CN104746058A - Tungsten-molybdenum nanometer film-coated diamond and preparation method thereof - Google Patents
Tungsten-molybdenum nanometer film-coated diamond and preparation method thereof Download PDFInfo
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Abstract
The invention discloses tungsten-molybdenum nanometer film-coated diamond and a preparation method thereof and belongs to the field of metal-based composite materials. The preparation method comprises the following steps of 1, taking diamond materials with different shapes and sizes and carrying out surface coarsening on the diamond materials, 2, preparing molybdenum oxide-tungsten oxide composite sol and optionally adding a stabilizing agent into the composite sol, 3, adding the diamond materials into the composite sol for surface impregnation and carrying out drying, and 4, carrying out hydrogenthermal reduction to obtain a diamond matrix/tungsten-molybdenum carbide interface/tungsten-molybdenum alloy structure, wherein the thickness of the coating is controlled in a nanometer level. The preparation method has simple processes. The molybdena-tungsten oxide composite sol has stability and film forming performance superior to those of single-ingredient tungsten oxide sol and solves the problem that a sol film easily cracks in high-temperature hydrogenthermal treatment. The preparation method realizes uniform product coating with small thickness, reduces composite material interface thermal resistance so that thermal conductivity is high, and is suitable for industrial preparation of a diamond-reinforced metal-based composite material.
Description
Technical field
The present invention relates to field of metal matrix composite, be specifically related to diamond of a kind of coated tungsten nanometer rete and preparation method thereof, product can be used for the preparation preparing high-thermal conductive metal based composites, and object is that improving composite material interface combines, increases bonding strength, reduces interface resistance, improves heat conductivity.
Background technology
Diamond has multiple excellent properties, and especially it has the highest thermal conductivity and minimum thermal expansivity, becomes the preferred component of latest generation thermal management materials.Diamond strengthen metal-base composites worldwide become study hotspot at present, but pure metal and adamantine reaction too poor or too strong.The metal of heat conduction as high in some is as poor with adamantine boundary moisture in silver, copper, aluminium etc., interface cohesion is bad, thus causes matrix material to have lower thermal conductivity, higher thermal expansivity and lower mechanical property; Some other metal such as metals such as iron, cobalt and nickel then have stronger reactive behavior with diamond, composite material interface wettability is better, but interface cohesion is excessively strong, under high temperature, the carbide of Interface debond is blocked up, add interface resistance, thus reduce the thermal conductivity of matrix material, make matrix material cannot play the performance of its high heat conduction.
Tungsten has that thermal conductivity is high, thermal expansivity is moderate, and can at high temperature react generation wolfram varbide with diamond, therefore diamond surface plating tungsten not only can improve the hold of itself and metallic matrix, improve interface cohesion, greatly can also improve the heat conductivility of metal-base composites, simultaneously because tungsten is relative to diamond particles, its difference of thermal expansion coefficient is less simultaneously, therefore, it is possible to reduce the interfacial stress caused due to thermal mismatching, thus improve material work-ing life in the application.But because traditional plating, chemical plating method cannot prepare ultra-thin tungsten nanometer rete at diamond surface, and adopt the methods such as High temperature diffusion, vapour deposition and magnetron sputtering, then preparation cost is expensive, equipment is complicated and be difficult to ensure diamond surface plate integrity and the homogeneity of tungsten layer or molybdenum layer.There is although come in people to propose and adopt sol-gel process to prepare ultra-thin tungsten layer at diamond surface, but because the coated rete of single Tungsten oxide 99.999 exists the problems such as collosol stability difference, heat-treatment temperature range is narrower, rete easily chaps in hydrogen thermal reduction process, be therefore badly in need of the method finding solution.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, diamond of a kind of coated tungsten nanometer rete and preparation method thereof is provided.
To achieve these goals, technical scheme of the present invention is as follows:
A diamond for coated tungsten nanometer rete, its structure is that diamond body Surface coating has tungsten nanometer rete, there is the transition layer that micro-carbonic acid tungsten and carbonic acid molybdenum are formed between diamond body and tungsten nanometer rete; In tungsten nanometer rete, the mol ratio of Mo, W is 0.01 ~ 1:1.
The thickness of above-mentioned tungsten nanometer rete is 20nm ~ 1000nm.
Above-mentioned diamond body can be granular, fibrous, rope form, tabular, sheet or the film like diamond of 0 to 3 dimension.
The adamantine preparation method of above-mentioned coated tungsten nanometer rete, concrete preparation method comprises the steps:
(1) Feedstock treating: added by diamond in acid with strong oxidizing property, heated and boiled 0.5-2h, carries out roughening treatment to diamond surface;
(2) colloidal sol configuration: according to the mol ratio of Mo:W=0.01 ~ 1:1, molybdenum powder and tungsten powder are mixed, tungsten mixed powder is added H
2o
2in and constantly stir, total molar content of W and Mo and H
2o
2the ratio of molar content be 1:0.5 ~ 4, carry out oxidizing reaction at 0 ~ 10 DEG C; React completely in backward mixing solutions and add Glacial acetic acid and organic solvent successively, total molar content of W and Mo is 0.2-0.5:1:2 ~ 4 with the ratio of the molar content of Glacial acetic acid, organic solvent; Stir 0.5-72h at 60 DEG C ~ 90 DEG C after mixing, removing precipitation, obtains the complex sol of Tungsten oxide 99.999 and molybdenum oxide;
Or, according to the mol ratio of Mo:W=0.01 ~ 1:1, sodium wolframate and sodium molybdate solution are mixed, after the process of strong acidic ion resin post, obtain molybdenum oxide and Tungsten oxide 99.999 mixing solutions, in mixing solutions, add H successively
2o
2with organic solvent, total molar content of W and Mo and H
2o
2, organic solvent the ratio of molar content be 0.5-1:1:2 ~ 4, then add catalyzer Platinic chloride, stir 0.5-72h at 60 DEG C ~ 90 DEG C after mixing, removing precipitation, obtains Tungsten oxide 99.999 and molybdenum oxide complex sol;
(3) impregnation is with dry: the diamond after alligatoring is put into Tungsten oxide 99.999 and molybdenum oxide complex sol, carry out impregnation to diamond surface, then dry;
(4) hydrogen thermal reduction: dried product exhibited puts into tube furnace, under the flowing atmosphere of water vapour and hydrogen, is warming up to 700 DEG C ~ 1000 DEG C, and insulation 0.1 ~ 5h, obtains the diamond of Surface coating tungsten nanometer rete.
An adamantine preparation method for preferred coated tungsten nanometer rete, in the Tungsten oxide 99.999 prepared in step (2) and the complex sol of molybdenum oxide, adds stablizer; This stablizer is the one in water glass, silicon-dioxide, titanium oxide, boron oxide; In stablizer, the molar content of Si, Ti or B is 0.001 ~ 0.02:1 with the ratio of total molar content of W and Mo.
By adding modulus 2.1 ~ 3.4 in Tungsten oxide 99.999 and molybdenum oxide complex sol, the water glass of concentration 40wt% introduces water glass; Silicon-dioxide is introduced by the tetraethoxy adding 28wt% in Tungsten oxide 99.999 and molybdenum oxide complex sol; Titanium oxide is that the tetrabutyl titanate of purity more than 99% obtains through hydrolysis; By add in Tungsten oxide 99.999 and molybdenum oxide complex sol purity be more than 99% boric acid introduce boron oxide.
Acid with strong oxidizing property in step (1) is one or both mixing acid formed of concentrated nitric acid, sulfuric acid, concentrated nitric acid.
Molybdenum powder in step (2) and the granularity of tungsten powder are 250 orders, H
2o
2volume fraction be 30%, organic solvent is ethanol or acetone.
In step (2), the concentration of Platinic chloride is 0.10g/L, and add-on is 0.5% of mixed liquor volume.
The temperature of impregnation described in step (3) is 20 DEG C ~ 80 DEG C; Dry temperature is 50 DEG C ~ 90 DEG C, and time of drying is 0.5h ~ 10h; The thickness of diamond surface tungsten nanometer rete can be regulated and controled by repetition impregnation and drying step.
In the flowing atmosphere of water vapour and hydrogen described in step (4), the volume ratio of water vapour and hydrogen is 5 ~ 10:90 ~ 95, hydrogen flowing quantity 0.05L/min ~ 10L/min.
Beneficial effect of the present invention is: the diamond of coated tungsten nanometer rete of the present invention, and its thicknesses of layers is only 20-1000nm, compared to prior art, and even film layer, without exposed flawless; Preparation method of the present invention, uses pure tungsten powder and molybdenum powder to be oxidized and prepares mixed sols, there are raw material powder wide material sources, the obvious advantage of cost advantage; And the colloidal sol using sodium wolframate and sodium molybdate solution ion exchange method to prepare is more even; In addition, the interpolation of stablizer effectively can improve the viscosity of colloidal sol, stability and dip-coating performance, the problem that when can improve hydrogen thermal reduction, glued membrane is easy to crack; The present invention carries out modification to nanometer film according to actual needs, increases it and becomes film uniformity and solve hydrogen thermal reduction stage glued membrane performance easy to crack, and cushioned the stress problem between rete and diamond surface.
Embodiment
Below by way of specific embodiment, the present invention will be described in detail, but content not thereby limiting the invention.
Material that following embodiment uses is enough all from commercial channels, wherein adds Glacial acetic acid but not acetum that HAc is direct 99wt%, adds EtOH and directly adds the dehydrated alcohol of 99.7wt% but not aqueous ethanolic solution.
Comparative example one
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution heated and boiled 30min carry out surface coarsening process; Tungsten powder used is 250 orders, takes 0.01mol tungsten powder, is slowly joined by powder in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content be 0.05mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip the HAc of 0.02mol wherein, then add the EtOH of 0.02mol, after mixing, stir 24h at 80 DEG C, the white precipitate of container bottom is filtered, obtains the faint yellow colloidal sol of corresponding Tungsten oxide 99.999; Diamond after alligatoring is immersed in above-mentioned colloidal sol at 20 DEG C, takes out rear 50 DEG C of air drying 0.5h; Rise to 700 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min, obtains the diamond product with tungsten nanometer coating layer with wolfram varbide transition layer after process.Coating thickness 200nm, but there is crackle, cracking in coating layer.
Comparative example two
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution heated and boiled 30min carry out surface coarsening process; Molybdenum powder used is 250 orders, takes 0.01mol molybdenum powder, and powder slowly being joined concentration is in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content be 0.05mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip the HAc of 0.02mol wherein, then add the EtOH of 0.02mol, after mixing, stir 24h at 80 DEG C, the white precipitate of container bottom is filtered, obtains corresponding molybdenum oxide pale red colloidal sol; Diamond after alligatoring is immersed in above-mentioned colloidal sol at 20 DEG C, takes out rear 50 DEG C of air drying 0.5h; Rise to 700 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min, obtains the diamond product with molybdenum nanometer coating layer with molybdenum carbide transition layer after process.Coating thickness 232nm, but coating layer has the problem of exposed, the became uneven in local and cracking.
Comparative example three
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution heated and boiled 30min carry out surface coarsening process; Tungsten powder used is 250 orders, takes 0.01mol tungsten powder, and powder slowly being joined concentration is in the hydrogen peroxide of 30% volume fraction, H in this solution
2o
2content be 0.05mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip the HAc of 0.02mol wherein, then add the EtOH of 0.02mol, after mixing, stir 24h at 80 DEG C, the white precipitate of container bottom is filtered, obtains the faint yellow colloidal sol of corresponding Tungsten oxide 99.999; Ti:W=1:1 is taken the TiO 2 sol obtained by tetrabutyl titanate aquation and adds in Tungsten oxide 99.999 colloidal sol and obtain Tungsten oxide 99.999-titanium oxide mixed sols in molar ratio; Diamond after alligatoring is immersed in above-mentioned colloidal sol at 20 DEG C, takes out rear 50 DEG C of air drying 0.5h; Rise to 700 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min, obtains the diamond product with tungsten nanometer coating layer with wolfram varbide transition layer after process.Coating thickness 235nm, but there is be full of cracks, combination situation loosely in coating layer.
Embodiment one
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution heated and boiled 30min carry out surface coarsening process; Tungsten powder used and molybdenum powder are 250 orders, take 0.001mol tungsten powder and 0.00001mol molybdenum powder fully mixes, and are slowly joined by powder in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content 0.005mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip the HAc of 0.002mol wherein, then add the EtOH of 0.02mol, after mixing, stir 24h at 80 DEG C, the white precipitate of container bottom is filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide; Diamond after alligatoring is immersed in above-mentioned colloidal sol at 20 DEG C, takes out rear 50 DEG C of air drying 0.5h; Rise to 700 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 20nm, thickness is even, without exposed flawless.
Embodiment two
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution and concentration be 98.4% sulfuric acid mixture liquid heated and boiled 30min carry out surface coarsening process; Tungsten powder used and molybdenum powder are 250 orders, take 0.01mol tungsten powder and 0.01mol molybdenum powder fully mixes, and powder slowly being joined concentration is in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content be 0.08mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip 0.1mol HAc wherein, then add 0.4mol EtOH, after mixing, stir 72h at 20 DEG C, the white precipitate of container bottom is filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide; Diamond after alligatoring is immersed in above-mentioned colloidal sol at 20 DEG C, takes out rear 90 DEG C of air drying 10h; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 5h, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 10:90, hydrogen flowing quantity 10L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 242nm, thickness is even, without exposed flawless.
Embodiment three
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution and concentration be 36% hydrochloric acid mixed solution heated and boiled 2h carry out surface coarsening process; Tungsten powder used and molybdenum powder are 250 orders, take 0.01mol tungsten powder and 0.005mol molybdenum powder fully mixes, and powder slowly being joined concentration is in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content be 0.06mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip 0.075mol HAc wherein, then add 0.3mol EtOH, after mixing, stir 72h at 60 DEG C, the white precipitate of container bottom is filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide; Diamond after alligatoring is immersed in above-mentioned colloidal sol at 80 DEG C, takes out rear 80 DEG C of air drying 2h; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 1h, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 8:92, hydrogen flowing quantity 5L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 255nm, thickness is even, without exposed flawless.
Embodiment four
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution and concentration be 36% hydrochloric acid mixed solution heated and boiled 2h carry out surface coarsening process; Tungsten powder used and molybdenum powder are 250 orders, take 0.01mol tungsten powder and 0.005mol molybdenum powder fully mixes, and powder slowly being joined concentration is in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content be 0.06mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip 0.075mol HAc wherein, then add 0.3mol EtOH, after mixing, stir 72h at 60 DEG C, the white precipitate of container bottom is filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide; Immersed in above-mentioned colloidal sol at 20 DEG C by diamond after alligatoring, take out rear 80 DEG C of air drying 2h, impregnation-drying process carries out 10 times repeatedly; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 1h, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min,, after process, obtain the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer.Coating thickness 1000nm, thickness is even, without exposed flawless.
Embodiment five
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution and concentration be 36% hydrochloric acid mixed solution heated and boiled 2h carry out surface coarsening process; Tungsten powder used and molybdenum powder are 250 orders, take 0.01mol tungsten powder and 0.005mol molybdenum powder fully mixes, and powder slowly being joined concentration is in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content be 0.06mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip 0.075mol HAc wherein, then add 0.3mol EtOH, after mixing, stir 72h at 60 DEG C, the white precipitate of container bottom is filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide; Be 0.001:1 according to the ratio of the molar content of B, total molar content of W and Mo, the boric acid adding 0.1wt% wherein stirs, and the boron oxide formed after adding boric acid is as stablizer; Immersed in above-mentioned colloidal sol at 20 DEG C by diamond after alligatoring, take out rear 80 DEG C of air drying 2h, impregnation-drying process carries out 8 times repeatedly; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 1h, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 800nm, thickness is even, without exposed flawless.
Embodiment six
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid solution and concentration be 36% hydrochloric acid mixed solution heated and boiled 2h carry out surface coarsening process; Tungsten powder used and molybdenum powder are 250 orders, take 0.01mol tungsten powder and 0.005mol molybdenum powder fully mixes, and powder slowly being joined concentration is in the hydrogen peroxide solution of 30% volume fraction, H in this solution
2o
2content be 0.06mol, react in a water bath, temperature controls at 0 DEG C ~ 10 DEG C, Keep agitation is until dissolve completely, then drip 0.075mol HAc wherein, then add 0.3mol EtOH, after mixing, stir 72h at 60 DEG C, the white precipitate of container bottom is filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide.Be 0.02:1 according to the ratio of the molar content of Ti, total molar content of W and Mo, add titanium oxide sol wherein, titanium oxide sol is obtained by tetrabutyl titanate aquation, stirs.Immersed in above-mentioned colloidal sol at 60 DEG C by diamond after alligatoring, take out rear 80 DEG C of air drying 2h, impregnation-drying process carries out 5 times repeatedly; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 1h, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 900nm, thickness is even, without exposed flawless.
Embodiment seven
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid and concentrated hydrochloric acid solution heated and boiled 30min carry out surface coarsening process; 0.0001mol Sodium orthomolybdate and 0.01mol sodium wolframate wiring solution-forming mixed solution, mixed solution flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and Tungsten oxide 99.999 mixing solutions, adds the hydrogen peroxide containing 30% volume fraction, make H in solution in mixed sols
2o
2content be 0.0101mol, then add the acetone of 0.0202mol, then add the catalyzer Platinic chloride that concentration is 0.10g/L, its volume is 0.5% of molybdenum oxide and Tungsten oxide 99.999 mixing solutions.Prepare rear 60 DEG C of heating in water bath and fully stir 24h, the precipitation of container bottom being filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide; Diamond after alligatoring is immersed above-mentioned colloidal sol and carries out impregnation, impregnation temperature is 80 DEG C, takes out rear 60 DEG C of dry 2h; Rise to 700 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 10L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 230nm, coating layer is even, intact.
Embodiment eight
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid and concentrated hydrochloric acid solution heated and boiled 30min carry out surface coarsening process; 0.01mol Sodium orthomolybdate and 0.01mol sodium wolframate wiring solution-forming mixed solution, mixed solution flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and Tungsten oxide 99.999 mixing solutions, adds the hydrogen peroxide of 30% volume fraction, make H in solution in mixed sols
2o
2content be 0.04mol, then add the acetone of 0.16mol, then add the catalyzer Platinic chloride that concentration is 0.10g/L, its volume is 0.5% of molybdenum oxide and Tungsten oxide 99.999 mixing solutions.Prepare rear 60 DEG C of heating in water bath and fully stir 24h, the precipitation of container bottom being filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide; Diamond after alligatoring is immersed above-mentioned colloidal sol and carries out impregnation, impregnation temperature 60 C, take out rear 60 DEG C of dry 2h, repeatedly impregnation-drying 2 times; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 10:90, hydrogen flowing quantity 5L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 350nm, coating layer is even, intact.
Embodiment nine
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid and concentrated hydrochloric acid solution heated and boiled 30min carry out surface coarsening process; 0.01mol Sodium orthomolybdate and 0.02mol sodium wolframate wiring solution-forming mixed solution, mixed solution flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and Tungsten oxide 99.999 mixing solutions, adds the hydrogen peroxide of 30% volume fraction, make H in solution in mixed sols
2o
2content be 0.04mol, then add the acetone of 0.08mol, then add the catalyzer Platinic chloride that concentration is 0.10g/L, its volume is 0.5% of molybdenum oxide and Tungsten oxide 99.999 mixing solutions.Prepare rear 60 DEG C of heating in water bath and fully stir 24h, the precipitation of container bottom being filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide.Be 0.001:1 according to the ratio of the molar content of Si, total molar content of W and Mo, add the tetraethoxy that concentration is 28wt% wherein, the titanium dioxide formed after adding tetraethoxy is as stablizer.Diamond after alligatoring is immersed above-mentioned colloidal sol and carries out impregnation, impregnation temperature 80 DEG C, take out rear 60 DEG C of dry 2h, repeatedly impregnation-drying 2 times; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 10:90, hydrogen flowing quantity 5L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 400nm, coating layer is even, intact.
Embodiment ten
Adopt particulate state diamond, its granularity is 140/170 order, get 10g diamond particles put into concentration be 65% concentrated nitric acid and concentrated hydrochloric acid solution heated and boiled 30min carry out surface coarsening process; 0.01mol Sodium orthomolybdate and 0.02mol sodium wolframate wiring solution-forming mixed solution, mixed solution flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and Tungsten oxide 99.999 mixing solutions, adds the hydrogen peroxide of 30% volume fraction, H in this solution in mixed sols
2o
2content be 0.04mol, then add the acetone of 0.12mol, then add the catalyzer Platinic chloride that concentration is 0.10g/L, its volume is 0.5% of molybdenum oxide and Tungsten oxide 99.999 mixing solutions.Prepare rear 60 DEG C of heating in water bath and fully stir 24h, the precipitation of container bottom being filtered, obtains corresponding Tungsten oxide 99.999 and the faint yellow complex sol of molybdenum oxide.According to the molar content of Si, the ratio 0.02:1 of the total molar content of W and Mo, adding modulus is wherein 2.1, and concentration is the water glass of 40wt%, add that water glass formed water glass as stablizer.Diamond after alligatoring is immersed above-mentioned colloidal sol and carries out impregnation, impregnation temperature 20 DEG C, take out rear 60 DEG C of dry 2h, repeatedly impregnation-drying 3 times; Rise to 1000 DEG C after first rising to 250 DEG C of insulations during hydrogen thermal reduction and carry out insulation 30min, water vapour and the hydrogen stream volume ratio of water vapour and hydrogen in atmosphere of taking offence is 10:90, hydrogen flowing quantity 5L/min, obtains the diamond product with tungsten nanometer coating layer with tungsten wolfram varbide transition layer after process.Coating thickness 600nm, coating layer is even, intact.
Although content of the present invention has carried out relatively detailed introduction by above-mentioned preferred embodiment, the description of above-described embodiment should not become restriction of the present invention.Therefore, protection scope of the present invention should have appended claim to limit.
Claims (10)
1. a diamond for coated tungsten nanometer rete, is characterized in that, diamond body Surface coating has tungsten nanometer rete, there is the transition layer that micro-carbonic acid tungsten and carbonic acid molybdenum are formed between diamond body and tungsten nanometer rete; In described tungsten nanometer rete, the mol ratio of Mo, W is 0.01 ~ 1:1.
2. the diamond of coated tungsten nanometer rete according to claim 1, is characterized in that, the thickness of described tungsten nanometer rete is 20nm ~ 1000nm.
3. the adamantine preparation method of the coated tungsten nanometer rete described in claim 1 to 2, it is characterized in that, concrete preparation method comprises the steps:
(1) Feedstock treating: added by diamond in acid with strong oxidizing property, heated and boiled 0.5-2h, carries out roughening treatment to diamond surface;
(2) colloidal sol configuration: according to the mol ratio of Mo:W=0.01 ~ 1:1, molybdenum powder and tungsten powder are mixed, tungsten mixed powder is added H
2o
2in and constantly stir, total molar content of W and Mo and H
2o
2the ratio of molar content be 1:0.5 ~ 4, carry out oxidizing reaction at 0 ~ 10 DEG C; React completely in backward mixing solutions and add Glacial acetic acid and organic solvent successively, total molar content of W and Mo is 0.2-0.5:1:2 ~ 4 with the ratio of the molar content of Glacial acetic acid, organic solvent; Stir 0.5-72h at 60 DEG C ~ 90 DEG C after mixing, removing precipitation, obtains the complex sol of Tungsten oxide 99.999 and molybdenum oxide;
Or, according to the mol ratio of Mo:W=0.01 ~ 1:1, sodium wolframate and sodium molybdate solution are mixed, after the process of strong acidic ion resin post, obtain molybdenum oxide and Tungsten oxide 99.999 mixing solutions, in mixing solutions, add H successively
2o
2with organic solvent, total molar content of W and Mo and H
2o
2, organic solvent the ratio of molar content be 0.5-1:1:2 ~ 4, then add catalyzer Platinic chloride, stir 0.5-72h at 60 DEG C ~ 90 DEG C after mixing, removing precipitation, obtains Tungsten oxide 99.999 and molybdenum oxide complex sol;
(3) impregnation is with dry: the diamond after alligatoring is put into Tungsten oxide 99.999 and molybdenum oxide complex sol, carry out impregnation to diamond surface, then dry;
(4) hydrogen thermal reduction: dried product exhibited puts into tube furnace, under the flowing atmosphere of water vapour and hydrogen, is warming up to 700 DEG C ~ 1000 DEG C, and insulation 0.1 ~ 5h, obtains the diamond of Surface coating tungsten nanometer rete.
4. preparation method according to claim 3, is characterized in that, in Tungsten oxide 99.999 and molybdenum oxide complex sol described in step (2), add stablizer; Described stablizer is the one in water glass, silicon-dioxide, titanium oxide or boron oxide; In stablizer, the molar content of Si, Ti or B is 0.001 ~ 0.02:1 with the ratio of total molar content of W and Mo.
5. preparation method according to claim 4, is characterized in that, by adding modulus 2.1 ~ 3.4 in Tungsten oxide 99.999 and molybdenum oxide complex sol, the water glass of concentration 40wt% introduces water glass; Silicon-dioxide is introduced by the tetraethoxy adding 28wt% in Tungsten oxide 99.999 and molybdenum oxide complex sol; Titanium oxide is that the tetrabutyl titanate of purity more than 99% obtains through hydrolysis; By add in Tungsten oxide 99.999 and molybdenum oxide complex sol purity be more than 99% boric acid introduce boron oxide.
6. the preparation method according to any one of claim 3-5, is characterized in that, acid with strong oxidizing property described in step (1) is one or both mixing acid formed of concentrated nitric acid, sulfuric acid, concentrated nitric acid.
7. the preparation method according to any one of claim 3-5, is characterized in that, described in step (2), the granularity of molybdenum powder and tungsten powder is 250 orders, H
2o
2volume fraction be 30%, organic solvent is ethanol or acetone.
8. the preparation method according to any one of claim 3-5, is characterized in that, described in step (2), the concentration of Platinic chloride is 0.10g/L, and add-on is 0.5% of mixed liquor volume.
9. the preparation method according to any one of claim 3-5, is characterized in that, the temperature of impregnation described in step (3) is 20 DEG C ~ 80 DEG C; Dry temperature is 50 DEG C ~ 90 DEG C, and time of drying is 0.5h ~ 10h; The thickness of diamond surface tungsten nanometer rete can be regulated and controled by repetition impregnation and drying step.
10. the preparation method according to any one of claim 3-5, is characterized in that, in the flowing atmosphere of water vapour and hydrogen described in step (4), the volume ratio of water vapour and hydrogen is 5 ~ 10:90 ~ 95, hydrogen flowing quantity 0.05L/min ~ 10L/min.
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