CN1254628A - Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt - Google Patents
Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt Download PDFInfo
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Abstract
An industrial process for prearing hard alloy powder uses the compound containing W and Co and crystal inhibitor as raw materials and includes such steps as spray thermolysis to obtain the precursor powder of compound oxide, loading in fluidized bed, reduction at 450-850 deg.C by introducing hydrogen, carbonizing at 750-1500 deg.C by carbon-contained gas, supplementary carbonizing at 700-1200 deg.C by carbon-contained gas and hydrogen and regulating carbon content at 500-900 deg.C by carbon-contained gas and hydrogen to obtain nm-class non-eta-plase WC-Co compound powder. Its advantages are simple process, easy control, no pollution and low cost.
Description
The invention belongs to the preparation of industrialization technology of cemented carbide powder.
The tungsten-cobalt carbide of superfine crystal particle (WC-Co) Wimet has high rigidity, high-intensity " two high " performance, is mainly used in to make surface-mounted integrated circuit microbit, dot-matrix printer printing syringe needle, whole aperture knife tool, wood working tool, accurate tool and mould, dental drill, difficult-to-machine material cutter etc.
The WC-Co Wimet of superfine crystal particle and the key distinction of ordinary rigid alloy are that the crystal grain that alloy grain reaches ultra-fine (＜0.5 μ m), raw material powder reaches nano level (＜0.1 μ m).The crystal grain of WC Wimet is thin more, and defective is more little, bonding mutually as Co mean free path reduce, bending strength and hardness just can both keep high value.In fact, under the situation that other tangent condition is equal to, each performance of WC base cemented carbide---hardness, modulus, wear resistance, ultimate compression strength etc. are all along with the mean particle size of hard composition WC diminishes, size distribution narrow and being enhanced.Similarly, though be in a liquid state under sintering temperature, the dispersivity of bonding phase metal such as Co is also improved by thin starting material.
Required ultra-fine-nano level WC-Co the composite powder of preparation superfine crystal particle WC-Co Wimet mainly contains following method:
(1) makes tungsten oxide be become tungsten powder with methods such as fixed bed, rotary kiln, hydrogen plasmas, tungsten (W) powder is mixed with carbon (C) sphere of powder mill, change into wolfram varbide (WC), mix with ready-formed cobalt (Co) sphere of powder mill again through pyrocarbon by hydrogen reducing;
(2) make mixture direct reduction and carbonization in high-temperature hydrogen of tungsten oxide and carbon dust become WC with rotary kiln, mix with ready-formed Co sphere of powder mill again;
(3) be that the spray-dried method of raw material is made tungsten cobalt/cobalt oxide precursor powder with the tungsten cobalt salt, they are mixed with the carbon dust ball milling, become tungsten-cobalt carbide (WC-Co) composite powder (Byoung-Kee Kim through the high temperature reduction carbonization, Gil-Geun Lee, Gook-Hyun Ha, Dong-Won Lee.Mechanochemical Process for Producing Fine WC/Co Composite Powder, US Pat.5882376, Mar.16,1999);
(4) be that the spray-dried method of raw material is made tungsten cobalt/cobalt oxide precursor powder with the tungsten cobalt salt, they are placed fluidized-bed, feed H
2/ CO/CO
2Gas makes it at a certain temperature continuously reduction and carbonization and becomes WC-Co powder (L.E.McCandlish, B.H.Kear, Byoung-KeeKim.Carbothermic Reaction Process for Making Nanophase WC-Co Powder, World Pat.WO 93/02962, Feb.18,1993; L.E.McCandliah, B.H.Kear, SwarnJeet Bhatia.Spray conversion process for the production ofnanophase composite powders, World Pat.WO 91/07244, May 30,1991);
(5) compound with tungstenic (W), cobalt (Co) element is that raw material is made tungsten cobalt/cobalt oxide precursor powder through sol-gel method, coprecipitation method, spray-drying process, they are placed fluidized-bed, feeding rare gas element/hydrogen/carbonaceous gas makes it at a certain temperature continuously reduction and carbonization and becomes WG-Co powder (Wei Mingkun, Zhang Hanlin, Wang Zhu, Mao Jingyuan. use the fluid bed reduction and carbonization one-step preparing hard alloy compound powder, Chinese invention patent ZL93108446.6, on July 20th, 1993).
Obviously, above-mentioned (4), (5) kind method is that the method for the continuous reduction and carbonization of fluidized-bed gas phase has been simplified technical process, can guarantee the uniform distribution of Co in composite powder and alloy, the existence of Co can accelerate to reduce the speed with carbonization, and reduces the required temperature of carburizing reagent significantly.Because the continuity of technological process and composite powder fully contact with reactant gases, have kept the high reactivity of powder, and the crystal grain of powder can keep tiny even.Simultaneously, the requirement to equipment also reduces significantly.Therefore, the method for preparing the WC-Co nano composite powder with the continuous reduction and carbonization of fluidized-bed has tempting industrial prospect.
The objective of the invention is:
A kind of industrialization technology that the required nano level of superfine crystal particle WC-Co Wimet does not have η phase WC-Co composite powder for preparing is proposed.
The objective of the invention is to realize as follows:
Compound and crystallizing inhibitor with tungstenic, cobalt element are raw material, send into immediately in the spray pyrolysis unit after making it to mix, and make the tungsten cobalt/cobalt oxide precursor powder that contains the crystallizing inhibitor composition.The oxide precursor powder is placed fluidized-bed, make it through reduction, carbonization, once or for several times apace cooling-intensifications with additional carbonization, accent carbon process, thereby make no η phase nano WC-Co composite powder end.
Carrying out to prepare suitable oxide precursor powder before the continuous reduction and carbonization operation.What this moment, the easiest quilt was expected is exactly spray-drying process.
Spray-drying process is employed widely in research and production powdered material field, if but produce tungsten cobalt/cobalt oxide precursor powder with this method, then there are shortcomings such as decomposition temperature is not enough, powder flowbility is relatively poor, element segregation, the form of mixtures that made powder majority is a salt exists, but not oxide compound completely, this will bring disadvantageous effect to follow-up reduction and carbonization process.
The present invention uses the spray pyrolysis preparation to contain the tungsten cobalt/cobalt oxide precursor powder of crystallizing inhibitor composition, can fundamentally overcome above-mentioned shortcoming, this method is finished spraying nodularization and decomposition course simultaneously at short notice, make tungsten, cobalt compound and the quick uniform mixing of crystallizing inhibitor raw material, decomposition, nodularization, drying, reached the purpose of introducing crystallizing inhibitor in earlier stage, preparing the precursor powder that helps later stage fluidization operation.
In addition, raw material powder is in fluidized state all the time in fluidized-bed, and not only difficult gathering of the particle behind the reduction and carbonization grows up, and mutual collision also helps gas-solid mass transfer, evenly refinement.At reduction phase, the control reduction temperature can change reaction path, walks around WO
2.72And WO
2The formation stage, thereby obtain thinner reduzate; At carbonation stage, before thermodynamically stable WC-Co generated mutually, carbide in the middle of always forming earlier prolonged the carbonization time that generates the WC-Co phase, the scantlings of the structure that powder particle alligatoring and restriction finally can be reached.Therefore, the present invention take once or for several times fast cooling-temperature-rise period replenishing carbonization, and with carbonaceous gas/hydrogen/nitrogen adjusting carbon amount, thus for the carbonization deficiency or carbonization is excessive can both regulate effectively.
Main technique flow process of the present invention:
See accompanying drawing, below technical process is illustrated.
1, raw material:
Compound and crystallizing inhibitor with tungstenic, cobalt element are raw material, take water-soluble, alkali is molten, acid is molten, evenly suspend or force stirring method to make it to mix or dissolving, three kinds of proportion of raw materials are by the Wimet composition of required preparation and decide.In the weight of tungsten-cobalt carbide (WC-Co), tungsten compound is 60～97wt%, and cobalt compound is 3～40wt%, and crystallizing inhibitor is 0～10wt%, wherein:
(1) tungsten compound can be selected a kind of in following for use: ammonium metawolframate AMT ((NH
4)
6(H
2W
12O
40) 4H
2O), ammonium paratungstate APT ((NH
4)
10(H
2W
12O
42) 4H
2O), positive ammonium tungstate (NH
4)
2WO
4, wolframic acid H
2WO
4, metatungstic acid H
6(H
2W
12O
40);
(2) cobalt compound can be selected a kind of in following for use: nitric hydrate cobalt Co (NO
3)
26H
2O, hydration cobaltous acetate Co (CH
3COO)
24H
2O, cobalt oxalate CoC
2O
4, hydrated cobalt chloride CoCl
26H
2O, hydration rose vitriol CoSO
47H
2O, cobaltous carbonate CoCO
3
(3) the crystallizing inhibitor raw material can be selected a kind of in following or several for use: oxide compound, ammonium salt, nitrate, acetate, oxalate, villaumite, the vitriol of vanadium (V), molybdenum (Mo), chromium (Cr), tantalum (Ta), niobium (Nb), titanium (Ti), zirconium (Zr), hafnium (Hf).
2, spray pyrolysis:
Can take flame, electric heating, microwave, plasma, laser spray pyrolysis, the melting concn of the compound of tungstenic, cobalt element and crystallizing inhibitor raw material is controlled at 30～70wt%; Dissimilar according to raw material, can increase warm, and atomizing tolerance, temperature can have nothing in common with each other, but heat decomposition temperature should be controlled at 200～700 ℃ all the time.Make the tungsten cobalt/cobalt oxide precursor powder that contains the crystallizing inhibitor composition thus.
3, reduction, carbonization, additional carbonization, accent carbon:
The tungsten cobalt/cobalt oxide precursor powder that will contain the crystallizing inhibitor composition places fluidized-bed, be rapidly heated to 450～850 ℃, in 1: 0.5～1: 10 ratio feed hydrogen and rare gas element make it to be reduced into W, Co, V (Mo, Cr ...) wait metal simple-substance; Be rapidly heated to 750～1500 ℃ after the reduction fully, feed carbonaceous gas, hydrogen and rare gas element (wherein the ratio of carbonaceous gas and hydrogen is 1: 20～1: 0.5) make W, V (Mo, Cr ...) wait carbonization (Co not carbonization under this study condition); Then through once or for several times fast cooling-temperature-rise period (wherein rate of temperature fall is 100～400 ℃/hour, temperature rise rate is 200～500 ℃/hour), replenish carbonization (wherein the ratio of carbonaceous gas and hydrogen is 1: 100～1: 10) at 700～1200 ℃ with carbonaceous gas, hydrogen and rare gas element; Regulate carbon amount (wherein the ratio of carbonaceous gas and hydrogen is 1: 100～1: 20) at 500～900 ℃ with carbonaceous gas, hydrogen and rare gas element at last, thereby make no η phase (being intact carbon phase) nano WC-Co composite powder end.Rare gas element among the present invention comprises Ar, He, Ne, Kr, Xe and N
2
Characteristics of the present invention:
With spray pyrolysis spraying nodularization and decomposition course are finished at short notice simultaneously, in fluidized-bed through reduction, carbonization, once or for several times apace cooling-intensifications with additional carbonization, adjusting carbon amount process, guaranteed for the carbonization deficiency or carbonization is excessive can both regulate effectively, become possibility thereby make preparation of industrialization not have η phase nano WC-Co composite powder end.
Therefore, simple, the control easily of technology of the present invention, do not pollute, cost of investment is low, be suitable for commercial scale production.
The present invention can be generalized to research and production fields such as preparation composite carbide, titanium carbide base hard alloy, Steel Bond Hard Alloy, sintering metal.
Embodiment 1:
Ammonium metawolframate AMT ((NH
4)
6(H
2W
12O
40) 4H
2O), nitric hydrate cobalt Co (NO
3)
26H
2It is miscible in distilled water that the O raw material is pressed the 85wt%WC+15wt%Co proportioning, makes tungsten cobalt/cobalt oxide precursor powder through spray pyrolysis.This composite powder is put into fluidized-bed, use H at 500-750 ℃
2/ N
2(=1: 2) reduction; Use CH at 800～900 ℃
4/ H
2/ N
2(=1: 10: 10) carbonization; Through cooling-temperature-rise period fast once, use CH at 850～900 ℃
4/ H
2/ N
2(=0.1: 10: 10) replenishes carbonization; Use CO at 500～700 ℃
2/ H
2/ N
2(=0.1: 5: 10) regulates the carbon amount.The crystalline phase of the WC-15Co composite powder of making thus is WC+Co, and recording the powder mean grain size with the X ray wide-angle diffraction is 35.6nm.Embodiment 2:
Ammonium metawolframate AMT ((NH
4)
6(H
2W
12O
40) 4H
2O), hydration cobaltous acetate Co (CH
3COO)
24H
2O, ammonium meta-vanadate NH
4VO
3It is miscible in distilled water that raw material is pressed the 91.5wt%WC+8wt%Co+0.5wt%VC proportioning, makes tungsten cobalt barium oxide precursor powder through spray pyrolysis.This composite powder is put into fluidized-bed, use H at 550～800 ℃
2/ N
2Reduction (=1: 3); Use CH at 850～980 ℃
4/ H
2/ N
2(=1: 10: 9) carbonization; Through cooling-temperature-rise period fast once, use CH at 850～980 ℃
4/ H
2/ N
2(=0.1: 10: 9) replenishes carbonization; Use CO at 700～900 ℃
2/ H
2/ N
2(=0.1: 5: 10) regulates the carbon amount.The crystalline phase of the WC-8Co-0.5VC composite powder of making thus is WC+Co+VC, and recording the powder median size with the X ray wide-angle diffraction is 45.8nm.Embodiment 3:
Ammonium paratungstate APT ((NH
4)
10(H
2W
12O
42) 4H
2O), cobalt oxalate CoC2O4, ammonium molybdate (NH
4)
6Mo
7O
244H
2The O raw material is pressed 93.7wt%WC+6wt%Co+0.3wt%Mo
2The C proportioning is miscible in ammoniacal liquor, makes tungsten cobalt molybdenum oxide precursor powder through spray pyrolysis.This composite powder is put into fluidized-bed, use H at 500～800 ℃
2/ Ar (=1: 2) reduction; Use CH at 1000～1500 ℃
4/ H
2/ Ar (=1: 5: 14) carbonization; Through cooling-temperature-rise period fast once, use CH at 1000～1500 ℃
4/ H
2/ Ar (=0.1: 5: 14) replenishes carbonization; Use CO at 800～900 ℃
2/ H
2/ Ar (=0.1: 4: 10) regulates the carbon amount.The WC-6Co-0.3Mo that makes thus
2The crystalline phase of C composite powder is WC+Co+Mo
2C, recording the powder median size with the X ray wide-angle diffraction is 72.1nm.Embodiment 4:
Positive ammonium tungstate (NH
4)
2WO
4, hydrated cobalt chloride CoCl
26H
2O, hydration chromium chloride CrCl
36H
2The O raw material is pressed 88.7wt%WC+11wt%Co+0.3wt%Cr
3C
2Proportioning is miscible in distilled water, makes tungsten cobalt chromated oxide precursor powder through spray pyrolysis.This composite powder is put into fluidized-bed, use H at 500～800 ℃
2/ Ar reduction (=1: 2); Use CH at 1000～1500 ℃
4/ H
2/ Ar (=1: 10: 10) carbonization; Through cooling-temperature-rise period fast once, use CH at 1000～1500 ℃
4/ H
2/ Ar (=0.1: 10: 10) replenishes carbonization; Use CO at 700～900 ℃
2/ H
2/ Ar (=0.1: 5: 10) regulates the carbon amount.The WC-11Co-0.3Cr that makes thus
3C
2The crystalline phase of composite powder is WC+Co+Cr
3C
2, recording the powder median size with the X ray wide-angle diffraction is 63.1nm.Embodiment 5:
Wolframic acid H
2WO
4, hydration rose vitriol CoSO
47H
2O, tantalum oxide (Ta
2O
5), niobium oxides (Nb
2O
5) raw material presses 88.0wt%WC+10wt%Co+2.0wt% (Ta, Nb) the C proportioning is miscible in ammoniacal liquor, makes tungsten cobalt tantalum niobium oxide precursor powder through spray pyrolysis.This composite powder is put into fluidized-bed, use H at 550～850 ℃
2/ Ar reduction (=1: 2); Use CH at 1000～1500 ℃
4/ H
2/ Ar (=2: 8: 10) carbonization; Through cooling-temperature-rise period fast once, use CH at 1000～1500 ℃
4/ H
2/ Ar (=0.2: 8: 10) replenishes carbonization: use CO at 500～900 ℃
2/ H
2/ Ar (=0.1: 7: 10) regulates the carbon amount.(Ta, Nb) crystalline phase of C composite powder is that (record the powder median size with the X ray wide-angle diffraction is 67.8nm to WC+Co+ for Ta, Nb) C to the WC-10Co-2.0 that makes thus.Embodiment 6:
Metatungstic acid H
6(H
2W
12O
40), cobaltous carbonate CoCO
3, ammonium meta-vanadate NH
4VO
3It is miscible in distilled water that raw material is pressed the 84.3wt%WC+15wt%Co+0.7wt%VC proportioning, makes tungsten cobalt barium oxide precursor powder through spray pyrolysis.This composite powder is put into fluidized-bed, use H at 450～750 ℃
2/ N
2Reduction (=1: 2.5); Use CH at 850～950 ℃
4/ H
2/ N
2(=1: 15: 11) carbonization; Through cooling-temperature-rise period fast once, use CH at 850～950 ℃
4/ H
2/ N
2(=0.1: 15: 11) replenishes carbonization; Use CO at 500～700 ℃
2/ H
2/ N
2(=0.1: 6: 10) regulates the carbon amount.The crystalline phase of the WC-15Co-0.7VC composite powder of making thus is WC+Co+VC, and recording the powder median size with the X ray wide-angle diffraction is 42.1nm.
Claims (7)
1. the preparation of industrialization technology of nm-class non-eta-phase compound powder of tungsten carbide and cobalt, it is characterized in that compound and crystallizing inhibitor with tungstenic (W), cobalt (Co) element are raw material, make the oxide precursor powder through spray pyrolysis, this powder is placed fluidized-bed, make it reduction at 450～850 feeding hydrogen and rare gas element; Feed carbonaceous gas, hydrogen and rare gas element at 750～1500 ℃ and carry out carbonization; Then through cooling-temperature-rise period fast once or for several times, at 700～1200 ℃ with the additional carbonization of carbonaceous gas, hydrogen and rare gas element; Regulate the carbon amount at 500～900 ℃ with carbonaceous gas, hydrogen and rare gas element at last, thereby make no η phase (being intact carbon phase) nanometre tungsten carbide-cobalt (WC-Co) composite powder.
2. according to the preparation of industrialization technology of the described nm-class non-eta-phase compound powder of tungsten carbide and cobalt of claim 1, it is characterized in that the weight of three kinds of proportion of raw materials in WC-Co, tungsten compound is 60～97wt%, and cobalt compound is 3～40wt%, crystallizing inhibitor is 0～10wt%, wherein:
(1) tungsten compound can be selected a kind of in following for use: ammonium metawolframate AMT ((NH
4)
6(H
2W
12O
40) 4H
2O), ammonium paratungstate APT ((NH
4)
10(H
2W
12O
42) 4H
2O), positive ammonium tungstate (NH
4)
2WO
4, wolframic acid H
2WO
4, metatungstic acid H
6(H
2W
12O
40);
(2) cobalt compound can be selected a kind of in following for use: nitric hydrate cobalt Co (NO
3)
26H
2O, hydration cobaltous acetate Co (CH
3COO)
24H
2O, cobalt oxalate CoC
2O
4, hydrated cobalt chloride CoCl
26H
2O, hydration rose vitriol CoSO
47H
2O, cobaltous carbonate CoCO
3
(3) the crystallizing inhibitor raw material can be selected a kind of in following or several for use: oxide compound, ammonium salt, nitrate, acetate, oxalate, villaumite, the vitriol of vanadium (V), molybdenum (Mo), chromium (Cr), tantalum (Ta), niobium (Nb), titanium (Ti), zirconium (Zr), hafnium (Hf).
3. according to the preparation of industrialization technology of the described nm-class non-eta-phase compound powder of tungsten carbide and cobalt of claim 1, the processing parameter that it is characterized in that spray pyrolysis is: the melting concn of the compound of tungstenic, cobalt element and crystallizing inhibitor raw material is 30～70wt%, and heat decomposition temperature is controlled at 200～700 ℃.
4. according to the preparation of industrialization technology of the described nm-class non-eta-phase compound powder of tungsten carbide and cobalt of claim 1, it is characterized in that the ratio of control hydrogen and rare gas element is 1: 0.5～1: 10 in reduction process.
5. according to the preparation of industrialization technology of the described nm-class non-eta-phase compound powder of tungsten carbide and cobalt of claim 1, it is characterized in that the ratio of control carbonaceous gas and hydrogen is 1: 20～1: 0.5 in carbonization process.
6. according to the preparation of industrialization technology of the described nm-class non-eta-phase compound powder of tungsten carbide and cobalt of claim 1, it is characterized in that the processing parameter that replenishes carbonization is: the ratio control of carbonaceous gas and hydrogen was at 1: 100～1: 10, rate of temperature fall is 100～400 ℃/hour, temperature rise rate is 200～500 ℃/hour, according to the degree of replenishing carbonization, can carry out once or continuous cooling-temperature-rise period for several times.
7. according to the preparation of industrialization technology of the described nm-class non-eta-phase compound powder of tungsten carbide and cobalt of claim 1, it is characterized in that the ratio of control carbonaceous gas and hydrogen is 1: 100～1: 20 in regulating carbon amount process.
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