical carbon amount is 10%, adopts dielectric barrier discharge plasma auxiliary high-energy ball milling method that mixed powder is carried out ball milling; The abrading-ball cumulative volume accounts for ball grinder volume 70%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 15%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 80%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, V 2O 5Volume of powder accounts for 3100% of space between the abrading-ball; The ball powder ratio of ball milling is 50:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 10mm, motor speed 1200r/min; The ball milling time is 3h;
Step 2: with the W behind the described ball milling, C, Co, V 2O 5The mixed powder mould of packing into, press forming, unit pressure is 300MPa, and the dwell time is 3min, and the demoulding subsequently obtains green compact;
Step 3: in vacuum/low pressure sintering stove, adopt the method for vacuum sintering in conjunction with pressure sintering, 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 4MPa subsequently, and continuation insulation 35min, speed with 10 ℃/min is cooled to room temperature then, makes the WC-10Co-0.4VC Wimet.
The WC-10Co-0.4VC Wimet Rockwell hardness HRA that makes is 91.6, and bending strength (TRS) is 3260MPa, and its XRD spectra is seen Fig. 6.From the diffraction peak of Fig. 6 as can be known, add V 2O 5The Wimet that makes as inhibitor with add VC mutually identical as in the inhibitor gained sample, promptly only exist WC and Co mutually, the existence of scarce carbon phase.But because V 2O 5Addition less, therefore in the XRD curve, do not find V yet 2O 5The diffraction peak of the VC that forms after the carbonization.
Embodiment 5
Preparation WC-3Co Wimet, Wimet jar liner is the WC-3Co Wimet; Concrete steps are:
Step 1: W, C, each raw material of Co, VC are carried out proportioning according to WC-3Co-0.09VC, and mend carbon, the mass ratio of mending carbon amount and theoretical carbon amount is 7.5%; The abrading-ball cumulative volume accounts for ball grinder volume 72%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 13%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 78%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 80% of space between the abrading-ball; The ball powder ratio of ball milling is 60:1; Described discharge gas medium is a neon; Described exciting piece adopts double-amplitude 8mm, motor speed 1400r/min; The ball milling time is 6h; 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-0.09VC Wimet.
Embodiment 6
Preparation WC-8Co Wimet, described Wimet jar liner is the WC-8Co Wimet; Concrete steps are:
Step 1: W, C, Co, VC are pressed the WC-8Co-0.7VC proportioning, and mend carbon 10%; The abrading-ball cumulative volume accounts for ball grinder volume 74%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 11%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 77%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 50% of space between the abrading-ball; Described discharge gas medium is a radon gas; Described exciting piece adopts double-amplitude 90mm, motor speed 1000r/min; Ball powder ratio is 40:1, 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-8Co-0.7VC Wimet.
Embodiment 7
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-12Co Wimet, and Wimet jar liner is the WC-12Co Wimet, and concrete steps are:
Step 1: W, C, Co, VC are pressed the WC-12Co-0.9VC proportioning, and mend carbon 8%; The abrading-ball cumulative volume accounts for ball grinder volume 70%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 10%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 80%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 90% of space between the abrading-ball; Described discharge gas medium is a nitrogen; Described exciting piece adopts double-amplitude 6mm, motor speed 980r/min; Ball powder ratio is 40:1, 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-12Co-0.9VC Wimet.
Embodiment 8
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-16Co Wimet, and Wimet jar liner is the WC-16Co Wimet, and concrete steps are:
Step 1: W, C, Co, VC are pressed the WC-16Co-1.6VC proportioning, and mend carbon 10%; The abrading-ball cumulative volume accounts for ball grinder volume 75%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 12%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 78%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 90% of space between the abrading-ball; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 5mm～10mm, motor speed 930～1400r/min; The ball milling time is 5h.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-16Co-1.6VC Wimet.
Embodiment 9
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-20Co Wimet, and Wimet jar liner is the WC-20Co Wimet; Concrete steps are:
Step 1: W, C, Co, VC are pressed the WC-20Co-2.4VC proportioning, and mend carbon 10%; The abrading-ball cumulative volume accounts for ball grinder volume 74%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 12%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 76%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 90% of space between the abrading-ball; The ball powder ratio of ball milling is 10:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 6mm, motor speed 1160r/min; 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-2.4VC Wimet.
Embodiment 10
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-3Co Wimet, and Wimet jar liner is the WC-3Co Wimet, and concrete steps are:
Step 1: with W, C, Co, V 2O 5Each raw material is according to WC-3Co-0.2 V 2O 5Carry out proportioning, and mend carbon 7.5%; The abrading-ball cumulative volume accounts for ball grinder volume 72%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 12%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 79%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 30%～130% of space between the abrading-ball; The ball powder ratio of ball milling is 100:1; Described discharge gas medium is a nitrogen; Described exciting piece adopts double-amplitude 6mm, motor speed 1260r/min; 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-0.14VC Wimet.
Embodiment 11
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-8Co Wimet, and Wimet jar liner is the WC-8Co Wimet, and concrete steps are:
Step 1: with W, C, Co, V 2O 5Press WC-8Co-1.2V 2O 5Proportioning, and mend carbon 10%; The abrading-ball cumulative volume accounts for ball grinder volume 74%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 14%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 78%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 110% of space between the abrading-ball; The ball powder ratio of ball milling is 150:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 9mm, motor speed 1280r/min; 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-8Co-0.84VC Wimet.
Embodiment 12
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-12Co Wimet, and Wimet jar liner is the WC-12Co Wimet, and concrete steps are:
Step 1:W, C, Co, V 2O 5Press WC-12Co-1.4 V 2O 5Proportioning, and mend carbon 8%; The abrading-ball cumulative volume accounts for ball grinder volume 72%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 12%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 78%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 80% of space between the abrading-ball; The ball powder ratio of ball milling is 200:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 8mm, motor speed 980r/min; 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 WC-12Co-0.94 VC Wimet.
Embodiment 13
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-16Co Wimet, and the Wimet jar liner of high energy ball mill is the WC-16Co Wimet, and concrete steps are:
Step 1:W, C, Co, V 2O 5Press WC-16Co-2.4V 2O 5Proportioning, and mend carbon 10%; The abrading-ball cumulative volume accounts for ball grinder volume 72%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 13%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 76%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 120% of space between the abrading-ball; The ball powder ratio of ball milling is 50:1; Described discharge gas medium is an xenon; Described exciting piece adopts double-amplitude 6mm, motor speed 1380r/min; 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-16Co-1.68VC Wimet.
Embodiment 14
Employing originally contains the W-C-Co composite powder of inhibitor and the preparation method of Wimet prepares the WC-20Co Wimet, and the Wimet jar liner of high energy ball mill is the WC-20Co Wimet, and concrete steps are:
Step 1: with W, C, Co, V 2O 5Press WC-20Co-3.2 V 2O 5Proportioning, and mend carbon 10%; The abrading-ball cumulative volume accounts for ball grinder volume 75%, and wherein the abrading-ball of diameter 20～22mm accounts for total abrading-ball quantity 12%, and the abrading-ball of diameter 15～18mm accounts for total abrading-ball quantity 78%, and the abrading-ball of diameter 10mm accounts for total abrading-ball quantity 10%; Described W, C, Co, VC volume of powder account for 120% of space between the abrading-ball; The ball powder ratio of ball milling is 10:1; Described discharge gas medium is an argon gas; Described exciting piece adopts double-amplitude 9mm, motor speed 1180r/min; 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 WC-20Co-2.24 VC Wimet.
As mentioned above, just can realize the present invention preferably, the foregoing description is part 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.

Claims (7)

1. contain the W-C-Co powder of inhibitor and the preparation method of Wimet thereof, it is characterized in that: may further comprise the steps:
(1) adopts the method for dielectric barrier discharge plasma auxiliary high-energy ball milling, W, C, Co, each raw material of grain growth inhibitor and the mixed powder of additionally mending carbon are carried out ball milling, obtain containing the W-C-Co composite powder of grain growth inhibitor; Described grain growth inhibitor is VC or V 2O 5
(2) with the described W-C-Co composite powder press forming that contains grain growth inhibitor, obtain green compact;
(3) described green compact are put into thermal source environment sintering and prepared the W-C-Co Wimet.
2. according to the described W-C-Co powder of inhibitor and the preparation method of Wimet thereof of containing of claim 1, it is characterized in that: described W, C, Co, VC or V 2O 5Raw material is according to WC-XCo-YV 2O 5Perhaps WC-XCo-YVC carries out proportioning; Wherein, the span of X is 3≤X≤20, and the span of Y is 0.09≤Y≤2.4, and described X, Y all are weight percentage.
3. according to the described W-C-Co powder of inhibitor and the preparation method of Wimet thereof of containing of claim 1, it is characterized in that: the mass ratio of described extra benefit carbon and C raw material is 7.5%～15%.
4. according to the described W-C-Co powder of inhibitor and the preparation method of Wimet thereof of containing of claim 1, it is characterized in that: described medium is a kind of in helium, neon, argon gas, xenon, krypton gas or the nitrogen.
5. according to the described W-C-Co powder of inhibitor and the preparation method of Wimet thereof of containing of claim 1, it is characterized in that: the mode of described press forming is a single way stempressing, and unit pressure is 50MPa～1000 MPa.
6. according to the described W-C-Co powder of inhibitor and the preparation method of Wimet thereof of containing of claim 1, it is characterized in that: described thermal source environment is vacuum/low pressure sintering stove, and the temperature of thermal source environment is 1320 ℃～1480 ℃.
7. according to the described W-C-Co powder of inhibitor and the preparation method of Wimet thereof of containing of claim 1, it is characterized in that: described agglomerating mode is that vacuum sintering is in conjunction with hot pressed sintering or vacuum sintering.
CN 201110100182 2011-04-21 2011-04-21 Preparation method of inhibitor-containing W-C-Co powder and hard alloy thereof Pending CN102181679A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106271489A (en) * 2016-08-29 2017-01-04 河源富马硬质合金股份有限公司 A kind of carbide bit and manufacture method thereof
CN106702247A (en) * 2016-11-29 2017-05-24 华南理工大学 Preparing method for hard alloy with adjustable and controllable platy WC grain arrangement state

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CN1804067A (en) * 2006-01-17 2006-07-19 武汉理工大学 Preparation process of tungsten carbide/inhibitor composite powder and superfine hard alloy thereof
CN101285134A (en) * 2008-05-30 2008-10-15 华南理工大学 Preparation method for WC-Co cemented carbide
CN101892411A (en) * 2010-08-09 2010-11-24 中国地质大学（北京） Novel WC-based hard alloy material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1804067A (en) * 2006-01-17 2006-07-19 武汉理工大学 Preparation process of tungsten carbide/inhibitor composite powder and superfine hard alloy thereof
CN101285134A (en) * 2008-05-30 2008-10-15 华南理工大学 Preparation method for WC-Co cemented carbide
CN101892411A (en) * 2010-08-09 2010-11-24 中国地质大学（北京） Novel WC-based hard alloy material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106271489A (en) * 2016-08-29 2017-01-04 河源富马硬质合金股份有限公司 A kind of carbide bit and manufacture method thereof
CN106702247A (en) * 2016-11-29 2017-05-24 华南理工大学 Preparing method for hard alloy with adjustable and controllable platy WC grain arrangement state
CN106702247B (en) * 2016-11-29 2019-04-09 华南理工大学 A kind of preparation method of the hard alloy of controllable plate-like shape WC grains ordered state

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Application publication date: 20110914