CN102350506A - Preparation method of nano-structure WC-Co composite powder - Google Patents
Preparation method of nano-structure WC-Co composite powder Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano-structure WC-Co composite powder, and belongs to the field of an alloy preparation method. The method comprises the following steps in sequence: adding a carbonic powder material which is excessive to tungsten, vanadium and chromium carbides into water-soluble saturated mixed aqueous solution of tungsten-containing compound, cobalt-containing compound, chromium-containing compound and vanadium-containing compound to adsorb the saturated composite salt solution; dehydrating and drying to form a nano-scale composite salt thin layer on the surface of the carbonic powder material; removing crystal water out of the composite salt at the temperature below 500 DEG C under a condition of isolating air, and decomposing the composite salt into composite oxide of tungsten oxide, chromium hemitrioxide, vanadium oxide and cobalt oxide, further heating, and reducing and carbonizing the composite oxide on the surface of the carbonic powder material to generate the WC-Co nano-structure composite powder at the temperature below 850 DEG C. The preparation is a simpler and more reliable novel preparation method of the nano WC-Co composite powder by a direct carbonization method.
Description
Technical field
The invention belongs to the alloy preparation method field, relate in particular to nanoscale WC-Co preparation method.
Background technology
Usually carbide alloy cutting tool is with the manufacturing of micron order WC-Co powder.Along with to the improving constantly of sintered-carbide tool performance requirement, the researcher finds: improve hardness, wearability and the corrosion resistance of product, need to increase the content of WC; Improve intensity, toughness and the processing characteristics of product, need to increase the content of Co, this has produced contradiction between raising hardness and intensity.People have begun to adopt thinner powder for this reason, because research shows, when the WC grain size is reduced to sub-micron when following, the hardness of material, toughness, intensity, anti-wear performance all are improved, and simultaneously, reach that densified required temperature is low more fully.Especially nanometer WC material can improve the toughness of material significantly under the prerequisite that improves hardness.In nanometer WC base cemented carbide is produced, seek the focus that the new method (comprising powder preparation, inhibitor, sintering process) that effectively suppresses grain growth is just becoming world today's carbide alloy area research.
Existing research and discovery:
1, Nanodyne company is successfully with spraying conversion processing new technology large-scale production nano powder of tungsten carbide (NanocarbTM).Its WC grain degree can be at 20～50 nm, are 1/10～1/20 of the thinnest common microcrystalline powder granularity.Typical NanocarbTM powder particle is that hollow 75 μ m spheroids (typical case is 20～100 μ m) are formed, and contains millions upon millions of WC grains and is distributed in the cobalt-based body.Because technology begins from solution, so being molecular level, mixes in Nano carbTM powder, need not to grind, and from the beginning, technology is just not affected by environment.
2, utilize CO reduction and carbonization WO3 and Co2O3 composite powder, the long reaction time makes particle alligatoring and limited can getable final structure size.Therefore, be necessary that CO/ CO2 is made carbon source does further research.
3, people have worked out a kind of method that can replace gas carburization.This method is made original carbon source with the polymer of polyacrylonitrile.Earlier polyacrylonitrile is dissolved in and produces clear liquid in the dimethyl formamide, W and Co mixed-powder are dissolved in this solution, dry on hot plate this mixed liquor again, at last the dried powder calcining is made required powder.It has reduced the reaction time through powder being dissolved in the evolving path that solution has improved the uniformity that carbon distributes, reduced carbon, has suppressed growing up of crystal grain.In this technology, calcining heat, time and atmosphere have intense influence to product.For example calcining heat is crossed when hanging down, and can obtain product W, rather than WC.
Summary of the invention
The objective of the invention is to: propose the method that the more simple and reliable new direct carborization of a kind of technology prepares the nano WC-Co composite powder end.
The object of the invention realizes through following technical proposals:
A kind of nanostructured WC-Co composite powder preparation method is characterized in that may further comprise the steps successively:
A, at water miscible Tungstenic compound, cobalt compound, contain to add in the saturated mixed aqueous solution of chromium compound and vanadium-containing compound tungsten, vanadium, the excessive carbonaceous powder body material of chromium carbide adsorbed saturated complex salt solution, the specific area of said carbonaceous powder body material is greater than 1500m
2/ g;
B, dehydrate, form the complex salt thin layer of nanoscale at the carbonaceous powder body material surface;
C, under the secluding air condition; Heat said carbonaceous powder body material and complex salt mixture; Below 500 ℃ said complex salt is removed the crystallization water; And be decomposed into the composite oxides of tungsten oxide, chromium oxide, vanadium oxide, cobalt oxide; Further heating; Below 850 ℃, above-mentioned composite oxides are generated WC-Co nanostructured composite powder in reduction of carbonaceous powder body material surface and carbonization.
Said to tungsten, vanadium, the excessive carbonaceous powder body material of chromium carbide, be meant the stoichiometry of the carbonaceous powder quantity of material of use greater than the required C of preparation WC under the thermodynamical reaction temperature.
As optimal way, said carbonaceous powder body material is metallurgical carbon black and/or porous carbon.Used carbonaceous powder is the high purity carbon with huge specific area; Utilize its huge specific area absorption complex chemical compound solution; Form the liquid film of several molecule layer thickness, after drying, obtain nanoscale complex chemical compound particle, as the presoma of composite oxides and double carbide.With conventional method with carbon black as just reducing agent and carbide carbon source difference; Utilization of the present invention has huge specific area carbonaceous powder and obtains the complex chemical compound of nanoscale and the composite oxide particle of nanoscale; The charcoal particle surface of excessive huge specific area is as nano-carbide crystallization nucleation point; The reaction temperature of the big more reduction-carbonization of area is low more, forming core point is many more; The low more grain growth of carburizing temperature is more difficult, and then crystal grain is more little; Simultaneously excessive carbon granule stops carbide grain to be grown up.
As optimal way, the particle mean size of said metallurgical carbon black is less than 0.1 μ m, and specific area is greater than 1800m
2/ g, sulfur content is less than 10ppm.
As optimal way, said porous carbon specific area is greater than 1800m
2/ g, carbon content is greater than 99.5%wt, and sulfur content is less than 10ppm.
As optimal way, said Tungstenic compound is selected from one or more in ammonium metatungstate, the metatungstic acid.
As optimal way, said cobalt compound is selected from one or more in cobalt nitrate, cobalt chloride, the cobalt acetate.
As optimal way, the said chromium compound that contains is selected from high chromic acid content ammonium, the chromic acid one or more.
As optimal way, said vanadium-containing compound is an ammonium metavanadate.
The course of work is: utilize surface adsorption tungsten salt, the chromic salts of the huge specific area of excessive carbonaceous powder body material, the saturated aqueous solution of vanadic salts, obtain the mixture of various composition high degree of dispersion.Through behind the drying and dehydrating; In heating process; Tungsten salt, chromic salts, vanadic salts are decomposed into the composite oxides of tungsten oxide, chromium oxide, vanadium oxide, cobalt oxide; Along with heating-up temperature increases; These oxides are reduced carbonization gradually on carbonaceous powder material granule surface, composite oxides generation reduction and carbonization reaction under the high temperature:
(1)?WO
3?+?4C?=?WC?+?3CO↑
(2)?2WO
3?+?5C?=?2WC?+?3CO
2↑
(3)?2Co
2O
3?+?3C?=?4Co?+?3CO
2↑
Obtain the nano WC-Co composite powder end at last.In reduction-carbonisation; The composite oxides that are adsorbed on carbonaceous powder material granule surface generate carbide on carbonaceous powder material granule surface; Carbonaceous powder material granule is grown up to carbide and is played mechanical isolation; The carbonaceous powder body material promotes the forming core of carbide simultaneously; In reduction-carbonisation; In the oxide of cobalt and tungsten and chromium, vanadium, the oxide of cobalt is reduced easily, can quicken the reduction-carbonisation of other several oxides.Make reduction-carbonization accomplish at lower temperature with in the short period.
Beneficial effect of the present invention:
1. in the aqueous solution, mix various metallic compounds, can reach the even mixing of molecular level degree;
2. utilize the huge specific area of excessive carbonaceous powder material nano size granule; Not only can adsorb complex salt solution; Obtain the complex salt liquid film of several molecule layer thickness on the carbon blacksurface; For subsequent preparation nanoscale oxide lays the foundation, overcome the thick complex salt crystallization that existing method possibly occur simultaneously in complex salt solution dry run;
3. in the aqueous solution, sneak into excessive carbonaceous powder body material particle and avoided the issuable micro Distribution non-uniform phenomenon of existing method mechanical mixture carbon black in oxide powder;
4. technology is more simple and reliable; The present invention adopts the even adsorption reaction thing of huge specific area of carbonaceous powder body material and becomes the matrix in its reduction-carbonisation as previously mentioned, has realized carbide forming core and crystal grain-growth inhibition equably effectively through this mode; Adopt the complex salt calcining and decomposing to become composite oxides; The composite oxides reduction merges with the carbonization flow process; Make the complex salt calcining; Composite oxides reduction and carbonization flow process is accomplished in the different heating temperature; In same equipment, accomplish, can under lower temperature and short period, prepare the nano WC-Co composite powder end.
Description of drawings
Fig. 1 is the nanostructured WC-Co composite powder scanning electron microscope sem pattern phase of the embodiment of the invention 1;
Fig. 2 is the nanostructured WC-Co composite powder transmission electron microscope TEM phase of the embodiment of the invention 1;
Fig. 3 is the crystal structure X-ray diffractogram of the nanostructured WC-Co composite powder of the embodiment of the invention 1;
Fig. 4 is the nanostructured WC-Co composite powder scanning electron microscope sem pattern phase of the embodiment of the invention 2.
The specific embodiment
Following non-limiting examples is used to illustrate the present invention.
Embodiment 1:
According to WC-10%Co, 0.15%VC, 0.15%Cr
3C
2The metal ingredient ratio (contain 10% metallic cobalt in the powder, 0.15%VC, 0.15% Cr
3C
2, all the other WC), calculate and take by weighing metatungstic acid, cobalt nitrate, ammonium metavanadate, ammonium chromate, put into bucket, add appropriate amount of deionized water then and stir, the deionized water dosage is dissolved as maximum dosage fully with various slaines.19% (weight ratio) of pressing tungstic acid content adds ultra-fine metallurgical carbon black, and metallurgical carbon black requires particle mean size less than 0.1 μ m, and specific area is greater than 1800m
2/ g, sulfur content continues stirring and is paste less than 10ppm, in the pressure atomization drier, is dried to granulated powders.320～350 ℃ of drier EATs, 180～200 ℃ of leaving air temps.Dry composite salt and black stock powder are put into quartz or alumina crucible, put into the tube furnace heating.The water seal of tube furnace two ends, so that secluding air gets in the stove, the gas pressure that the complex salt heating and decomposition discharges is during greater than atmospheric pressure, decomposition gas overflows from the water seal end of fire door.500 ℃ of following temperature; Main chemical reactions is that the complex salt decomposition and inversion is composite oxides; Cobalt oxide more than 500 ℃ in the temperature composite oxides at first is reduced into metallic cobalt; Tungsten oxide is reduced to WO2 or WO at a low price; Along with heating-up temperature is elevated to about 750 ℃; Reduction process is accomplished basically, the compound and the metal of minor amount of carbide occur.Release gas is CO/CO
2The ratio of the high more CO gas of mist, temperature is big more, and longer release of time gas is few more.Be transformed into carbide at 850 ℃ of following temperature W, V, Cr more than 750 ℃, subcarbide crystal grain is more little more for temperature.Carbonisation is at CO/CO
2Carry out in the mist, last remaining excessive carbon black is through changing CO/CO
2CO2 content makes its oxidation and eliminates its reaction equation in the mist: C+ CO
2=CO.Obtain meeting the nanostructured WC-Co composite powder that comprises grain growth inhibitor of sintering WC-Co carbide alloy requirement.The granularity and the chemical composition of the WC-10%Co composite powder of this method preparation are as shown in table 1; Its method of testing is the method for testing of conventional concerned countries standard, is specially: specific area is used nitrogen adsorption method (assay method of GB.T 13390-92 metal dust specific area); Testing graininess laser particle analyzer, equipment are Britain Ma Erwen laser particle analyzer, and principle is that the powder particle size is corresponding with its sinking speed in liquid, i.e. the Stocks principle; (the mensuration infra-red detection method and technology of sulphur and carbon content corrects errors in printing 1 in the ISO 11873 Technical Corrigendum 1-2008 hard metal cobalt metal powders) carbon content is tested with carbometer; The free carbon test; Earlier add hydrofluoric acid dissolved carbon thing and metal with sulfuric acid; Dissolving remnants are free carbon, test with carbometer; Oxygen-nitrogen analyzer is used in oxygen content test (GB/T 5158.4-2001 metal dust oxygen content testing standard), produces like Beijing nanogram.The ESEM of powder such as Fig. 1 and transmission electron microscope are as shown in Figure 2.The crystal structure X-ray diffraction result of powder is (method of testing: the mensuration low-angle scattering of X-rays method of standard GB/T13221-2004 nanometer powder size distribution) as shown in Figure 3.
Embodiment 2:
According to WC-10%Co, 0.15%VC, 0.15%Cr
3C
2The metal ingredient ratio (contain 10% metallic cobalt in the powder, 0.15%VC, 0.15% Cr
3C
2, all the other WC), calculate and take by weighing ammonium metatungstate, cobalt chloride, ammonium metavanadate, chromic acid, put into bucket, add appropriate amount of deionized water then and stir, the deionized water dosage is dissolved as maximum dosage fully with various slaines.19% (weight ratio) of pressing tungsten oxide content adds porous carbon, and like active carbon powder, activated carbon requires specific area greater than 1800m
2/ g, carbon content is greater than 99.5%wt, and sulfur content continues stirring and is paste less than 10ppm, in the pressure atomization drier, is dried to granulated powders.320～350 ℃ of drier EATs, 180～200 ℃ of leaving air temps.Dry composite salt and black stock powder are put into quartz or alumina crucible, put into the tube furnace heating.The water seal of tube furnace two ends, so that secluding air gets in the stove, the gas pressure that the complex salt heating and decomposition discharges is during greater than atmospheric pressure, decomposition gas overflows from the water seal end of fire door.500 ℃ of following temperature, main chemical reactions is that the complex salt decomposition and inversion is composite oxides, and the cobalt oxide more than 500 ℃ in the temperature composite oxides at first is reduced into metallic cobalt, and tungsten oxide is reduced to WO at a low price
2Or WO, along with heating-up temperature is elevated to about 750 ℃, reduction process is accomplished basically, the compound and the metal of minor amount of carbide occur.Release gas is CO/CO
2The ratio of the high more CO gas of mist, temperature is big more, and longer release of time gas is few more.Be transformed into carbide at 850 ℃ of following temperature W, V, Cr more than 750 ℃, subcarbide crystal grain is more little more for temperature.Carbonisation is at CO/CO
2Carry out in the mist, last remaining excessive carbon black is through changing CO/CO
2CO in the mist
2Content makes its oxidation and eliminates its reaction equation: C+ CO
2=CO..Obtain meeting the nanostructured WC-Co composite powder that comprises grain growth inhibitor of sintering WC-Co carbide alloy requirement.Granularity and the chemical composition such as the table 2 of the compound WC-Co powder of gained, its method of testing is with embodiment 1.The ESEM picture as shown in Figure 4.
Embodiment 3:
According to WC-10%Co, 0.15%VC, 0.15%Cr
3C
2The metal ingredient ratio (contain 10% metallic cobalt in the powder, 0.15%VC, 0.15% Cr
3C
2, all the other WC), calculate and take by weighing metatungstic acid, cobalt acetate, ammonium metavanadate, ammonium chromate, put into bucket, add appropriate amount of deionized water then and stir, the deionized water dosage is dissolved as maximum dosage fully with various slaines.19% (weight ratio) of pressing tungsten oxide content adds active carbon, and active carbon requires specific area greater than 1800m
2/ g, carbon content is greater than 99.5%wt, and sulfur content continues stirring and is paste less than 10ppm, in the pressure atomization drier, is dried to granulated powders.320～350 ℃ of drier EATs, 180～200 ℃ of leaving air temps.Dry composite salt and black stock powder are put into quartz or alumina crucible, put into the tube furnace heating.The water seal of tube furnace two ends, so that secluding air gets in the stove, the gas pressure that the complex salt heating and decomposition discharges is during greater than atmospheric pressure, decomposition gas overflows from the water seal end of fire door.500 ℃ of following temperature, main chemical reactions is that the complex salt decomposition and inversion is composite oxides, and the cobalt oxide more than 500 ℃ in the temperature composite oxides at first is reduced into metallic cobalt, and tungsten oxide is reduced to WO at a low price
2Or WO, along with heating-up temperature is elevated to about 750 ℃, reduction process is accomplished basically, the compound and the metal of minor amount of carbide occur.Release gas is CO/CO
2The ratio of the high more CO gas of mist, temperature is big more, and longer release of time gas is few more.Be transformed into carbide at 850 ℃ of following temperature W, V, Cr more than 750 ℃, subcarbide crystal grain is more little more for temperature.Carbonisation is at CO/CO
2Carry out in the mist, last remaining excessive carbon black is through changing CO/CO
2CO in the mist
2Content makes its oxidation and eliminates its reaction equation: C+CO
2=CO..Obtain meeting the nanostructured WC-Co composite powder that comprises grain growth inhibitor of sintering WC-Co carbide alloy requirement.The granularity of its WC-Co composite powder and chemical composition such as table 3, its method of testing is with embodiment 1.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. nanostructured WC-Co composite powder preparation method is characterized in that may further comprise the steps successively:
A, at water miscible Tungstenic compound, cobalt compound, contain to add in the saturated mixed aqueous solution of chromium compound and vanadium-containing compound tungsten, vanadium, the excessive carbonaceous powder body material of chromium carbide adsorbed saturated complex salt solution, the specific area of said carbonaceous powder body material is greater than 1500m
2/ g;
B, dehydrate, form the complex salt thin layer of nanoscale at the carbonaceous powder body material surface;
C, under the secluding air condition; Heat said carbonaceous powder body material and complex salt mixture; Below 500 ℃ said complex salt is removed the crystallization water; And be decomposed into the composite oxides of tungsten oxide, chromium oxide, vanadium oxide, cobalt oxide; Further heating; Below 850 ℃, above-mentioned composite oxides are generated WC-Co nanostructured composite powder in reduction of carbonaceous powder body material surface and carbonization.
2. nanostructured WC-Co composite powder preparation method as claimed in claim 1 is characterized in that: said carbonaceous powder body material is metallurgical carbon black and/or porous carbon.
3. nanostructured WC-Co composite powder preparation method as claimed in claim 2 is characterized in that: the particle mean size of said metallurgical carbon black is less than 0.1 μ m, and specific area is greater than 1800m
2/ g, sulfur content is less than 10ppm.
4. nanostructured WC-Co composite powder preparation method as claimed in claim 2 is characterized in that: said porous carbon specific area is greater than 1800m
2/ g, carbon content is greater than 99.5%wt, and sulfur content is less than 10ppm.
5. the nanostructured WC-Co composite powder preparation method described in arbitrary claim in the claim 1 to 4, it is characterized in that: said Tungstenic compound is selected from one or more in ammonium metatungstate, the metatungstic acid.
6. the nanostructured WC-Co composite powder preparation method described in arbitrary claim in the claim 1 to 4, it is characterized in that: said cobalt compound is selected from one or more in cobalt nitrate, cobalt chloride, the cobalt acetate.
7. the nanostructured WC-Co composite powder preparation method described in arbitrary claim in the claim 1 to 4 is characterized in that: the said chromium compound that contains is selected from high chromic acid content ammonium, the chromic acid one or more.
8. the nanostructured WC-Co composite powder preparation method described in arbitrary claim in the claim 1 to 4, it is characterized in that: said vanadium-containing compound is an ammonium metavanadate.
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