CN103045887B - Fine pure plate-shaped grain cemented carbide and preparation method thereof - Google Patents
Fine pure plate-shaped grain cemented carbide and preparation method thereof Download PDFInfo
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- CN103045887B CN103045887B CN201310017459.8A CN201310017459A CN103045887B CN 103045887 B CN103045887 B CN 103045887B CN 201310017459 A CN201310017459 A CN 201310017459A CN 103045887 B CN103045887 B CN 103045887B
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Abstract
The invention discloses a fine pure plate-shaped grain cemented carbide and a preparation method thereof, wherein the microstructure of the carbide is composed of a fine pure plate-shaped crystalline WC hard phase and an alloy bonding phase which is uniformly distributed; in the alloy, the regular triangle average side length of a regular triangular prism-shaped WC plate-shaped grain is shorter than 0.8microns, and the average height of the prism is lower than 0.25microns; WC-Co nano composite powder with WC grain size lower than 100nm is taken as a raw material; the alloy contains a Cr+V+rare earth trinary grain growth regulating agent, the additive amounts of the Cr, V and rare earth respectively account 5-8wt%, 3-4wt% and 0.3-0.6wt% of Co in the alloy; the additive amounts of the Cr and V are measured in terms of Cr3C2 and VC, and the additive amount of the rare earth is measured in terms of oxide; a rolling wet-grinding process is adopted to prepare an alloy mixing material, and the wet-grinding duration is 40-60hours and ball-to-power mass ratio is at (4:1)-(6:1); and a pressure sintering process is adopted to sinter the alloy, and the sintering temperature is at 1360-1400 DEG C.
Description
Technical field
The present invention relates to a kind of tiny pure tabular cemented carbide, the invention still further relates to the preparation method of this tiny pure tabular cemented carbide.
Background technology
Tabular cemented carbide refers in alloy the Wimet with the brilliant WC grain volume of feature of tabular and ratio (the being called for short plate-like WC grain volume fraction) > 20% of WC grain cumulative volume in alloy.In Japan, tabular cemented carbide is also referred to as sheet cemented carbide or disk like cemented carbide.Tabular cemented carbide is divided into the pure tabular cemented carbide containing tabular cemented carbide and plate-like WC grain volume fraction > 80%.The Hardness and toughness of conventional rigid alloy is a pair conflicting parameter, and improving hardness will to sacrifice toughness for cost, and vice versa.Pure tabular cemented carbide has the feature such as high rigidity, high tenacity.Because crystallization is more complete, under the condition that hardness is suitable, pure tabular cemented carbide has the wear resistance higher compared with conventional rigid alloy.
Preparation method about tabular cemented carbide all has report both at home and abroad.The W raw material that contains of current preparation tabular cemented carbide is mainly divided into 3 classes, i.e. WC powder raw material; W
xco
yc powder stock and simple substance W powder stock.Chinese patent CN101117673A and CN101376931A discloses " preparation method containing the Wimet of (bulk) slab-shaped tungsten carbide crystal grain ".The method is with slab-shaped tungsten carbide monocrystalline for crystal seed, WC and Co is raw material, adopts high-energy ball milling to prepare compound.In alloy, the plate-like WC grain crystal grain length of side is generally at 3 ~ 8 μm, and crystal grain is comparatively thick, and in alloy, WC grain is the brilliant duplex grain structure formed with conventional die of tabular, and namely alloy is for containing tabular cemented carbide.Chinese patent CN1068067C discloses " Wimet and preparation method thereof containing plate crystal tungsten carbide ".The method adopts two-step process, first adopts W, C, Co etc. to be raw material, prepares platelet WC and forms powder (as Co
3w
3c, Co
6w
6c etc.); Adopting platelet WC to form powder is again that alloy prepared by raw material, and in alloy, platelet WC volume fraction is not less than 20%.Chinese patent CN1990888A discloses " having the manufacture method of the tungsten-cobalt hard alloy of fibrous WC crystal ".The nanocrystalline W supersaturated solid solution containing Co, C that the method adopts high-energy ball milling to prepare is raw material, but does not announce weave construction and the performance of alloy.Pei Yanbin, waits and reports " W – Co – CNT (carbon nano-tube) reaction sintering prepares height-oriented Wimet " (Materials Science and Engineering of Powder Metallurgy, 2005, Vol10, No3, P160 – 165).This report adopts micron order W powder, Co powder and multiple-wall carbon nanotube (diameter 10nm) to be raw material, long-time wet-grinding technology and relative device (72h) is adopted to prepare compound, realize the preferred orientation of alloy structure perpendicular to (0001) crystal face of pressing direction by the template action of CNT (carbon nano-tube), the method is difficult to the effective control realizing alloy uniform texture.Wu Enxi, etc. reporting " research containing plate-like shape WC grains Wimet preparation method " (Wimet, 2006, Vol23, No2, P75 – 78), KINOSHITA S etc. reports " adopting W and C to be the Forming Mechanism of the tabular triangular prism WC grain that WC – Co Wimet camber prepared by raw material aligns " (Mechanisms for formation of highlyoriented plate – like triangular prismatic WC grains in WC – Cobase cemented carbides prepared from W and C instead of WC.Journal of the Japan Society of powder and Powder Metal lurgy, 2001, Vol48, No1, P51 – 60).Comprise these 2 sections to be reported in other interior similar reports and all to adopt micron order W powder, Co powder and flake graphite in powder to be raw material, the transformation of W polyhedron to W tabular body is realized by carrying out flaky process to W powder, by improving sintering temperature and extending sintering time preparation containing tabular cemented carbide, WC grain prepared by the method is thick, be difficult to the Effective Regulation realizing the brilliant ratio of WC tabular in alloy, and plate-like WC grain crystal grain has the preferred orientation feature of (0001) crystal face perpendicular to pressing direction, thus result in the anisotropy of alloy property.Chinese patent CN102061401B discloses " a kind of preparation method with the two high-performance WC base cemented carbide of high hardness high toughness ".The method provides a kind of can prepare the preparation method with high crystalline perfection, pure tabular crystal structure, isotropic WC base cemented carbide, and its reasonable offer raw material is W nanopowder and Nano graphite powder.
The tabular cemented carbide reported at present all has the feature of the brilliant coarse grains of tabular, and usually there is the defects such as alloy bonding Entropy density deviation uniformity coefficient is not good enough, therefore the bending strength of alloy is lower, usual < 2500MPa.Pure tabular cemented carbide can realize " two high " characteristic that alloy has high hardness high toughness, and the ultra-fine cemented carbide of alloy grain degree < 0.5 μm can realize " two high " characteristic that alloy has high strength and high hardness.The maximum weak point of ultra-fine cemented carbide is that fracture toughness property is on the low side, Palmqvist fracture toughness property K
1cusual < 10.5MPam
1/2.While acquisition high strength and high hardness, put forward the main direction of studying that heavy alloyed fracture toughness property is Wimet.Reported at present about the regulate and control method all not relating to plate-like WC grain grain size in the preparation method of pure tabular cemented carbide, there is no the report of the tiny pure tabular cemented carbide with high strength and high hardness high tenacity " three is high " characteristic at present.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of tiny pure tabular cemented carbide with high strength, high rigidity and high tenacity.
Second technical problem to be solved by this invention is to provide the preparation method with the Wimet of high strength, high rigidity and high tenacity that a kind of energy preparation has the heterogeneous microstructure characteristic such as high crystalline perfection, tiny pure tabular crystal structure.
In order to solve above-mentioned first technical problem, tiny pure tabular cemented carbide provided by the invention, containing Cr+V+ rare earth three constituent element grain growing adjusting control agent in alloy, the WC – Co nano composite powder adopting WC grain degree < 100nm is raw material, described Cr, V and the addition of rare earth control accounting for 5% ~ 8%, 3% ~ 4% and 0.3% ~ 0.6% of Co massfraction in alloy respectively, and described Cr and V addition is with Cr
3c
2, VC meter, described rare earth addition is with oxide basis.
Described rare earth is the one in the common rare earth element of La, Ce and Y.
In order to solve second technical problem, the preparation method of tiny pure tabular cemented carbide provided by the invention, the WC – Co nano composite powder adopting WC grain degree < 100nm is raw material, using Cr+V+ rare earth three constituent element additive as grain growing adjusting control agent; In order to prevent the formation containing grain growing adjusting control agent third phase, described Cr, V and the addition of rare earth control accounting for 5% ~ 8%, 3% ~ 4% and 0.3% ~ 0.6% of Co massfraction in alloy respectively, and the addition of described Cr and V is with Cr
3c
2, VC meter, the addition of described rare earth is with oxide basis; In order to prevent the lattice distortion that powder transition is broken and appearance is serious, adopt rolling wet-grinding technology and relative device to prepare alloy compound, control the wet-milling time between 40 ~ 60h, ball material mass ratio is between 4:1 ~ 6:1; Adopt pressure sintering technique alloy to sinter, in order to prevent causing the misgrowth of WC grain and the uneven of alloy microstructure because sintering temperature is too high, sintering temperature controls between 1360 ~ 1400 DEG C; In order to realize the full densification of alloy, adopt pressure sintering technique alloy to sinter, sintered heat insulating stage sintering oven internal pressure > 5MPa, pressure sintering furnace can select 6MPa or 10MPa pressure sintering furnace two kinds of type of furnaces.
Described WC – Co nano composite powder adopts the preparation of solution spray conversion-in-situ reducing carbonization technique, before solution atomization, composite powder constituent element element reaches molecular level mixing in the solution, and described Cr+V+ rare earth three constituent element grain growing adjusting control agent adds in WC – Co nano composite powder preparation process; In WC – Co nano composite powder preparation process, add fashionable, described Cr, V and rare earth adds with salts solution form, described rare earth is the one in the common rare earth element of La, Ce and Y.
Described grain growing adjusting control agent Cr, V and rare earth added in the wet-milling stage; Add fashionable in the wet-milling stage, described Cr, V are with Cr
3c
2, VC form adds, described rare earth adds with salts solution form, and described rare earth is the one in the common rare earth element of La, Ce and Y.
Described rolling wet-grinding technology and relative device refers to and adopts roller ball mill; In order to prevent the oxidation of nano-powder in wet-milling process, improve the grinding distribution efficiency of wet-milling, in wet-milling process, add the macromolecular compound containing paraffin and PEG having oxidation inhibitor, dispersion agent and binder function concurrently accounting for alloy compound total mass mark 2% ~ 3%, wherein the mass ratio of paraffin and PEG is 1:1; Wet grinding media be can dissolve paraffin and PEG simultaneously mix organic medium.
The present invention does not adopt high-energy ball milling, does not adopt the high temperature sintering methods improving sintering temperature to prepare alloy.
The tiny pure tabular cemented carbide adopting technique scheme to prepare, has high strength and high hardness high tenacity " three is high " characteristic.The preparation method of tiny pure tabular cemented carbide, utilizes the high uniformity of Co distribution in WC – Co nano composite powder, realizes the regulation and control to WC solution modeling behavior uniformity coefficient in Co Binder Phase under grain growing adjusting control agent environment.Grain growing adjusting control agent Cr+V+ rare earth is added by combining, change in alloy and dissolve the composition of group member and the distribution of interface element in liquid Co, realize effective suppression of WC grain abnormal growth in the regulation and control of liquid towards Co/WC interfacial energy and alloy sintering process.Utilize that the high solution modeling of nano-powder is active, the high uniformity characteristic of solution modeling behavior and the controllable characteristic of Co/WC interfacial energy in WC – Co nano composite powder, realize the controllable growth of high crystalline perfection under grain growing high-drag environment, tiny pure plate-like WC grain crystal grain.
In sum, the present invention has high crystalline perfection, tiny pure tabular crystal structure, isotropic WC base cemented carbide a kind of can preparation, realizes tiny pure tabular cemented carbide of " three is high " characteristic of alloy and preparation method thereof.
Accompanying drawing explanation
Fig. 1 is WC – 12Co – 0.96Cr
3c
2– 0.36VC – 0.072La
2o
3the 3D high resolution scanning electromicroscopic photograph on cemented carbide sintered body surface;
Fig. 2 is WC – 12Co – 0.6Cr
3c
2– 0.48VC – 0.036Y
2o
3the high resolution scanning electromicroscopic photograph of Wimet polishing section.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
Employing WC grain degree is the WC – 12Co nano composite powder of 90nm, Cr
3c
2, VC and anhydrous nitric acid lanthanum be raw material, preparation WC – 12Co – 0.96Cr
3c
2– 0.36VC – 0.072La
2o
3wimet.Rolling wet-grinding technology and relative device is adopted to prepare alloy compound, the wet-milling time is 40h, ratio of grinding media to material is 5:1, in wet-milling process, add the paraffin that accounts for alloy compound total mass mark 1.5% and the PEG4000 accounting for alloy compound total mass mark 1.5%, adopting volume ratio to be the alcohol of 1:1 and normal hexane mixing solutions is wet grinding media.Adopt conventional moulded technique compacting alloy sample, in 6MPa pressure sintering furnace, alloy sample sinters, and sintering temperature is 1380 DEG C, and soaking time is 1h, and holding stage furnace pressure is 5.6MPa.Fig. 1 is the 3D high resolution scanning electromicroscopic photograph of alloy sintering surface.Can find out, clearly, have good crystalline perfection, in alloy microstructure, WC grain (0001) crystal face (equilateral triangle) orientation has randomness for alloy intermediate cam rib WC grain smooth in appearance, densification, corner angle.Measuring result shows, in alloy, the equilateral triangle average side length of regular triangular prism shaped WC plate-like grain is 0.6 μm, prism center line average is 0.18 μm, alloy bending strength is 4161MPa, alloy Rockwell hardness is 92.5HRA, alloy Vickers' hardness is 1680HV30, and alloy Palmqvist fracture toughness property is 12.03MPam
1/2.The brilliant ultra-fine cemented carbide of the non-tabular of the tradition that alloy Palmqvist fracture toughness property is suitable compared with hardness improves about 20%.
Embodiment 2:
Employing WC grain degree is the WC – 12Co nano composite powder of 90nm, Cr
3c
2, VC and anhydrous nitric acid yttrium be raw material, preparation WC – 12Co – 0.6Cr
3c
2– 0.48VC – 0.036Y
2o
3wimet.Rolling wet-grinding technology and relative device is adopted to prepare alloy compound, the wet-milling time is 60h, ratio of grinding media to material is 6:1, in wet-milling process, add the paraffin that accounts for alloy compound total mass mark 1.0% and the PEG4000 accounting for alloy compound total mass mark 1.0%, adopting volume ratio to be the alcohol of 1:1 and normal hexane mixing solutions is wet grinding media.Adopt conventional moulded technique compacting alloy sample, in 10MPa pressure sintering furnace, alloy sample sinters, and sintering temperature is 1360 DEG C, and soaking time is 1h, and holding stage furnace pressure is 9.5MPa.Alloy sintering surface 3D microtexture measuring result shows, in alloy, the equilateral triangle average side length of regular triangular prism shaped WC plate-like grain is 0.56 μm, prism center line average is 0.17 μm, alloy bending strength is 4126MPa, alloy Rockwell hardness is 92.6HRA, alloy Vickers' hardness is 1700HV30, and alloy Palmqvist fracture toughness property is 12.11MPam
1/2.Fig. 2 is the high resolution scanning electromicroscopic photograph of alloy polishing section.Can find out, in alloy, WC grain presents rectangular pattern mostly.Because in alloy, the distribution of tabular crystalline substance has isotropic character, the pattern degree of irregularity of regular triangular prism shaped WC plate-like grain on polishing section increases.The brilliant ultra-fine cemented carbide of the non-tabular of the tradition that alloy Palmqvist fracture toughness property is suitable compared with hardness improves about 20%.
Embodiment 3:
Employing WC grain degree is the WC – 12Co – 0.72Cr of 80nm
3c
2– 0.36VC – 0.054CeO
2nano composite powder is raw material, preparation WC – 12Co – 0.72Cr
3c
2– 0.36VC – 0.054CeO
2wimet.Rolling wet-grinding technology and relative device is adopted to prepare alloy compound, the wet-milling time is 50h, ratio of grinding media to material is 4:1, in wet-milling process, add the paraffin that accounts for alloy compound total mass mark 1.2% and the PEG4000 accounting for alloy compound total mass mark 1.2%, adopting volume ratio to be the alcohol of 1:1 and normal hexane mixing solutions is wet grinding media.Adopt conventional moulded technique compacting alloy sample, in 6MPa pressure sintering furnace, alloy sample sinters, and sintering temperature is 1400 DEG C, and soaking time is 1h, and holding stage furnace pressure is 5.6MPa.Alloy sintering surface 3D microtexture measuring result shows, in alloy, the equilateral triangle average side length of regular triangular prism shaped WC plate-like grain is 0.55 μm, prism center line average is 0.16 μm, alloy bending strength is 4201MPa, alloy Rockwell hardness is 92.6HRA, alloy Vickers' hardness is 1715HV30, and alloy Palmqvist fracture toughness property is 12.26MPam
1/2.The brilliant ultra-fine cemented carbide of the non-tabular of the tradition that alloy Palmqvist fracture toughness property is suitable compared with hardness improves about 20%.
Claims (1)
1. one kind tiny pure tabular cemented carbide, it is characterized in that: containing Cr+V+ rare earth three constituent element grain growing adjusting control agent in alloy, the WC – Co nano composite powder adopting WC grain degree < 100nm is raw material, described Cr, V and the addition of rare earth control accounting for 5% ~ 8%, 3% ~ 4% and 0.3% ~ 0.6% of Co massfraction in alloy respectively, and described Cr and V addition is with Cr
3c
2, VC meter, described rare earth addition is with oxide basis, described WC – Co nano composite powder adopts the preparation of solution spray conversion-in-situ reducing carbonization technique, before solution atomization, composite powder constituent element element reaches molecular level mixing in the solution, described Cr+V+ rare earth three constituent element grain growing adjusting control agent adds in WC – Co nano composite powder preparation process, add fashionable in WC – Co nano composite powder preparation process, described Cr, V and rare earth add with salts solution form, and described rare earth is the one in La, Ce and Y; This tiny pure tabular cemented carbide has high strength and high hardness high tenacity " three is high " characteristic.
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| CN103710604B (en) * | 2013-12-27 | 2015-11-18 | 株洲硬质合金集团有限公司 | A kind of Wimet, preparation method and application thereof |
| CN104120322B (en) * | 2014-08-01 | 2016-08-17 | 中南大学 | A kind of hard alloy and the method improving its PVD coating film-substrate cohesion |
| US11060155B2 (en) * | 2016-04-01 | 2021-07-13 | Pramet Tools, S.R.O. | Surface hardening of cemented carbide body |
| CN106086571B (en) * | 2016-07-15 | 2017-12-01 | 中南大学 | A kind of high-performance WC-Co regeneration hard alloy and preparation method thereof |
| CN110616345B (en) * | 2018-06-19 | 2020-11-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Fine-grain hard alloy and preparation method thereof |
| CN110629060B (en) * | 2018-06-25 | 2020-11-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Grain refiner containing rare earth elements and preparation method and application thereof |
| CN109280798B (en) * | 2018-11-28 | 2020-01-17 | 湖南众鑫新材料科技股份有限公司 | Preparation method of low-oxygen vanadium-nitrogen alloy |
| CN114318040B (en) * | 2021-12-29 | 2023-04-07 | 江西理工大学 | Rare earth-added hard alloy and preparation method thereof |
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| CN1544675A (en) * | 2003-11-17 | 2004-11-10 | 株洲硬质合金集团有限公司 | Process for preparing ultra-fine cemented carbide |
| CN101824575A (en) * | 2010-05-27 | 2010-09-08 | 中南大学 | Ultrafine grain wolfram carbide/ cobalt hard alloy and preparation method thereof |
| CN102061401A (en) * | 2010-12-10 | 2011-05-18 | 中南大学 | Method for preparing WC base hard alloy with high hardness and high toughness |
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|---|---|---|---|---|
| CN1544675A (en) * | 2003-11-17 | 2004-11-10 | 株洲硬质合金集团有限公司 | Process for preparing ultra-fine cemented carbide |
| CN101824575A (en) * | 2010-05-27 | 2010-09-08 | 中南大学 | Ultrafine grain wolfram carbide/ cobalt hard alloy and preparation method thereof |
| CN102061401A (en) * | 2010-12-10 | 2011-05-18 | 中南大学 | Method for preparing WC base hard alloy with high hardness and high toughness |
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