CN101397614B - Method for preparing Ni cementing WC base cemented carbide - Google Patents
Method for preparing Ni cementing WC base cemented carbide Download PDFInfo
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- CN101397614B CN101397614B CN2008100464528A CN200810046452A CN101397614B CN 101397614 B CN101397614 B CN 101397614B CN 2008100464528 A CN2008100464528 A CN 2008100464528A CN 200810046452 A CN200810046452 A CN 200810046452A CN 101397614 B CN101397614 B CN 101397614B
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Abstract
The invention disclose a method for preparing a hard alloy by bonding WC group with Ni, which is characterized by comprising the steps that: firstly, the mixing powder of WC and Ni is subjected to wet grinding, drying and pressing in absolute ethyl alcohol, and then subjected to vacuum sintering at the temperature of 1440 DEG C to 1480 DEG C; when the sintering is finished, nitrogen is introducedto a furnace simultaneously for carrying out vacuum quenching, the pressure of the nitrogen is 0.1MPa to 0.4MPa, and the quenching time is 5min to 10min; after tapping, deep cooling treatment is carried out in liquid nitrogen, the treatment temperature is 150 DEG C to 196 DEG C, and the heat-preservation time is: the hard alloy weight multiplied by weight factor plus the Ni percent content of thehard alloy weight multiplied by component factor, wherein, the weight factor is 5min/g to 25min/g and the component factor is 10min to 20 min; and drawing temper is carried out in a vacuum furnace atthe temperature of 120 DEG C to 200 DEG C, the temperature-preservation time is 1h to 3h. By adopting the method for preparing the hard alloy by bonding the WC group with Ni, the contact ratio of theWC can be controlled, the solubility of the WC in Ni is improved, furthermore, the surface stress condition of the alloy after treatment is compressive stress which improves the shock resistance capability of the alloy, thus being capable of realizing the substitution of Ni to Co and obtaining the performances corresponding to WC-Co series hard alloys.
Description
Technical field
The present invention is a kind of Wimet preparation method, particularly is the preparation method of the WC base cemented carbide of binding agent with Ni.
Background technology
Since the Wimet invention, Co is the main binding agent of Wimet always.Because Co has good wettability and cohesiveness to hard phase WC, and C, the dissolving of W in Co makes the WC-Co series hard metal have high rigidity, high strength, high-wearing feature.Co is rare strategic resource, and at present world Co reserves (not containing China) are about 4,500,000 tons, and the reserves basis is 9,600,000 tons, and mainly is distributed in African country's supply of material and conditions of demand complexity of political turbulence, very unstable (in non-turbulent political situation, supply of material difficulty; The Russia economy instability, prospect of export is uncertain), cause the price volalility amplitude of Co bigger.And it is reported that lung cancer is relevant with the powder that suction contains Co.Therefore cemented carbide industry wishes to reduce the consumption of Co and the substitute of searching Co.Ni and Co belong to the iron family metal together in the periodic table of elements, density, and fusing point, atomic radius is close, and physics, chemical property are close.And Ni also shows good wettability to WC, than Co better oxidation-resistance and corrosion stability is arranged, and especially after the alloying, the Wimet performance is more superior, also has non-magnetic advantage at low carbon content following.And the world saving of Ni is 70 times of Co, and aboundresources is the low-cost metal of a kind of relative Co.Therefore, Ni is counted as the first-selected surrogate of Co.In order to solve the problem that the Co inadequate resource brings, produce so-called " Ni is for the Co Wimet " and will reduce the cost of Wimet greatly, have vast market prospect and remarkable social benefit, economic benefit.
The scientific worker has carried out number of research projects both at home and abroad, and has obtained certain success.Zhou Yonggui has reported partly nickel for the toughness of Co Wimet, and with the toughness of the P20 alloy of the full Co of identical composition relatively, the result shows 30% and 50%, and to replace the Ni of Co for the bending strength of Co alloy all suitable with conventional P 20; Impression fracture toughness property value is lower than conventional P 20 alloys, and anti-tipping blade ability and durability are higher.People such as Yang Bihua have studied the influence of mixed carbon comtent and Ni/Co comparison WC-9 (Ni-Co) Wimet bending strength.The result shows: when the mixed carbon comtent of WC-3Ni-6Co was 6.04wt%, its bending strength and WC-9Co were suitable.People such as Wang Shiyuan are 1.6% yttrium oxide (Y by interpolation massfraction in Ni
20
3), make the bending strength of WC-8%Ni alloy be increased to 1900MPa, but hardness does not have considerable change from the 1250MPa that makes binding agent with pure nickel.Open the upright a kind of La of using (NO that introduced
3)
3Doping WC produces the method for Wimet, has inquired into the influence of La to WC-9 (Co-75%Ni) alloy physics mechanical property, and alloy has been carried out the on-the-spot rock drilling experiment in mine, works as La
2O
3/ (Co+Ni) be 0.3% o'clock, growing up unusually of WC grain can be effectively suppressed in the N309R alloy, and alloy structure homogenizing degree improves, and the wear resistance of alloy obviously improves, and has reached the level of YJI mine alloy.Xiong Ji has studied the influence of mishmetal CeLa to the WC-6%Ni alloy property, and the result shows, when content of rare earth is 0.5%, and best results, under the situation that hardness slightly rises, bending strength improves more than 10%, and performance is suitable with the WC-6Co alloy property.In Wimet, add rare earth, can play reinforced alloys, increase toughness, change impurity and have effects such as form and distribution.US Patent 4497660 has announced that Ni substrate adds the tungsten carbide base carbide alloy of elements such as a certain amount of Cr, Mo, Mn, Co, Al, Si, Cu for the bonding phase.The intensity of this alloy, toughness, hardness and relative wear resistance value all can accomplish to be better than similar traditional Wimet.This patent is thought: may be that Cr causes tested alloys to have high tenacity and high rigidity with the interaction that bonding influences mutually with Mo to carbide mutually.So it is necessary, in addition that Cr and Mo add simultaneously,, must adds Al, Si or the Cu of some amount in addition, otherwise can produce the fragility phase in the Wimet if when the add-on of Cr and Mo is high.It is that WC and the granularity of 14.4 μ m is 2.0,3.0,4.4 that people such as Zhou Jianhua adopt Fisher particle size, and the reduction Ni powder of 5.5,7.0 μ m has prepared the WC-9% Wimet.Result of study shows that the alloy cross-breaking strength attenuates along with the nickel powder granularity and improves, and intensity improved quite remarkable after mean particle size was lower than 3.0 μ m.The alloy cross-breaking strength has reached 2854MPa when mean particle size is 2.0 μ m.Alloy rigidity nickel powder mean particle size obviously descends along with granularity increases alloy rigidity during greater than 3 μ m.And during less than 3 μ m, granularity is not obvious to the alloy rigidity influence.The alloy Coercive Force is along with the nickel powder mean particle size increases and mild increasing; Alloy density is then opposite.People such as Yong Zhihua substitute the nanometer nickel powder of the binding agent in the WC-8Ni Wimet with different ratios, adopt the prepared of conventional Wimet to go out alloy sample, test its physical and mechanical property, the nanometer Ni powder of research different ratios and different sintering temperatures are to the alloy Effect on Performance.The result shows that when nanometer Ni accounted for 40%～60% left and right sides of total Ni content, the WC-8Ni Wimet was under the nano-nickel powder and sintering temperature of suitable proportion, and the performance of alloy is greatly improved.
From above report as can be seen, at present main by as by multiple interpolation alloying element, the refinement WC grain, by strict process control, methods such as minimizing hole and defective are improved the performance of Ni for the Co Wimet.But at present mainly at wear part, field such as mine instrument or other less demanding occasions have obtained limited application to Ni for the Co Wimet.And Ni for the Co Wimet on hardness and wear resistance with the gap of traditional Wimet, make its application on the big typical carbide product (as cutting tool) of usage quantity be restricted.The method that vacuum hardening of the present invention and sub-zero treatment combine is improved its performance.
Summary of the invention
It is not high to the present invention is directed to present Ni bonding WC Wimet over-all properties, and uses few present situation in the cutting tool field, has invented the preparation method that a kind of vacuum air-quenching and sub-zero treatment combine, and makes alloy obtain good performance.
The preparation method of Ni cementing WC base cemented carbide of the present invention is characterized in that elder generation carries out the mixed powder of WC and Ni to carry out vacuum sintering after wet-milling, drying, the compacting in dehydrated alcohol; Feed nitrogen when sintering is finished in the stove and carry out vacuum hardening; Come out of the stove then and in liquid nitrogen, carry out sub-zero treatment, and in vacuum oven, carry out temper;
The preparation method of Ni cementing WC base cemented carbide of the present invention, it is further characterized in that:
(1) wet-milling of WC and Ni powder mix is carried out in the roller milling machine, and rotational speed of ball-mill is 50～80r/min, and milling time is 48～56h, and mill ball is the WC-8wt%Co sintered carbide ball of diameter of phi 10mm, and ball material weight ratio is 5: 1; Wet grinding media is a dehydrated alcohol, and adds the forming agent polyoxyethylene glycol of 1.0～2.0wt%, and the dehydrated alcohol dosage is 250～300ml/kg; Powder behind the filtration drying is at the forming under the pressure of 300～400MPa; Sintering carries out in vacuum oven, takes off forming agent and is higher than under 10～15Pa in vacuum tightness and carries out, and is incubated 2～4h between 400 ℃～600 ℃; Sintering vacuum tightness is higher than 1～5 * 10
-2Carry out under the Pa, sintering temperature is 1440 ℃～1480 ℃, and soaking time is 1～1.5h.
(2) nitrogen pressure is 0.1～0.4MPa during vacuum hardening, and the cool time is 5～10 minutes;
During sub-zero treatment, be cooled to-150～-196 ℃ with the speed of 20～60 ℃/min; Soaking time is: the Ni percentage composition * composition coefficient of the weight * weight coefficient of Wimet+Wimet, and the wherein wt coefficient is 5～25min/g, the composition coefficient is 10～20min; Speed with 20～60 ℃/min after insulation finishes is raised to room temperature; The temperature that vacuum tempering is handled is 120～200 ℃, and soaking time is 1～3h, and vacuum tightness is 2～5 * 10
-2Pa.
The invention has the advantages that:
The employing vacuum nitrogen quenches, and cooling makes the WC contact rate controlled fast; Sub-zero treatment can make the solubleness of WC in Ni improve, and improve the strengthening effect of WC, and the alloy surface stressed condition is a stress after handling, and the alloy impact resistance is improved.Adopt Ni cementing WC base cemented carbide preparation method of the present invention, can realize the replacement of Ni, obtain the performance suitable with the WC-Co series hard metal to Co.
Description of drawings
The microtexture pattern (1500X) of the Ni cementing WC base cemented carbide of example 1 among Fig. 1 the present invention
The microtexture pattern (1500X) of the Ni cementing WC base cemented carbide of example 2 among Fig. 2 the present invention
Embodiment
Example 1: composition is that the powder mix of WC-6wt%Ni carries out wet-milling in the roller milling machine, and rotational speed of ball-mill is 50～80r/min, and milling time is 48～56h, and mill ball is the WC-8wt%Co sintered carbide ball of diameter of phi 10mm, and ball material weight ratio is 5: 1; Wet grinding media is a dehydrated alcohol, and adds the forming agent polyoxyethylene glycol of 1.0～2.0wt%, and the dehydrated alcohol dosage is 250～300ml/kg; Powder behind the filtration drying becomes TNMG220404-ZM under the pressure of 300～400MPa, its weight is 13.4g; Sintering carries out in vacuum oven, takes off forming agent and is higher than under 10～15Pa in vacuum tightness and carries out, and is incubated 2-4h between 400 ℃～600 ℃; Sintering vacuum tightness is higher than 1～5 * 10
-2Carry out under the Pa, sintering temperature is 1440 ℃～1480 ℃, and soaking time is 1～1.5h.Nitrogen pressure is 0.1～0.4MPa during vacuum hardening, and the cool time is 5～10 minutes; During sub-zero treatment, be cooled to-150～-196 ℃ with the speed of 20～60 ℃/min; Soaking time is 150～220min; Speed with 20-60 ℃/min after insulation finishes is raised to room temperature; The temperature that vacuum tempering is handled is 120～200 ℃, and soaking time is 1～3h, and vacuum tightness is 2～5 * 10
-2Pa.Its hardness is 91.1HRA, and microtexture is seen Fig. 1.
Example 2: composition is that the powder mix of WC-8wt%Ni carries out wet-milling in the roller milling machine, and rotational speed of ball-mill is 50～80r/min, and milling time is 48～56h, and mill ball is the WC-8wt%Co sintered carbide ball of diameter of phi 10mm, and ball material weight ratio is 5: 1; Wet grinding media is a dehydrated alcohol, and adds the forming agent polyoxyethylene glycol of 1.0～2.0wt%, and the dehydrated alcohol dosage is 250～300ml/kg; Powder behind the filtration drying becomes WNMG120408-ZM under the pressure of 300～400MPa, its weight is 9.8g; Sintering carries out in vacuum oven, takes off forming agent and is higher than under 10～15Pa in vacuum tightness and carries out, and is incubated 2-4h between 400 ℃～600 ℃; Sintering vacuum tightness is higher than 1～5 * 10
-2Carry out under the Pa, sintering temperature is 1440 ℃～1480 ℃, and soaking time is 1～1.5h.Nitrogen pressure is 0.1～0.4MPa during vacuum hardening, and the cool time is 5～10 minutes; During sub-zero treatment, be cooled to-150～-196 ℃ with the speed of 20～60 ℃/min; Soaking time is 100～160min; Speed with 20-60 ℃/min after insulation finishes is raised to room temperature; The temperature that vacuum tempering is handled is 120～200 ℃, and soaking time is 1～3h, and vacuum tightness is 2～5 * 10
-2Pa.Its hardness is 90.4HRA, and microtexture is seen Fig. 2.
Claims (1)
1. the preparation method of a Ni cementing WC base cemented carbide, it is characterized in that elder generation carries out wet-milling with the mixed powder of WC and Ni in the roller milling machine, rotational speed of ball-mill is 50～80r/min, milling time is 48～56h, mill ball is the WC-8wt%Co sintered carbide ball of diameter of phi 10mm, and ball material weight ratio is 5: 1, and wet grinding media is a dehydrated alcohol, and adding the forming agent polyoxyethylene glycol of 1.0～2.0wt%, the dehydrated alcohol dosage is 250～300ml/kg; Filter, dried powder is at the forming under the pressure of 300～400MPa; Sintering carries out in vacuum oven, takes off forming agent and is higher than under the 15Pa in vacuum tightness and carries out, and is incubated 2～4h between 400 ℃～600 ℃, and sintering is higher than 5 * 10 in vacuum tightness
-2Carry out under the Pa, sintering temperature is 1440 ℃～1480 ℃, and soaking time is 1～1.5h; Feed nitrogen when sintering is finished in the stove and carry out vacuum hardening, nitrogen pressure is 0.1～0.4MPa during vacuum hardening, and the cool time is 5～10 minutes; Come out of the stove then and in liquid nitrogen, carry out sub-zero treatment, during sub-zero treatment, be cooled to-150～-196 ℃ with the speed of 20～60 ℃/min; Soaking time is: the Ni percentage composition * composition coefficient of the weight * weight coefficient of Wimet+Wimet, and the wherein wt coefficient is 5～25min/g, and the composition coefficient is 10～20min, and the speed with 20～60 ℃/min after insulation finishes is raised to room temperature; And in vacuum oven, carry out temper, and the temperature that vacuum tempering is handled is 120～200 ℃, and soaking time is 1～3h, and vacuum tightness is 2～5 * 10
-2Pa.
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Cited By (2)
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| CN104894452A (en) * | 2015-07-03 | 2015-09-09 | 中南大学 | Novel WC-Fe-Ni hard alloy roll ring and preparation method thereof |
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| CN104894452A (en) * | 2015-07-03 | 2015-09-09 | 中南大学 | Novel WC-Fe-Ni hard alloy roll ring and preparation method thereof |
| CN104894452B (en) * | 2015-07-03 | 2017-09-12 | 中南大学 | A kind of WC Fe Ni carbide roll rings and preparation method thereof |
| CN106399794A (en) * | 2016-10-28 | 2017-02-15 | 技锋精密刀具（马鞍山）有限公司 | Material for hard alloy slitting tool and preparation method of material |
| CN106399794B (en) * | 2016-10-28 | 2017-10-10 | 技锋精密刀具（马鞍山）有限公司 | A kind of hard alloy cutting tool material and preparation method thereof |
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