CN106811652A - A kind of preparation method of VC VN cold work die steel in high alloy through base steel bonded carbide - Google Patents

A kind of preparation method of VC VN cold work die steel in high alloy through base steel bonded carbide Download PDF

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CN106811652A
CN106811652A CN201710074660.8A CN201710074660A CN106811652A CN 106811652 A CN106811652 A CN 106811652A CN 201710074660 A CN201710074660 A CN 201710074660A CN 106811652 A CN106811652 A CN 106811652A
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powder
steel
slurry
preparation
sintering
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王爱华
丁家伟
丁刚
耿德英
鹿薇薇
鹿策
施孟达
陈志和
朱坚
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DANYANG HUIDA MOLD MATERIAL TECHNOLOGY CO LTD
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DANYANG HUIDA MOLD MATERIAL TECHNOLOGY CO LTD
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1017Multiple heating or additional steps
    • B22F3/1021Removal of binder or filler
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • C22C1/051Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0207Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Powder Metallurgy (AREA)

Abstract

The present invention relates to a kind of preparation method of VC VN cold work die steel in high alloy through base steel bonded carbide, comprise the following steps:Proportionally weigh carbonized titanium powder and cold work die steel in high alloy through matrix powder, alloyed powder is put into ball mill and is mixed and is crushed, wherein addition absolute ethyl alcohol is process control agent, wet mixed powder is put into vacuum drying chamber after ball milling is dried, standby after drying.Organic monomer and initiator are added in solvent and prepare premixed liquid;Add the additive for improving slurry fluidity and dispersiveness;Add catalyst and pH adjusting agent and stir, obtain slurry;The slurry solidifying mould of injection note is vacuumized or shaken degasification, base substrate is put into vacuum drying chamber after slurry curing shaping is dried, dried base substrate is carried out into integrated degumming and sintering in vacuum sintering furnace, prepare steel bonded carbide.The present invention has the advantages that relatively low process is simple, cost, easily prepared large scale, Irregular Shaped Parts on the basis of it ensure that steel bonded carbide macro property.

Description

A kind of preparation method of VC-VN cold work die steel in high alloy through base steel bonded carbide
Technical field
The present invention relates to a kind of preparation method of VC-VN high alloys cold mold base steel steel bonded carbide, belong to Metal Substrate Field of composite material preparation.
Background technology
Steel bonded carbide is a kind of composite with ceramic phase and with steel as bonding matrix, and its performance is between common hard Between matter alloy and steel, while having a series of other advantages, it is set to be widely used in many fields.In recent years, To obtain some particular tissues and performance of steel bonded carbide, and alleviate due to conventional rigid alloy material Main Resources W, Co Increasingly deficient the problems such as, steel bonded carbide is carried out both at home and abroad more extensively and in-depth study, particularly to addition not With the research (such as addition A1203, TiN, NbC, TiCN, TiB2, Mo2FeB2, Mo2C, Cr3C2, VC, NV etc.) of New Rigid phase. In recent years, some new hard phase steel-bonded carbides are continued to bring out.Mitsubishi metal company is relatively low but resistance to using TiCN hardness The characteristics of mill property is very strong, high speed comminuted steel shot is mixed with titanium carbonitride additive, shape, is dewaxed, then by high temperature insostatic pressing (HIP), Re Chu The TiCN base steel-bonded carbides that reason and method for fine finishing are produced, with uniform microstructure, segregation-free, alloying level spy high Point.Rubbing action is small between TiN and ferrite, and antisticking ability is more stronger than TiC, and free energy is smaller, oxidation resistance temperature scope Greatly.Sandvik AB of Sweden has developed a kind of new steel-bonded carbide CORONlTE based on TiN.They use a kind of special work Skill, the TiN powder of superfine (about 0.1 micron) is equably added in heat treatable steel matrix, and its volume content can be from 35% to 60%, because TiN powder is thin and performance and its stabilization, obtained CORONITE alloys have hard concurrently by this method The wearability of alloy and the toughness of high-speed steel.
TiB2 has heat-resisting quantity good, and density and resistivity are small, and conductibility is good, and metal adhesiveness is low and friction factor It is low, the features such as inoxidizability is strong, it is considered to be a kind of preferable steel-bonded carbide hard phase.Because of the solid solubility between Fe and TiB2 Low, wetability is good, and Mo can also improve its wetability, therefore the advantage of synthesis TiB2 and Fe, Mo, has made TiB.FeMo composite woods each Material.
Japanese certain company develops and a kind of does not contain W, Co but the boride-based composite KMH of the M02FeB2 types containing Cr. Such polynary boride-based alloy be prepared using water atomization Fe-Cr-B alloy powders, boride powder and Fe, Cr, Mo, The metal dusts such as Ni make raw material, are manufactured through wet-milling mixing, compressing and vacuum-sintering method.
In addition to above-mentioned new steel bonded carbide, Japanese some companies also utilize a variety of hard compounds (such as TiC, VC, Cr3C2, SiC, ZrC, AlN etc.) and its mixed compound make hard phase, make binding agent with various steel or ferrous alloy, Develop some advanced composite material (ACM)s.
Meanwhile, people are also constantly seeking the combination of new hard phase and new Binder Phase, to develop with optimal The MC type particulate reinforced composites of tissue and performance.In steel-bonded carbide, the hard particulate carbide species as wear-resistant phase Compare many, there is the ceramic particles such as WC, TiC, Cr7C3, NbC, VC, SiC and alloy carbide and cementite.MC type carbide Thermodynamic stability putting in order from high to low be:TiC > NbC > VC > WC, putting in order for its hardness be:TiC > VC > WC > NbC.It is known that TiC is poor with Fe intermiscibilities.Sintering temperature is high, and strength ratio WC is poor, and its advantage is light weight, thermally-stabilised Property, frictional property are good;WC high temperature is bad with Fe intermiscibilities, is easily dissolved in Fe during high temperature, and high high-temp stability, calorific intensity are poor, Separated out in cooling procedure so as to form bridge joint, deteriorate the mechanical performance of alloy;As carbide V element, with Ti elements are similar to, and V is also a kind of very active alloying element, first with C, N etc. to have very strong affinity.The parent of V element and C With power more than Cr elements and the affinity of C, two kinds of stable carbides of VC and V2C are easily formed.In carbide ceramics, VC's is hard Degree highest, and have good heat endurance, it is a kind of preferable hard enhancing phase.
VC extremely stablizes, and is generally distributed in alloy substrate with tiny graininess, one side crystal grain thinning, improves matrix The intensity and wearability of alloy;On the other hand, the creep rupture strength and the drag to creep of matrix are increased.The microhardness of VC It is very high, more than 2800MPa is reached, it is a kind of wear-resistant phase of preferable alloy carbide.Take VC as the Novel steel knot hard for strengthening phase Alloy, VC and Fe has extraordinary intermiscibility, and the two joint interface is good, and high high-temp stability, red hardness are good, is TiC, WC Reinforcement is substituted well.Also between TiC and WC, vanadium can shape in Hi-Stren steel for the fusing point and thermal coefficient of expansion of VC Precipitated into tiny vanadium carbide and effectively facilitate the crystal grain refinement of steel and strengthen;Vanadium carbide mutually can pinning dislocation and crystal boundary, obstruction position Wrong and crystal boundary migration, improves the intensity of steel;The presence of vanadium carbide phase simultaneously can also improve the recrystallization temperature of material and high temperatures Energy.Existing research shows:Vanadium carbide is added in steel can also improve wearability, corrosion resistance, toughness, ductility and the hardness of steel And the comprehensive mechanical performance such as thermal fatigue resistance, and make steel that there is good solderability, and play elimination field trash and extend etc. and make With.Therefore, vanadium carbide is used widely in steel.
Meanwhile, this novel hard alloy it is alternative traditional in industries such as automobile, metallurgy, mine, building materials and moulds High-abrasive material, increases substantially parts service life, economizes on resources, with good economic results in society.Additionally, with work The wilderness demand of industry production and inevitably artificial waste, China or even worldwide W, Co resource are quite poor Weary, price rises steadily, and each national capital Efforts To Develop seeks the research and development of the substitute material of W, Co.And China V ore resources are abundant, Replace W with V has feasibility very high in resource.Therefore, VC bases steel bonded carbide either engineer applied is researched and developed Aspect, or be all significant in terms of Technological Economy.
VN is a kind of new microalloying additive, with outstanding alloying performance.V element in vanadium nitride Worked with the carbon and nitrogen in steel, generate hard metal carbides and nitride molecule.These compounds are played in steel The effect of crystal grain thinning and precipitation hardening, can optimize the performance of steel, can obviously improve the tissue of V-bearing microalloyed steel, carry The intensity of Gao Gang, toughness and wearability, corrosion resistance and thermal fatigue resistance, and steel is possessed excellent weldability. Alloy of vanadium nitride additive is more beneficial for vanadium carbide, the precipitation of vanadium nitride in steel, so that more effectively reinforcing and crystal grain thinning.With Compared using vanadium iron, alloy of vanadium nitride additive improves the service efficiency of vanadium, allow steel manufacturing enterprise save 20%~ 40% vanadium consumption, makes steel user save 10%~15% rolled steel dosage.
The method mainly powder metallurgy process of this kind of material, including compressing, cold isostatic compaction, note are prepared at present Shaping etc. is penetrated, vacuum-sintering is then carried out as final shaping.Larger part is prepared using compressing and cold isostatic compaction Required larger pressure and it is helpless, the parts for preparing complicated shape are more difficult, simultaneously for prepare ceramic crystalline grain size compared with When small and content composite higher, shape more difficult and crystal grain and easily grow up;Produce this kind of using ejection forming method The small parts of material, but this kind of method is not suitable for the preparation of the parts of large-size, while adulterated in this kind of technique Colloid is more, and usually time is more long, while the consistency of blank of material is relatively low, is unfavorable for quickly carrying out carrying for production and consistency It is high;Such material also is prepared using Self- propagating Sintering Synthetic reaction method, but the material for preparing often has relatively low densification Degree.Some using HIP sintering etc. as final sintering process, but it is costly.
The content of the invention
Exist in terms of shaping and sintering the present invention be directed to existing steel bonded carbide and be difficult to quick, economic preparation The difficulty of the aspects such as crystallite dimension is smaller and content is higher, large-size, complicated shape part, there is provided one kind prepare large scale, Complicated shape and simple production process, the preparation side of lower-cost VC-VN cold work die steel in high alloy through base steel bonded carbide Method.
The present invention provides a kind of preparation method of VC-VN cold work die steel in high alloy through base steel bonded carbide, including following Process:
(1)Proportionally weigh 20~50% carbonization vanadium powders, 2~10% nitridation vanadium powder and 28~58% cold work die steel in high alloy through bases Body powder, 0.03~0.3% Ce, 0.05~0.3% Nb, 0.1~0.8% SiMgRe, 0.2~0.6% graphite powder, 5~10% Carbonyl iron dust, the powder and rare earth, Nb powder are put into ball mill and are mixed and crushed, wherein addition absolute ethyl alcohol is Process control agent, mixed powder is put into vacuum drying chamber and is dried, standby after drying;
(2)Organic monomer and initiator are added in solvent and prepare premixed liquid;
(3)Dry mixed powder is added in premixed liquid and stirred, it is slurry that percentage by volume is added in whipping process The oleic acid of the 1~3% of material, to improve slurry fluidity and dispersiveness;
(4)Add catalyst and pH adjusting agent and stir, obtain slurry;Slurry is injected into mould and with vacuumizing or shake Method bubble removing, slurry curing shaping, the demoulding after the reaction regular hour obtains final product base substrate;
(5)Base substrate is put into vacuum drying chamber and is dried, dried base substrate is carried out into degumming and final sintering;
First, described cold work die steel in high alloy through matrix includes that one of Cr12, Cr12MoV, Cr12Mo1V1 are planted;
Second, described organic monomer is hydroxy-ethyl acrylate, solvent is toluene, initiator is benzoyl peroxide;Wherein have The volume ratio of machine monomer and solvent is 1:2~2:1, the content of initiator is 0.6~1.5 g in every 100 ml premixed liquids;
3rd, mixed powder percentage by volume in the slurry is 40~60%;
4th, initiator used is dimethylaniline, and the percentage that addition accounts for slurry volume is 0.1~0.2%;
5th, pH adjusting agent used is ammoniacal liquor, and regulation pH value is 7~8;
6th, degumming and sintering carry out integral sintering using vacuum sintering furnace, and technique is:Base substrate is incubated 1 at 400~500 DEG C ~3 h carry out degumming, and being incubated 1~2h at 1400~1450 DEG C is finally sintered.
Beneficial effect
Beneficial effects of the present invention are:
1st, the invention allows to quick, economic preparation crystallite dimension is smaller, the part of large-size, complicated shape.
2nd, Gelcasting Technique be in low viscosity, the powder-solvent concentrate suspension of solid volume fraction high, plus Enter organic monomer, organic monomer chemical crosslinking polymerization or physics in then making suspended substance in the presence of catalyst and initiator Tridimensional network is cross-linked into, so that suspended substance in-situ solidifying is molded, is finally discharged colloid a small amount of in base substrate, then carry out Sintering obtains compact components.Gel casting can reduce the quantity of gross blow hole in base substrate, and pore-size distribution is more uniform, improves The uniformity of base substrate;Gel casting cycle is short, the structure and even density of product are not in the segregation of particle, material It is stable and reliable for performance.Additionally, gel casting to mould without specific requirement, it is considered to be improve reliability of material, prepare One of large scale, most effectual way of complicated form part.The reunion of particle can be efficiently controlled due to gel casting, is made For the base substrate for going out structure and even density, so as to obtain high performance sintered body, the use reliability of material is improved.It is simultaneously solidifying Limitation of the glue casting to ceramic crystalline grain size and content is smaller, makes it use scope wider.During gel casting Can also by controlling the parameter of each additive, and then control solidification time and body crack defects etc., so that it is different to meet preparation The demand of parts.Low pressure sintering process can promote the mobility of liquid phase in liquid sintering process, can shorten sintering time, have Beneficial to the uniformity and compactness of tissue, moreover it is possible to ceramic phase and binder alloy boundary strength are improved, so as to improve the performance of material.
3rd, the present invention mutually manufactures new steel bonded carbide by enhancing of VC, and VC and Fe has extraordinary intermiscibility, two Person's joint interface is good, and high high-temp stability, red hardness are good, in carbide ceramics, the hardness highest of VC, and have well Heat endurance, is a kind of preferable hard enhancing phase, is that TiC, WC substitute reinforcement well.Vanadium carbide mutually can pinning dislocation with Crystal boundary, hinders dislocation and crystal boundary migration, improves the intensity of steel;The presence of vanadium carbide phase simultaneously can also improve the recrystallization temperature of material Degree and high-temperature behavior.Doing hard phase using vanadium carbide can also improve wearability, corrosion resistance, toughness, ductility and the hardness of steel And the comprehensive mechanical performance such as thermal fatigue resistance, and make steel that there is good solderability, and play elimination field trash and extend etc. and make With.Can be widely applied to the adverse circumstances of heavy duty, high speed, dry sliding friction or high temperature and high speed friction.
4th, to prevent serious adhesive wear, more preferably self-lubricating effect is obtained, the present invention is by steel bonded carbide The graphite of the middle certain content of addition, makes to contain the micro- graphite-phase of many self-lubricatings in materials microstructure, makes the friction of hard alloy Coefficient is greatly improved, so that friction factor reduction.
5th, in order to adjust the granularmetric composition of compound, improve suppression performance, greatly improve shaping density, the present invention A certain proportion of carbonyl iron dust is added in reduced iron powder.Substituting reduced iron powder with carbonyl iron dust can improve powder forming Can, make green density higher, acceleration of sintering process reduces sintering temperature.Make steel knot of the invention by adding carbonyl iron dust The mechanics of hard alloy is significantly improved, and hardness brings up to 81.8HRA by 77.5HRA, bending strength by 1123MPa or to 1447MPa。
6th, the present invention can more effectively be strengthened and crystal grain thinning by adding VN, and the performance of optimized alloy can substantially change The tissue of kind steel bonded carbide, improves intensity, toughness and wearability, corrosion resistance and the thermal fatigue resistance of alloy, and makes Steel possess excellent weldability energy.20%~40% vanadium consumption can be saved, steel user is saved 10%~15% steel Timber-used amount.
7th, the present invention is by adding Ce, SiMgRe, and makes Ce, SiMgRe powder content between 0.2% and 0.5%, can rise To rare earth reinforced effect.Because Ce, SiMgRe chemical property are active, in ball milling and sintering process, RE has to alloy powder Obvious deoxidation and carbon effect is protected, contribute to improving for wetability between different constituent elements, so as to be conducive to densification process, Reach the purpose for reducing porosity so that the porosity in steel bonded carbide is reduced, and the reduction of porosity will be helped In the raising of plasticity and bending strength.At a sintering temperature, rare earth is gathered in TiC particle surfaces, its surface is reduced, and hinders TiC crystallization of the dissolution and precipitation processes in the liquid phase, suppress growing up for TiC crystal grain;Ce, SiMgRe can be with metal dust interfaces simultaneously On impurity and oxide-film effect, play a part of to purify interface, the segregation of S, P, Sb in crystal boundary can be suppressed, play deoxidation, de- Sulphur, crystal grain thinning and improve Liquid phase flowability and wetability etc. and act on.So as to improve the performance of alloy material.
And because SiMgRe may also operate as inoculation(effect) in the alloy, the alloying pellet in matrix material is obtained ball Shape, so as to improve the toughness of Steel-bonded Cemented Carbide.Therefore intensity, the toughness of steel bonded carbide of the invention It is improved with consistency, bending strength can reach more than 1700MPa, consistency reaches more than 97.4%.
The present invention is by adding Ce, Nb, SiMgRe, it is suppressed that crystal grain is grown up, and plays a part of dispersion-strengtherning.
Specific embodiment
Embodiment 1:Weigh VC powder, 2%VN powder and 0.2% Ce that mass fraction is 50%, 0.2% Nb, 0.25% SiMgRe, 0.3% graphite powder, 5% carbonyl iron dust, Cr12 cold work die steel in high alloy through matrix material powder, by the powder and dilute Soil, Nb powder are put into ball mill and are mixed and crushed, wherein addition absolute ethyl alcohol is process control agent, wet mixed powder are put To enter be dried in vacuum drying chamber, it is standby after drying;According to volume ratio 1:1 measures organic monomer hydroxy-ethyl acrylate and solvent Toluene prepares premixed liquid, to the benzoyl peroxide that 1.2 g/100 ml are added in premixed liquid and stirs;Will be dry mixed Close powder to be added in premixed liquid, while 2% oleic acid being added dropwise and stirring, form slurry;To two of addition 0.15% in slurry Methylaniline and add ammoniacal liquor regulation PH be 7;Base substrate is put into vacuum sintering furnace after removing bubble with vacuumizing method is taken off Glue is sintered with final, and technique is:Being incubated 2 h at 500 DEG C carries out degumming, and being incubated 2h at 1450 DEG C is finally sintered;Finally Furnace cooling obtains steel bonded carbide part.
Embodiment 2:Weigh VC powder, 5%VN powder and 0.2% Ce that mass fraction is 60%, 0.2% Nb, 0.25% SiMgRe, 0.4% graphite powder, 7% carbonyl iron dust, Cr12MoV cold work die steel in high alloy through matrix material powder, by the powder and Rare earth, Nb powder are put into ball mill and are mixed and crushed, wherein addition absolute ethyl alcohol is process control agent, by wet mixed powder It is put into vacuum drying chamber and is dried, it is standby after drying;According to volume ratio 1:2 measure organic monomer hydroxy-ethyl acrylate and molten Agent toluene prepares premixed liquid, to the benzoyl peroxide that 0.6 g/100 ml are added in premixed liquid and stirs;Will be dry Mixed powder is added in premixed liquid, while 1% oleic acid being added dropwise and stirring, forms slurry;To two of addition 0.1% in slurry Methylaniline and add ammoniacal liquor regulation PH be 7.5;Base substrate is put into vacuum low-pressure sintering furnace after removing bubble with vacuumizing method Degumming and final sintering are carried out, technique is:Being incubated 1 h at 500 DEG C carries out degumming, and being incubated 2h at 1400 DEG C is finally burnt Knot;Last furnace cooling obtains the part of steel bonded carbide.
Embodiment 3:Weigh VC powder, 8%VN powder and 0.25% Ce that mass fraction is 40%, 0.25% Nb, 0.3% SiMgRe, 0.55 graphite powder, 8% carbonyl iron dust, Cr12Mo1V1 cold work die steel in high alloy through matrix material powder, by the powder It is put into ball mill with rare earth, Nb powder and is mixed and crushed, wherein addition absolute ethyl alcohol is process control agent, wet mixing is closed Powder is dried in being put into vacuum drying chamber, standby after drying;According to volume ratio 2:1 measure organic monomer hydroxy-ethyl acrylate and Solvent toluene prepares premixed liquid, to the benzoyl peroxide that 1.5 g/100 ml are added in premixed liquid and stirs;By drying Mixed powder be added in premixed liquid, while be added dropwise 3% oleic acid and stir, formed slurry;To addition 0.2% in slurry Dimethylaniline and add ammoniacal liquor regulation PH be 8;Base substrate is put into vacuum low-pressure sintering furnace after removing bubble with vacuumizing method Degumming and final sintering are carried out, technique is:Being incubated 3h at 400 DEG C carries out degumming, and being incubated 1h at 1450 DEG C is finally sintered; Last furnace cooling obtains the part of steel bonded carbide.
Embodiment 4:Weigh VC powder, 10%VN powder and 0.3% Ce that mass fraction is 30%, 0.3% Nb, 0.5% SiMgRe, 0.6% graphite powder, 10% carbonyl iron dust, Cr12Mo1V1 cold work die steel in high alloy through matrix material powder, by the powder Last being put into ball mill with rare earth, Nb powder is mixed and is crushed, wherein addition absolute ethyl alcohol is process control agent, by wet mixing Close during powder is put into vacuum drying chamber and be dried, it is standby after drying;According to volume ratio 2:1 measures organic monomer hydroxy-ethyl acrylate Premixed liquid is prepared with solvent toluene, to the benzoyl peroxide that 1.5 g/100 ml are added in premixed liquid and is stirred;Will be dry Dry mixed powder is added in premixed liquid, while 3% oleic acid being added dropwise and stirring, forms slurry;To adding 0.2% in slurry Dimethylaniline and add ammoniacal liquor regulation PH be 8;Base substrate is put into vacuum low-pressure sintering furnace after removing bubble with vacuumizing method In carry out degumming and final sintering, technique is:Being incubated 3h at 400 DEG C carries out degumming, and being incubated 1h at 1450 DEG C is finally burnt Knot;Last furnace cooling obtains the part of steel bonded carbide.

Claims (7)

1. a kind of preparation method of VC-VN cold work die steel in high alloy through base steel bonded carbide, it is characterised in that including following step Suddenly:
(1)Proportionally weigh 30~60% carbonization vanadium powder and 33~60% cold work die steel in high alloy through matrix powders, 0.03~0.3% Ce, 0.05~0.3% Nb, 0.1~0.8% SiMgRe, 0.2~0.6% graphite powder, 5~10% carbonyl iron dusts, by the powder Last being put into ball mill with rare earth, Nb powder is mixed and is crushed, wherein addition absolute ethyl alcohol is process control agent, will be mixed Powder is dried in being put into vacuum drying chamber, standby after drying;
(2)Organic monomer and initiator are added in solvent and prepare premixed liquid;
(3)Dry mixed powder is added in premixed liquid and stirred, it is slurry that percentage by volume is added in whipping process The oleic acid of the 1~3% of material, to improve slurry fluidity and dispersiveness;
(4)Add catalyst and pH adjusting agent and stir, obtain slurry;By the slurry solidifying mould of injection note and with vacuumizing or Lash method bubble removing, slurry curing shaping, the demoulding after the reaction regular hour obtains final product base substrate;
(5)Base substrate is put into vacuum drying chamber and is dried, dried base substrate is carried out into degumming and final sintering.
2. preparation method according to claim 1, it is characterised in that described cold work die steel in high alloy through matrix includes One of Cr12, Cr12MoV, Cr12Mo1V1 are planted.
3. preparation method according to claim 1, it is characterised in that described organic monomer is hydroxy-ethyl acrylate, solvent For toluene, initiator are benzoyl peroxide;Wherein the volume ratio of organic monomer and solvent is 1:2~2:1, every 100 ml premixs The content of initiator is 0.6~1.5 g in liquid.
4. preparation method according to claim 1, it is characterised in that mixed powder percentage by volume in the slurry is 40~ 60%。
5. preparation method according to claim 1, it is characterised in that initiator used is dimethylaniline, addition accounts for slurry The percentage for expecting volume is 0.1~0.2%.
6. preparation method according to claim 1, it is characterised in that pH adjusting agent used is ammoniacal liquor, regulation pH value is 7~ 8。
7. preparation method according to claim 1, it is characterised in that degumming and sintering carry out one using vacuum sintering furnace Change sintering, technique is:Base substrate is incubated 1~3 h and carries out degumming at 500 DEG C, and being incubated 1~2h at 1400~1450 DEG C is carried out finally Sintering.
CN201710074660.8A 2017-02-11 2017-02-11 A kind of preparation method of VC VN cold work die steel in high alloy through base steel bonded carbide Pending CN106811652A (en)

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Application publication date: 20170609