CN106825599B - A kind of preparation method for the WC-Co nanometer powder adding grain growth inhibitor - Google Patents
A kind of preparation method for the WC-Co nanometer powder adding grain growth inhibitor Download PDFInfo
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- CN106825599B CN106825599B CN201710038790.6A CN201710038790A CN106825599B CN 106825599 B CN106825599 B CN 106825599B CN 201710038790 A CN201710038790 A CN 201710038790A CN 106825599 B CN106825599 B CN 106825599B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
Abstract
The present invention provides a kind of preparation methods of WC-Co nanometer powder for adding grain growth inhibitor, belong to powder metallurgy powder preparation technical field.It is specific the preparation method comprises the following steps: using ammonium metatungstate, cobalt nitrate, fuel, ammonium nitrate, required addition grain growth inhibitor metal salt and organic carbon source as raw material; oxide/carbon composite powder is prepared using low-temperature combustion synthesis, is then carbonized to obtain the WC-Co nanometer powder of grain growth inhibitor doping under atmosphere protection or under vacuum.The low-temperature combustion synthesis that the present invention uses belongs to liquid phase synthesizing method, can achieve the other mixing of molecular level, and the diffusion path that this allows for carbonaceous in carbonisation is short, and reaction temperature and time requirement are lower.In addition the raw material of this method is simple and easy to get, and equipment is simple, and technique is quick, is appropriate for being mass produced.
Description
Technical field
The invention belongs to field of powder metallurgy, the method for being related to preparing WC-Co nanometer powder, in particular to a kind of addition crystalline substance
The preparation method of the WC-Co nanometer powder of the big inhibitor of grain length.
Background technique
WC-Co hard alloy has high intensity, high rigidity, high thermoconductivity, high temperature resistant and corrosion-resistant etc. a series of excellent
Performance, thus it achieves extensive use in industrial circles such as metal cutting process, rock drilling mining, molding die, wear parts.
Research shows that the crystal grain of refinement WC-Co hard alloy can effectively improve its mechanical performance.And to prepare the WC- of Ultra-fine Grained
Co hard alloy first has to prepare Ultra-fine WC-Co Cemented Carbide powder.Traditional WC-Co nanosized hardmetal powder for preparing
Method mainly has the methods of ball-milling method and self-propagating high-temperature combustion method (SHS).(the Journal of Alloy and such as Song
Compounds, 458 (2008), 366-371.) with WO2.9、Co3O4It is raw material with carbon black, by being carbonized after ball milling mixing
The ultra-fine cemented carbide powder that average grain size is 300nm is made.Zaitsev etc. (Materials Letters, 158
(2015), 329-332.) WC powder first is prepared using SHS method, then as ball milling, the WC powder by made from is mixed with Co powder
Superfine WC-Co powder is made.
But WC-Co hard alloy during sintering due to the generation of liquid phase, crystal grain can grow up rapidly, thus shadow
Ring its mechanical performance.Addition grain growth inhibitor is the method that one kind effectively inhibits that crystal grain is grown up during being sintered, crystal grain
Inhibitor of growing up mainly has VC, Cr3C2, NbC, TiC, TaC, ZrC etc..And grain growth inhibitor can be evenly dispersed in
The performance of hard alloy is served in WC-Co nanosized hardmetal powder conclusive.So far, most commonly used addition
The method of grain growth inhibitor is ball-milling method, but ball-milling method is difficult for a small amount of grain growth inhibitor to be evenly dispersed in
In WC-Co nanosized hardmetal powder, the uneven dispersion of inhibitor will cause in sintering process WC phase in Binder Phase not
Uniform dissolution, to cause the abnormal growth of crystal grain, non-uniform microscopic structure inevitably damages the performance of hard alloy.
Generally, wet chemical method is considered as the effective ways of accurate, the finely dispersed nano material of prepared composition.
Nan Lin etc. (Scripta Materialia, 67 (2012), 826-829.) is prepared for WO using the mode of co-precipitation3-V2O5
Core-shell structure powder, then by itself and carbon black and Co3O4Carbonization obtains WC-VC-Co nanometer powder after being mixed.Hua Lin
Hydrothermal synthesis and spray drying process is used to prepare forerunner Deng (Ceramics International, 39 (2013), 9671-9675.)
Then body has prepared WC-VC-Co nanometer powder by original position carbon thermal reduction.(the Ceramics such as Mardali
International, 42 (2016), 9382-9386.) use sol-gal process to prepare presoma, then by gel in hydrogen
The WC-Co nanometer powder of VC doping is prepared in middle calcining.But these preparation methods or energy consumption are larger, time loss is longer,
Preparation method is cumbersome, and scale is smaller, is not suitable for and is mass produced.Add so developing the simple and efficient preparation of one kind
Adding the method for the WC-Co nanometer powder of grain growth inhibitor has critically important scientific meaning.
Summary of the invention
It is an object of the invention to according in the prior art or energy consumption is larger, time loss is longer or preparation method is numerous
It is trivial, the shortcomings that being not suitable for large-scale production, provide the simple and quick addition grain growth inhibitor WC-Co nanometer powder of one kind
Preparation method,
The present invention comprises the following specific steps that:
(1) presoma is prepared using low-temperature combustion synthesis.The process for preparing presoma is: by ammonium metatungstate, cobalt nitrate,
Fuel, ammonium nitrate are dissolved in deionized water by certain molar ratio is configured to aqueous solution, and aequum is added in aqueous solution
Grain growth inhibitor metal salt and organic carbon source, make it dissolve.Solution is heated to combustion reaction occurs, be obtained fluffy
Precursor powder.
(2) obtained precursor powder is ground, is then placed in tube furnace or vacuum drying oven and is carbonized, can be obtained and add
Add the WC-Co nanometer powder of grain growth inhibitor.
Fuel in step (1) is at least one of glycine, urea, EDTA, thiocarbamide.
The grain growth inhibitor metal salt of required addition in step (1) is chromic nitrate, ammonium molybdate, ammonium vanadate, nitric acid
At least one of niobium acyl, nitric acid tantalum acyl, lanthanum nitrate, yttrium nitrate.
Required organic carbon source in step (1) is at least one of glucose, soluble starch, citric acid.
Ammonium metatungstate, cobalt nitrate, fuel and ammonium nitrate molar ratio in step (1) are 1:(2.5~13): (10~
15): (15~25).
The amount of the grain growth inhibitor metal salt of addition in step (1) is according to required inhibitor in final product
Mass fraction calculate, mass fraction be 0.1%~5%.
Carburizing temperature is 750~1200 DEG C in step (2), and heating rate is 1~10 DEG C/min, and soaking time is 1~8h.
Carburizing atmosphere is nitrogen, hydrogen or argon gas in tube furnace, and carbonization needs furnace pressure lower than 100Pa in vacuum drying oven.
Technology of the invention has advantage below:
(1) raw material is simple and easy to get, and equipment is simple, and technique is quick, can prepare a large amount of product in a short time.
(2) method of presoma is prepared using wet chemical method, each ingredient has reached the other mixing of molecular level in the solution,
Tungsten oxide, cobalt oxide, inhibitor metal oxide and agraphitic carbon are uniformly mixed in obtained presoma, the oxidation of inhibitor metal
Object is dispersed in presoma.
(3) due in presoma oxide particle reach nano-scale, the diffusion path of carbon is short during carbonization,
Reaction temperature is low, and the reaction time is short.The WC-Co nano-powder particles finally prepared are tiny, and inhibitor is uniformly dispersed.
(4) ingredient of Binder Phase and inhibitor can be by adjusting the additional amount of raw material come freely in WC-Co nanometer powder
Accurately regulate and control.
Detailed description of the invention
Fig. 1 is the XRD spectrum for adding the WC-Co nanometer powder of grain growth inhibitor.
Specific embodiment
Embodiment 1
By 9.44g ammonium metatungstate, 5g cobalt nitrate hexahydrate, 4.3g urea, 10g ammonium nitrate, 6.5g glucose and 0.14g vanadic acid
Ammonium, which is put into beaker and suitable water is added, to be dissolved to obtain clear solution, which is placed on electric furnace and is heated to reaction hair
It is raw, obtain fluffy precursor powder.Precursor powder is put into tube furnace and is carbonized, carburizing temperature is 950 DEG C, soaking time
For 2.5h, the rate of heat addition is 8 DEG C/min, and protective atmosphere is argon gas, and cooled to room temperature obtains VC doping after the completion of heat preservation
WC-Co nanometer powder.
Embodiment 2
By 9.44g ammonium metatungstate, 3.8g cobalt nitrate hexahydrate, 4.3g urea, 10g ammonium nitrate, 6.5g glucose and 0.14g vanadium
Sour ammonium, which is put into beaker, to be added suitable water and dissolves to obtain clear solution, and solution is placed on and is previously heated to 260 DEG C of horse
Not in furnace, is taken out after reacting and occurring and obtain precursor powder.The placement of its body powder is carbonized in a vacuum furnace, reaction temperature
It is 900 DEG C, soaking time 1.5h, heating rate is 5 DEG C/min, and vacuum degree is lower than 100Pa, and cooled to room temperature obtains VC
The WC-Co nanometer powder of doping.
Embodiment 3
By 18.7g ammonium metatungstate, 7.57g cobalt nitrate hexahydrate, 8.5g urea, 20g ammonium nitrate, 13g glucose and 0.5g nitre
Sour chromium, which is put into beaker, to be added suitable water and dissolves to obtain clear solution, and solution is placed on and is previously heated to 245 DEG C of horse
Not heat preservation to combustion reaction is completed in furnace, and taking-up obtains precursor powder.Precursor powder is ground, is then placed in tube furnace
Carbonization, carburizing temperature are 1000 DEG C, soaking time 3h, my 10 DEG C/min of heating rate, cooled to room temperature obtains Cr3C2
The WC-Co nanometer powder of doping.
Embodiment 4
By 9.44g ammonium metatungstate, 6.4g cobalt nitrate hexahydrate, 4.3g urea, 10g ammonium nitrate, 6.5g glucose, 0.6g nitric acid
Chromium and 0.1g ammonium vanadate, which are put into beaker, to be added suitable water and dissolves to obtain clear solution, which is placed on electric furnace plus
Heat to reaction occurs, and obtains fluffy precursor powder.Precursor powder is put into tube furnace and is carbonized, carburizing temperature 950
DEG C, soaking time 3h, the rate of heat addition is 5 DEG C/min, and protective atmosphere is nitrogen, and cooled to room temperature obtains after the completion of heat preservation
VC, Cr3C2The WC-Co nanometer powder of doping.
Embodiment 5
By 18.7g ammonium metatungstate, 7.57g cobalt nitrate hexahydrate, 8.5g urea, 20g ammonium nitrate, 13g glucose and 1.2g nitre
Sour yttrium, which is put into beaker, to be added suitable water and dissolves to obtain clear solution, and solution is placed on and is previously heated to 250 DEG C of horse
Not heat preservation to combustion reaction is completed in furnace, and taking-up obtains precursor powder.Precursor powder is ground, is then placed in tube furnace
Carbonization, carburizing temperature are 900 DEG C, soaking time 2h, and heating rate is 5 DEG C/min, and cooled to room temperature obtains Y2O3Doping
WC-Co nanometer powder.
Claims (3)
1. a kind of preparation method for the WC-Co nanometer powder for adding grain growth inhibitor, it is characterised in that preparation step is as follows:
(1) presoma is prepared using low-temperature combustion synthesis, the process for preparing presoma is: by ammonium metatungstate, cobalt nitrate, combustion
Material, ammonium nitrate are dissolved in deionized water by certain molar ratio and are configured to aqueous solution, are added in aqueous solution the desired amount of
The metal salt and organic carbon source of grain growth inhibitor, make it dissolve；Solution is heated to combustion reaction occurs, be obtained fluffy
Precursor powder；
(2) obtained precursor powder is ground, is then placed in tube furnace or vacuum drying oven and is carbonized, it is brilliant that addition can be obtained
The WC-Co nanometer powder of the big inhibitor of grain length；
Fuel in step (1) is at least one of glycine, urea, EDTA, thiocarbamide；
The grain growth inhibitor metal salt of required addition in step (1) be chromic nitrate, ammonium molybdate, ammonium vanadate, nitric acid niobium acyl,
At least one of nitric acid tantalum acyl, lanthanum nitrate, yttrium nitrate；
Required organic carbon source in step (1) is at least one of glucose, soluble starch, citric acid；
Ammonium metatungstate, cobalt nitrate, fuel and ammonium nitrate molar ratio in step (1) are 1:(2.5~13): (10~15): (15
~25).
2. a kind of preparation method for the WC-Co nanometer powder for adding grain growth inhibitor, feature exist as described in claim 1
Quality of the amount of the grain growth inhibitor metal salt of addition in step (1) according to required inhibitor in final product
Score calculates, and mass fraction is 0.1%~5%.
3. a kind of preparation method for the WC-Co nanometer powder for adding grain growth inhibitor, feature exist as described in claim 1
Carburizing temperature is 750~1200 DEG C in step (2), and heating rate is 1~10 DEG C/min, and soaking time is 1~8h；Tube furnace
Middle carburizing atmosphere is nitrogen, hydrogen or argon gas, and carbonization needs furnace pressure lower than 100Pa in vacuum drying oven.
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| CN101760685B (en) * | 2008-12-25 | 2012-02-15 | 北京有色金属研究总院 | Superfine WC-Co cemented carbide containing rare-earth elements |
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| CN104087790B (en) * | 2014-04-09 | 2018-05-18 | 湖南博云东方粉末冶金有限公司 | For the adding method of grain growth inhibitor prepared by ultra-fine cemented carbide |
| CN104338935B (en) * | 2014-10-30 | 2017-01-18 | 赣州有色冶金研究所 | Method for simply and rapidly preparing nano WC-Co composite powder |
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