CN103537702A - Preparing methods of high-bending-strength nanometer WC-Co alloy powder and WC-Co alloy product - Google Patents
Preparing methods of high-bending-strength nanometer WC-Co alloy powder and WC-Co alloy product Download PDFInfo
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Abstract
The invention relates to a preparing method of high-bending-strength nanometer WC-Co alloy powder. The method includes conducting burdening on original WC powder and Co powder according to components of hard alloy under the vacuum condition, utilizing alcohol as a ball milling liquid medium, utilizing argon as protection gas used in a ball milling process, adopting a hard alloy milling ball to conduct ball milling preparing, adding nanometer rare earth oxide in the milling process and conducting drying and screening to obtain the high-bending-strength nanometer WC-Co hard alloy powder. A preparing method of a WC-Co alloy product is further disclosed. Burdening is conducted under the vacuum condition in the high energy ball milling WC-Co alloy powder preparing stage, a certain amount of alcohol is added to serve as the liquid medium, wet milling is conducted under protection of the argon, powder oxidation can be effectively avoided, and powder component evenness and dispersibility are improved. The nanometer rare earth oxide is added to conduct modification to restrain growth of grains of a WC-Co hard alloy material, and hard alloy performance is greatly improved.
Description
Technical field:
The present invention relates to Hardmetal materials technical field, refer in particular to a kind of preparation method of high-flexural strength nano WC-Co alloy powder and the preparation method of WC-Co alloy product.
Background technology:
Carbide alloy is to take WC, TiC or the two to form composite carbide be hard phase, take Co as Binder Phase, a kind of alloy material forming by powder metallurgical technique high-temperature liquid-phase sintering.Carbide alloy has that hardness is high, wear-resisting, intensity and a series of premium properties, particularly its high rigidity and wearability such as toughness is better, heat-resisting, corrosion-resistant, even also substantially remain unchanged at the temperature of 500 ℃, still has very high hardness in the time of 1000 ℃.
While manufacturing carbide alloy, select raw material powder particle size between 1～2 micron, and purity is very high.Raw material in accordance with regulations proportion of composing is prepared burden, and adds alcohol or the wet-milling in wet ball mill of other media, makes them fully mix, pulverize, and drying, adds the forming agent of classes such as wax or glue after sieving, then through super-dry, sieving makes compound.Mixture granulation, die mould, be heated to when approaching binding metal fusing point (1300～1500 ℃), sclerosis just forms eutectic alloy with binding metal.Through supercooling, sclerosis is distributed in the grid of binding metal composition mutually, closely links together each other, forms a firmly integral body.The hardness of carbide alloy depends on sclerosis phase content and crystallite size, hardens that phase content is higher, crystal grain is thinner, and hardness is also larger.The toughness that junction temperature reduces carbide alloy determines by binding metal, and binding metal content is higher, and bending strength is larger.
The traditional preparation method of WC-Co carbide alloy generates WC by W powder and C powder in 1400～1600 solid phase reactions, then with Co powder mixing and ball milling, cold moudling, densified finally by liquid-phase sintering.Generally at 1um～10um, there is the problems such as fragility is large, work softening in the alloy grain that this preparation method obtains.For example, though adjust some performance that WC/Co component can be improved final part, increase hardness increase wearability and corrosion resistance that WC content can improve part; Increasing Co content can improve strength and toughness and improve processing characteristics.Yet be difficult to for a long time, when improving hardness, improve intensity and toughness always.
Carbide alloy has become its development trend from traditional to ultra-fine, nano level conversion at present, and in the more than ten years in the past, in high-performance rigid alloy field, the research of ultra-fine cemented carbide and nanoscale hard alloy is a hot issue always.Yet undue preparation nanometer or the ultra-fine cemented carbide pursued, cost is increased sharply, the effect obtaining be not very obviously, and be difficult to control the grain growth in sintering process with this traditional handicraft production of powder metallurgy carbide alloy, cause the carbide alloy of acquisition small grains very difficult.
At present, the production technology of the large complicated different in nature goods of carbide alloy mainly contains two kinds:
A kind of is by compound compacting, comprises mold pressing and cold isostatic compaction, then through oversintering, produces hard alloy blank, and after sintering, allowance is large especially, and difficulty of processing is large, and length consuming time is extremely uneconomical; Another kind is that compound is contained in graphite jig, compacting and the one step completed heat pressing process of sintering.The feature of heat pressing process is that extrudate density is high, performance good, pressing pressure is little, can produces massive article.But the shape of goods is restricted, can only prepare the goods of simple shape, and this technique is only suitable for single-piece or small lot batch manufacture, productivity ratio is low, cost is high.Injection moulding is being widely applied aspect the preparation of small size cemented carbide with complicated shape parts as a kind of near-net-shape technique, but injection molding technology exists a lot of shortcomings, for example degumming tech is loaded down with trivial details, the percent defective that comes unstuck is high, product strength is low etc., and equipment and mold is had relatively high expectations, fact proved that injection moulding can only prepare small size parts.
Gel casting (gelcasting) equals early 1990s by U.S. Oak Ridge National Laboratory professor M.A.Janney to be invented, and is a kind of complicated shape pottery of in recent years receiving much attention or the original position solidification forming method of metal parts near net-shape.Gel casting technology is the combination of traditional colloidal state forming technology and chemical theory, compare with traditional wet-formed technique, there is easy shaping complicated shape, large-scale part, die cost is cheap, shaping base substrate component is even, even density, defect is few, intensity is high, do not need special degreasing process, be applicable to the unique advantages such as various metals powder, the base substrate of what is more important gel casting can carry out common turning processing, reduced to greatest extent the fine finishining amount of end article, for the precision form of metallic article, prepare a kind of low cost is provided, the process means of high reliability.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art part, a kind of preparation method of high-flexural strength nano WC-Co alloy powder and the preparation method of WC-Co alloy are provided.
The technical scheme that the present invention realizes its object employing is: a kind of preparation method of high-flexural strength nano WC-Co alloy powder, the method is: under vacuum condition, original WC, Co powder are prepared burden according to the composition ratio of carbide alloy, using alcohol as ball milling liquid medium, using the protective gas of argon gas during as ball milling, adopt carbide alloy mill ball to carry out ball milling preparation, and in process of lapping, add oxide nano rare earth; By being dried, sieving, obtain high-flexural strength nano WC-Co cemented carbide powder.
In the method, the weight of oxide nano rare earth is 1% of WC, Co grain weight amount.
In the method, the liquid-solid ratio of the alcohol adding and original WC, Co powder (being the ratio of weight with the weight of WC, Co powder of alcohol) is 1:1.
In the method, the ratio of grinding media to material of grinding (being the ratio of weight with the weight of WC, Co powder of mill ball) is 10:1-12:1.
In the method, the rotating speed of ball milling is 180r/min-200r/min, and Ball-milling Time is 24h-48h.
The present invention also provides a kind of preparation method's based on above-mentioned high-flexural strength nano WC-Co alloy powder WC-Co hard alloy production process, and this production technology comprises:
A. preparation WC-Co cemented carbide powder is ground in vacuum strengthening: under vacuum condition, original WC, Co powder are prepared burden according to the composition ratio of carbide alloy, using alcohol as ball milling liquid medium, using the protective gas of argon gas during as ball milling, adopt carbide alloy mill ball to carry out ball milling preparation, and in process of lapping, add oxide nano rare earth; By being dried, sieving, obtain high-flexural strength nano WC-Co cemented carbide powder;
B. prepare premixed liquid: by HEMA(hydroxyethyl methacrylate) be dissolved in toluene, be mixed with premixed liquid;
C. prepare WC-Co alloy pulp: by certain solid content, weigh high-flexural strength nano WC-Co cemented carbide powder and premixed liquid input ball mill mix and blend, and drop into appropriate dispersant;
D. mould molding: adopt gel injection-moulding equipment by the WC-Co alloy pulp Implanted Silicon sealing rubber die preparing, and add initator and catalyst when injecting, to control the slurry curing time;
E. the demoulding, dry, low pressure sintering moulding WC-Co hard metal article.
In above-mentioned production technology, during preparation WC-Co alloy pulp, better solid content is 50-60vol.%, and best solid content is 55vol.%, and best mixing time is 10h-12h.
In above-mentioned production technology, in described premixed liquid, the weight percentage of HEMA is 30%-40%, and the consumption of HEMA accounts for 1.7% of cemented carbide powder quality.
In above-mentioned production technology, described dispersant is hyper-dispersant Solsperse-6000, and content accounts for 0.3% of cemented carbide powder quality, and described initator is benzoyl peroxide (BPO), 0.7% of the consumption that its consumption is HEMA.
In above-mentioned production technology, described low pressure sintering comprises following steps:
1. alloy base substrate is heated to 400 ℃ through 2h, after insulation 1h, dewaxes;
2. the speed with 10 ℃/min makes furnace temperature be elevated to 1320 ℃, carries out solid-phase sintering, and sintering time is 40min;
3. be heated to liquidus temperature and carry out above liquid-phase sintering, sintering time is also 40min;
4. after liquid-phase sintering, apply the pressure of 4.5MPa, pressure carrier is common pure Ar gas, and compression rate is 0.3MPa/min, is incubated 15min after pressurization again, and pressure remains to furnace temperature lower than below 900 ℃ always;
5. finally cooling, the cooldown rate of temperature when more than 900 ℃ is 8 ℃/min, and the cooldown rate of temperature below 900 ℃ time is 10 ℃/min.
The present invention is in the preparation technology of preparation WC-Co alloy powder and WC-Co alloy product; the stage of preparing WC-Co alloy powder at high-energy ball milling; under vacuum condition, prepare burden; by adding a certain amount of alcohol to carry out wet-milling as liquid medium and under the protection of argon gas; can effectively prevent Powder Oxidation, improve uniformity and the dispersiveness of powder composition simultaneously.In this preparation method, can obtain BET powder size is 59.4rim, the nano WC-Co composite powder end that specific surface is 6.82m/g, and in powder, Co element is uniformly dispersed.And, by adding oxide nano rare earth modification, suppress the growing up of crystal grain of WC-Co Hardmetal materials, greatly promoted Cemented Carbide Properties.
Accompanying drawing explanation:
Fig. 1 is preparation technology's flow chart of WC-Co hard metal article in the present invention;
Fig. 2-1st, adopts oxide nano rare earth to WC-Co cemented carbide powder modified effect comparison diagram in the present invention;
Fig. 2-2nd, in the present invention, WC-Co alloy pulp viscosity is with the change curve of shear rate and monomer concentration;
Fig. 2-3rd, the influence curve figure of content of monomer to dry base substrate intensity and sintered body fracture strength in the present invention;
Fig. 2-4 are the influence curve figures of different dispersants to WC-Co alloy pulp viscosity;
Fig. 2-5 are the densogram of cemented carbide sintered body under different sintering temperatures in the present invention;
Fig. 2-6 are the firmness change curve map of cemented carbide powder after different temperatures sintering in the present invention;
The specific embodiment:
Below in conjunction with specific embodiments and the drawings, the present invention is further described.
The preparation method of high-flexural strength nano WC-Co alloy powder of the present invention is: under vacuum condition, original WC, Co powder are prepared burden according to the composition ratio of carbide alloy, using alcohol as ball milling liquid medium, using the protective gas of argon gas during as ball milling, adopt carbide alloy mill ball to carry out ball milling preparation, and in process of lapping, add oxide nano rare earth; By being dried, sieving, obtain high-flexural strength nano WC-Co cemented carbide powder.
In the method, the liquid-solid ratio of the alcohol adding and original WC, Co powder (being the ratio of weight with the weight of WC, Co powder of alcohol) is 1:1.In Process During High Energy Ball Milling, by adding a certain amount of alcohol to carry out wet-milling as liquid medium medium, can effectively prevent Powder Oxidation, improve uniformity and the dispersiveness of powder composition simultaneously.Under wet-milling condition, the addition of liquid medium has a great impact the uniformity of ball-milled powder composition and dispersiveness.The addition of liquid alcohol medium is that liquid-solid ratio exists a critical condition, when liquid-solid ratio is very little time, liquid can not fully soak each powder particle, and in ball grinding cylinder, viscosity of sludge is larger, viscosity flow resistance in mechanical milling process is larger, and effective motion can not occur with the rotation of ball grinding cylinder for ball and feed liquid; In addition, Elements C o has less density, and its effect of inertia is less, and Co powder can not mix fully with WC powder, thereby powder can not be disperseed and refinement effectively.Along with liquid-solid ratio increases, viscosity of sludge reduces, and the viscosity flow resistance of ball and powder motion reduces, and liquid is also gradually evenly coated on powder particle surface and between ball and powder, forms one deck liquid film as thin as a wafer.Liquid film on the one hand can reduce the direct contact of ball grinding cylinder effectively and the ball milling that produces is mingled with, and meanwhile, can stop the gathering of powder particle, and now the chemical composition in powder is more even.Along with the further increase of liquid-solid ratio, now, liquid medium is too much. and the collision mean free path degree between powder particle increases, effective collision effect reduces greatly, meanwhile, because the density contrast of liquid medium and powder is excessive, produce two and be separated, cause powder effectively evenly not mix and refinement.
When liquid-solid ratio is 1:1, in powder, the chemical composition of Co phase approaches the mixing match of starting powder most, and Co can be dispersed in WC powder preferably, and now mixed effect is best.
In the method, the ratio of grinding media to material of grinding (being the ratio of weight with the weight of WC, Co powder of mill ball) is 10:1-12:1.
The BET granularity of powder reduces with the increase of ratio of grinding media to material.When ratio of grinding media to material is 4:l, after ball milling, the BET granularity of powder is higher, for 103.4nm, along with ratio of grinding media to material increases, abrading-ball quantity in unit volume increases, in mechanical milling process, the collision frequency of interior abrading-ball of unit interval and powder particle increases, and abrading-ball is added the grinding area of powder, and fragmentation and the thinning effect of powder obviously increase.When ratio of grinding media to material is 10:1, fragmentation and the thinning effect of powder are more remarkable, and now powder BET granularity is only 69.3nm.And ratio of grinding media to material is between 10:1-12:1 time, the fragmentation of powder and refinement trend become gently, and when ratio of grinding media to material is 12:1, powder BET granularity is 67.8nm, and this is because suitable ratio of grinding media to material can promote fragmentation and the thinning effect of powder.Yet, after the further increase ratio of grinding media to material, although increased the collision opportunity of abrading-ball and powder particle in mechanical milling process, increased the process that powder is broken, tear, because abrading-ball collision is too fierce, certainly will cause the rising of ball milling temperature, increase the cold welding of powder and the process of reply, make powder fragmentation be tending towards dynamic equilibrium with reply, make powder particle change of granularity little, in mechanical milling process, energy consumption sharply increases simultaneously, and the wearing and tearing of abrading-ball and consumption increase, and are unfavorable for the carrying out of ball milling.Therefore, when best ratio of grinding media to material 12:1, can best fragmentation and the refinement that promotes powder.
In the method, the rotating speed of ball milling is 180r/min-200r/min, and Ball-milling Time is 24h-48h.
Along with rotational speed of ball-mill increases, powder BET granularity reduces gradually.When rotating speed is during at 140～160r/rain, powder BET granularity sharply declines, this is because of ball milling under the speed of 140r/min, ball milling speed is lower, abrading-ball and powder are at the bottom of tank, to roll or simple translation substantially, can not produce enough centripetal force and abrading-ball and powder particle be taken up effectively do parabolic motion, thereby reduce the process of powder fragmentation.And rise of rotational speed is during to 160r/min. some abrading-ball is done incomplete throwing in tank.Ball milling effect has clear improvement, therefore the decline of powder BET granularity is very fast.When rotating speed changes between 160～200r/min, abrading-ball all has throwing in various degree, the ratio of doing parabolic motion with the increase abrading-ball of rotating speed increases. urged the thinning process of powder, the BET granularity of powder decreases: when rotational speed of ball-mill reaches 200r/min, the more effective parabolic motion of doing of abrading-ball, now abrading-ball frequent and violent throwing, impact in tank, makes that powder is constantly torn, fragmentation, make the further refinement of powder BET granularity, under this state, ball milling effect is better.If but further improve rotating speed, for abrading-ball and powder particle are along with spherical tank revolution provides larger possibility, cause the decline of thinning effect.
In addition, the impact of Ball-milling Time.Powder BET granularity to ball milling 12h is higher, is 102.1nm, along with Ball-milling Time extends, powder BET granularity significantly declines, and after ball milling 36h, minimum (<60nm) appears in powder BET granularity, and when Ball-milling Time is long, the ET change of granularity of powder tends towards stability.This is because in suitable Ball-milling Time, and along with the prolongation of Ball-milling Time, abrading-ball increases powder particle collision frequency, has increased the thinning process of powder particle.And along with the further prolongation of Ball-milling Time, powder fining to a certain extent after, the refinement of particle and reunion trend towards dynamic equilibrium, particle size trends towards limiting value.When Ball-milling Time is 48h, the BET granularity of powder is compared with ball milling 36h, and powder does not obtain further refinement.Long Ball-milling Time can increase the degree of abrading-ball and grinding jar wearing and tearing simultaneously, introduces more impurity, and the performance of alloy has larger impact.Show that ball milling 36h is one of optimum condition that preparation is ultra-fine or nano WC-Co composite powder is last.
To sum up, high-energy-milling parameter is very important to obtaining the uniform nanometer WC-Co powder of composition.In the application, well suitedly in this project vacuum Intensive ball mill, prepare nanometer WC powder and nano WC-Co composite powder end technological parameter and be: liquid-solid ratio is that 1:l, ratio of grinding media to material are that 10:1, rotational speed of ball-mill are that 180-200r/min, Ball-milling Time are 36h.Under these process conditions, can obtain BET powder size is 59.4rim, the nano WC-Co composite powder end that specific surface is 6.82m/g, and in powder, Co element is uniformly dispersed.
In the method, the weight of oxide nano rare earth is 1% of WC, Co grain weight amount.
Oxide nano rare earth is being adsorbed in Hardmetal materials particle of densification well, thereby can well to WC-Co Hardmetal materials, carry out modification, promotes Cemented Carbide Properties, and its effect is mainly reflected in:
1. suppress growing up of crystal grain.In sintering process, WC particle mainly contains two kinds of growth patterns: a kind of is noncontinuity growth, and another kind is continuity growth.
Noncontinuity growth is that tiny hard phase WC contacts with each other by crystal grain, and polymerization is grown up, and is unified into thick WC or thick WC annexes tiny WC.After adding nano rare earth material modified, now, because the nano particle pinning of nanometer additive is in WC grain border, its aggregation growth is hindered, suppressed grain growth.Continuity growth, after in WC-Co hard alloy sintering process, liquid phase generates, the atom on solid phase WC particle surface is dissolved in liquid phase gradually, liquid phase has larger saturation solubility to WC granule, lower to the oarse-grained saturation solubility of WC, thereby WC granule first dissolves, and separate out on large WC particle surface, so bulky grain WC is tending towards growing up, can regard Os-wald growing mechanism as.Add nano rare earth modifier can stablize the liquid phase in hard alloy sintering process, delay separating out of WC, when WC separates out from the larger state of degree of supersaturation, WC grain forming core speed is far longer than growth rate, thereby reaches the object of crystal grain thinning like this.
2. improve carbide alloy toughness.WC is the skeleton of carbide alloy, and refinement WC can make the contact of this skeleton more abundant, and then can bear larger load, nano rare earth modifier add the hardness that can improve prepared carbide alloy.Therefore add after nano rare earth modifier, sample fracture toughness mean value is improved, and improves reason relevant with grain size, also relevant with intercrystalline strengthening, solution strengthening etc.Because crystal grain thinning increases crystal boundary greatly, because WC intensity is very large, more tiny crystal grain is conducive to reduce the defect of single crystal grain, fracture mainly occurs in crystal boundary like this, crackle forms and in crystal boundary expansion at crystal boundary, simultaneously due to solution strengthening crystal boundary, and the resistance increment of Crack Extension like this, expansion need consume more multipotency, therefore makes the toughness of Hardmetal materials be able to good raising.
Therefore, add nano rare earth as modification, can improve hardness and fracture toughness simultaneously, reduce coefficient of friction and improve wearability.Find in test, the hard alloy wear resistance that adds nano rare earth improves, and along with the increasing of nano rare earth addition, wear volume presents the trend that first declines and raise afterwards.Due to nano rare earth addition seldom time, the effect that often do not reach crystal grain thinning, purifies boundary, improves W, the C solid solubility in Binder Phase.And add too much, possibility segregation, on interface, has indirectly affected wearability thereby reduce its mechanical property.Be that nano rare earth addition exists an optimum value, the too low or too high wearability that all can reduce carbide alloy.In the application, 1% left and right by oxide nano rare earth addition in WC, Co grain weight amount, can reach optimum efficiency.
By aforementioned known, in the present invention, adopt vacuum strengthening to grind the WC-Co cemented carbide powder of preparation, performance is splendid, further prepares on this basis WC-Co hard metal article.WC-Co hard alloy production process comprises:
A. preparation WC-Co cemented carbide powder is ground in vacuum strengthening: under vacuum condition, original WC, Co powder are prepared burden according to the composition ratio of carbide alloy, using alcohol as ball milling liquid medium, using the protective gas of argon gas during as ball milling, adopt carbide alloy mill ball to carry out ball milling preparation, and in process of lapping, add oxide nano rare earth; By being dried, sieving, obtain high-flexural strength nano WC-Co cemented carbide powder;
B. prepare premixed liquid: by HEMA(hydroxyethyl methacrylate) be dissolved in toluene, be mixed with premixed liquid;
C. prepare WC-Co alloy pulp: by certain solid content, weigh high-flexural strength nano WC-Co cemented carbide powder and premixed liquid input ball mill mix and blend, and drop into appropriate dispersant;
D. mould molding: adopt gel injection-moulding equipment by the WC-Co alloy pulp Implanted Silicon sealing rubber die preparing, and add initator and catalyst when injecting, to control the slurry curing time;
E. the demoulding, dry, low pressure sintering moulding WC-Co hard metal article.
In above-mentioned production technology, during preparation WC-Co alloy pulp, better solid content is 50-60vol.%, and best solid content is 55vol.%, and best mixing time is 10h-12h.In described premixed liquid, the weight percentage of HEMA is 30%-40%, and the consumption of HEMA accounts for 1.7% of cemented carbide powder quality.Described dispersant adopts hyper-dispersant Solsperse-6000, and content accounts for 0.3% of cemented carbide powder quality.
The key of the shaping of gel injection-moulding is that to prepare solid content high, good fluidity, the suspended nitride of good stability.When shear rate 20s-1, lower than 1Pas guarantee, it fully fills mould to the viscosity number of slurry not by external force in the situation that.As shown in Fig. 2-2, WC-Co alloy pulp viscosity is with the change curve of shear rate and monomer concentration.
The Forming Theory of gel injection-moulding is exactly to rely on the polymerization of monomer in premixed liquid to connect to form a three-dimensional net structure metal dust is wrapped in to the inside forms an overall structure.So the content of monomer is most important to the performance of end article in premixed liquid.Content of monomer in premixed liquid is too low, the content of monomer being shaped in base substrate is too low, will cause base substrate low without intensity or intensity, and this is important is because too low content of monomer polymerization will form an incomplete network structure, can not wrap up all powders completely, so cause blank strength low.In the mixed system of gel and powder, monomer connects coated metal powder, so will keep a balance between content of monomer and the volume fraction of metal-powder, when the content of monomer surpasses this equilibrium valve, just there will be local monomer polymerization to form organic matter caking, after sintering, have the place of caking will form the inside that cavity remains in sintered body.
The key of content of monomer in the gel casting technique of carbide alloy, in the present invention, selecting hydroxyethyl methacrylate (HEMA) is organic monomer, because HEMA has hydroxyl-OH, in toluene, it can be adsorbed on the surface of the cemented carbide powder particle with water-wet behavior, serve as surfactant, the wetability of improving to a certain extent toluene and cemented carbide powder particle, is better disperseed powder particle, so the viscosity of slurry reduces the increase along with HEMA addition.
As shown in Fig. 2-2, organic monomer content is higher, and the organic three-dimensional net structure forming after gel is more complete, and powder consolidation is more firm, thereby blank strength is also just higher.Although increase the intensity that HEMA content is conducive to improve dry base substrate, from Fig. 2-3, also can find, when the content of HEMA is too much, can cause the fracture strength reduction of sintered body.Therefore, the organic monomer of the best of the present invention is that HEMA content is to account for 1.7% of cemented carbide powder quality.
Shown in Fig. 2-4, dispersant is selected and is controlled addition the solid content of gel injection-moulding is improved and has great role.Dispersant of the present invention adopts hyper-dispersant Solsperse-6000, and content: 0.3wt%(accounts for the quality of shaping powder); Compare with traditional dispersant, hyper-dispersant has following advantage: (1) forms multi-point-anchoring at particle surface, improves absorption fastness, is difficult for desorb; (2) carbon chain lengths of General Decentralized agent contains at most 18 carbon, and the solvent chain of hyper-dispersant is than traditional dispersant lipophilic group regimental commander, can play effective Steric stabilization.
In above-mentioned production technology, described initator is benzoyl peroxide (BPO), 0.7% of the consumption that its consumption is HEMA.
In gel casting, the addition of initator is the principal element that affects induction period.Be exactly slip hardening time induction period, and induction period is too short, and the experimental implementation time is short, can not well pour into a mould, and slurry can not well fill type; Induction period is long, and the easy sedimentation of powder in slurry can not guarantee the uniformity of base substrate.In order to extend the hardening time of slurry, conventionally reduce the interpolation content of initator, but too low initator by cause slurry do not solidify or solidification intensity low.In gel casting hard alloy process, because article shape is complicated, thus the demoulding of goods has been brought to difficulty, so must guarantee the intensity of shaping base substrate.The blank strength of goods and the content of initator have much relations, and along with the raising of initiator content, the intensity level of goods increases, so must select suitable amount of initiator, find the hardening time of slurry and a suitable equalization point of base substrate.In the present invention, selection initator is benzoyl peroxide (BPO), and content: 0.7wt%(accounts for the quality of organic monomer), can well realize the controllable cured of slurry.
In above-mentioned production technology, described low pressure sintering comprises following steps:
1. alloy base substrate is heated to 400 ℃ through 2h, after insulation 1h, dewaxes;
2. the speed with 10 ℃/min makes furnace temperature be elevated to 1320 ℃, carries out solid-phase sintering, and sintering time is 40min;
3. be heated to liquidus temperature and carry out above liquid-phase sintering, sintering time is also 40min;
4. after liquid-phase sintering, apply the pressure of 4.5MPa, pressure carrier is common pure Ar gas, and compression rate is 0.3MPa/min, is incubated 15min after pressurization again, and pressure remains to furnace temperature lower than below 900 ℃ always;
5. finally cooling, the cooldown rate of temperature when more than 900 ℃ is 8 ℃/min, and the cooldown rate of temperature below 900 ℃ time is 10 ℃/min.
In low pressure sintering, sintering temperature mainly has considerable influence to sintered body grain size, sintered density and sintered body hardness, is mainly reflected in:
(1) sintering temperature found through experiments the impact of sintered body grain size, and the crystal grain of WC is grown up along with the rising of sintering temperature.The main method that solves grain growth in sintering process is to add inhibitor, and the inhibitor that this project adopts is oxide nano rare earth, can well suppress growing up of crystal grain.In general, at lower temperature, during sintering, add a small amount of inhibitor just can suppress growing up of WC grain; At higher temperature, during sintering, just must increase the addition of inhibitor, could suppress the discontinuous of crystal grain and grow up.In the present invention, at 1320 ℃ during sintering, the crystal grain of WC is more tiny, the about 200nm of most of crystal grain, do not have the phenomenon of indivedual abnormal grain growths to occur, at 1400 ℃ during sintering, grain growth is to more than 2um, although the addition of inhibitor reaches 1.0%, also have the phenomenon of abnormal grain growth to occur. therefore, can learn: along with the rising of sintering temperature, WC grain has the trend of growing up, even if add sintering grain inhibitor, also cannot suppress the discontinuous of crystal grain and grow up, but during sintering, can obtain tiny WC grain at 1320 ℃.
(2) on the impact of sintered density in general, along with the rising of sintering temperature, the density of sintered body can increase sintering temperature, and this is due to the rising along with temperature, and the liquid content in sintered body increases, and is conducive to the diffusive migration of material.Figure below 2-5 is the density of cemented carbide powder powder sintered compact under different sintering temperatures, and from Fig. 2-5, along with the rising of sintering temperature, the density of sintered body is not to increase, but diminishes gradually.By the sample to after sintering, carry out zero-G test, find that the sintered body weightlessness under high temperature sintering is always greater than the weightlessness of the sintered body under low-temperature sintering, so causing the reason that sintered density declines along with the rising of sintering temperature is exactly the evaporation of Co.Known by the analysis to sintered density, the sintering temperature of 1320 ℃ is enough to make nanometer powder carbide alloy completely densified.
(3) sintering temperature on sintered body hardness to affect WC grain size less, the mean free path of Co phase is shorter, the hardness of alloy is higher, yet along with the rising of sintering temperature, WC grain size is grown up thereupon, the hardness of carbide alloy can decline thereupon.From Fig. 2-6, when sintering temperature is during lower than 1360 ℃, the hardness of carbide alloy is all higher, and far away higher than conventional carbide alloy, in the time of 1320 ℃, the hardness of sintered body is maximum, reaches HRA94.6, and this is that conventional carbide alloy is incomparable.When sintering temperature is during higher than 1360 ℃, the hardness of sintered body sharply declines, its hardness and conventional carbide alloy are almost suitable, this is mainly because the evaporation of Co causes that hole appears in sintered body inside, thereby affects the hardness of sintered body, and WC grain is sharply grown up, its crystallite dimension is almost suitable with conventional carbide alloy, and WC grain size is larger, the mean free path of Co phase is longer, thereby causes the hardness of alloy corresponding just lower.Therefore,, when sintering temperature is during at 1320 ℃, the hardness of sintered body is maximum.To sum up, the present invention adopts low pressure sintering mode to carry out sintering to base substrate, and sintering temperature is arranged on 1320 ℃, can reach best sintering effect, and assurance can obtain tiny WC grain, the highest hardness and good compactness.
In sum; the present invention is in the preparation technology of preparation WC-Co alloy powder and WC-Co alloy product; the stage of preparing WC-Co alloy powder at high-energy ball milling; under vacuum condition, prepare burden; by adding a certain amount of alcohol to carry out wet-milling as liquid medium and under the protection of argon gas; can effectively prevent Powder Oxidation, improve uniformity and the dispersiveness of powder composition simultaneously.In this preparation method, can obtain BET powder size is 59.4rim, the nano WC-Co composite powder end that specific surface is 6.82m/g, and in powder, Co element is uniformly dispersed.And, by adding oxide nano rare earth modification, suppress the growing up of crystal grain of WC-Co Hardmetal materials, greatly promoted Cemented Carbide Properties.
Experimental data surface, by adding oxide nano rare earth to carry out after modification, Cemented Carbide Hardness is than unmodified raising more than 30%, and coefficient of elasticity improves more than 10%, and Fracture Toughness has improved more than 73%.The key technical indexes that the WC-Co carbide alloy that adopts the inventive method to prepare can reach is as follows:
(1) hart metal product contains Co content 10%, grain size 6 μ m, and density 14.4g/cm3, hardness is greater than 92.5HRA, and bending strength reaches 4000Mpa, and bending strength is high, and combination property is outstanding.
(2) hard metal article of making by gel casting process, key property be density at 11-15g/cm3, bending strength >=1270, hardness >=90HRA.
Claims (10)
1. the preparation method of a high-flexural strength nano WC-Co alloy powder, it is characterized in that: the method is: under vacuum condition, original WC, Co powder are prepared burden according to the composition ratio of carbide alloy, using alcohol as ball milling liquid medium, using the protective gas of argon gas during as ball milling, adopt carbide alloy mill ball to carry out ball milling preparation, and in process of lapping, add oxide nano rare earth; By being dried, sieving, obtain high-flexural strength nano WC-Co cemented carbide powder.
2. the preparation method of high-flexural strength nano WC-Co alloy powder according to claim 1, is characterized in that: in the method, the weight of oxide nano rare earth is 1% of WC, Co grain weight amount.
3. the preparation method of high-flexural strength nano WC-Co alloy powder according to claim 1, is characterized in that: in the method, the liquid-solid ratio of the alcohol adding and original WC, Co powder (being the ratio of weight with the weight of WC, Co powder of alcohol) is 1:1.
4. the preparation method of high-flexural strength nano WC-Co alloy powder according to claim 1, is characterized in that: in the method, the ratio of grinding media to material of grinding (being the ratio of weight with the weight of WC, Co powder of mill ball) is 10:1-12:1.
5. the preparation method of high-flexural strength nano WC-Co alloy powder according to claim 1, is characterized in that: in the method, the rotating speed of ball milling is 180r/min-200r/min, and Ball-milling Time is 24h-48h.
6. the WC-Co hard alloy production process based on vacuum Intensive ball mill preparation method, is characterized in that: this production technology comprises:
A. preparation WC-Co cemented carbide powder is ground in vacuum strengthening: under vacuum condition, original WC, Co powder are prepared burden according to the composition ratio of carbide alloy, using alcohol as ball milling liquid medium, using the protective gas of argon gas during as ball milling, adopt carbide alloy mill ball to carry out ball milling preparation, and in process of lapping, add oxide nano rare earth; By being dried, sieving, obtain high-flexural strength nano WC-Co cemented carbide powder;
B. prepare premixed liquid: by HEMA(hydroxyethyl methacrylate) be dissolved in toluene, be mixed with premixed liquid;
C. prepare WC-Co alloy pulp: by certain solid content, weigh high-flexural strength nano WC-Co cemented carbide powder and premixed liquid input ball mill mix and blend, and drop into appropriate dispersant;
D. mould molding: adopt gel injection-moulding equipment by the WC-Co alloy pulp Implanted Silicon sealing rubber die preparing, and add initator and catalyst when injecting, to control the slurry curing time;
E. the demoulding, dry, low pressure sintering moulding WC-Co hard metal article.
7. WC-Co hard alloy production process according to claim 6, is characterized in that: during preparation WC-Co alloy pulp, better solid content is 50-60vol.%, and best solid content is 55vol.%, and best mixing time is 10h-12h.
8. WC-Co hard alloy production process according to claim 6, is characterized in that: in described premixed liquid, the weight percentage of HEMA is 30%-40%, and the consumption of HEMA accounts for 1.7% of cemented carbide powder quality.
9. WC-Co hard alloy production process according to claim 6, is characterized in that: described dispersant is hyper-dispersant Solsperse-6000, and content accounts for 0.3% of cemented carbide powder quality; Described initator is benzoyl peroxide (BPO), 0.7% of the consumption that its consumption is HEMA.
10. WC-Co hard alloy production process according to claim 6, is characterized in that:
Described low pressure sintering comprises following steps:
1. alloy base substrate is heated to 400 ℃ through 2h, after insulation 1h, dewaxes;
2. the speed with 10 ℃/min makes furnace temperature be elevated to 1320 ℃, carries out solid-phase sintering, and sintering time is 40min;
3. be heated to liquidus temperature and carry out above liquid-phase sintering, sintering time is also 40min;
4. after liquid-phase sintering, apply the pressure of 4.5MPa, pressure carrier is common pure Ar gas, and compression rate is 0.3MPa/min, is incubated 15min after pressurization again, and pressure remains to furnace temperature lower than below 900 ℃ always;
5. finally cooling, the cooldown rate of temperature when more than 900 ℃ is 8 ℃/min, and the cooldown rate of temperature below 900 ℃ time is 10 ℃/min.
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