CN104746058B - A kind of diamond for coating tungsten nanometer film layer and preparation method thereof - Google Patents
A kind of diamond for coating tungsten nanometer film layer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses diamond of a kind of cladding tungsten nanometer film layer for belonging to field of metal matrix composite and preparation method thereof, including：1）The diamond of different shape and yardstick is taken, roughening treatment is carried out to its surface；2）The complex sol of molybdenum oxide and tungsten oxide is prepared, stabilizer is optionally added into complex sol；3）Diamond is put into complex sol and carries out surface impregnation and drying；4）Hydrogen thermal reduction reaction is carried out, the structure of diamond body/tungsten carbide interface/tungsten-molybdenum alloy is formed, coating thickness is controlled in nanoscale.This method process is simple, molybdenum oxide has more preferable stability and filming performance with the more single tungsten oxide colloidal sol of tungsten oxide complex sol, solve the problem of dissolved glue film is easy to crack in high temperature hydrogen heat treatment process, product surface cladding film layer evenly, thicknesses of layers it is smaller, and composite material interface thermal resistance acquisition more high heat conductance can be reduced, suitable for preparation of industrialization diamond reinforced metal-base composite material.
Description
Technical field
The present invention relates to field of metal matrix composite, and in particular to a kind of diamond of cladding tungsten nanometer film layer and its
Preparation method, product can be used for the preparation for preparing high-thermal conductive metal based composites, it is therefore intended that improve composite material interface knot
Close, increase bond strength, reduction interface resistance, improve heat conductivity.
Background technology
Diamond has a variety of excellent properties, and especially it has highest thermal conductivity and minimum thermal coefficient of expansion, into
For the preferred component of latest generation thermal management materials.The enhanced metal-base composites of diamond worldwide turns at present
Study hotspot, but the reaction of simple metal and diamond is either too poor or too strong.Such as the metal such as silver, copper, aluminium of some high heat conductions
Deng with the boundary moisture of diamond is poor, interface cohesion is bad so that cause composite that there is relatively low thermal conductivity, it is higher
Thermal coefficient of expansion and relatively low mechanical property；And have stronger with diamond if some other metal such as metals such as iron, cobalt and nickel
Reactivity, preferably, but interface cohesion is too strong for composite material interface wetability, and the carbide of high temperature lower bound face generation is blocked up,
Interface resistance is added, so as to reduce the thermal conductivity of composite so that composite can not play the performance of its high heat conduction.
Tungsten has that thermal conductivity is high, thermal coefficient of expansion is moderate, and can react generation tungsten carbide at high temperature with diamond,
Therefore diamond surface plating tungsten can not only improve its hold with metallic matrix, improve interface cohesion, while can also be very big
The heat conductivility of metal-base composites is improved, simultaneously because tungsten is relative to diamond particles, its difference of thermal expansion coefficient is smaller,
Therefore, it is possible to reduce due to interfacial stress caused by thermal mismatching, so as to improve the service life of material in the application.But due to
Traditional plating, chemical plating method can not prepare ultra-thin tungsten nanometer film layer in diamond surface, and use High temperature diffusion, gas phase
Deposition and the method such as magnetron sputtering, then prepare costly, equipment complicated and be difficult to ensure that diamond surface plates tungsten layer or molybdenum
The integrality and uniformity of layer.Although coming in it is proposed that being prepared using sol-gel process in diamond surface ultra-thin
Tungsten layer, but because single tungsten oxide cladding film layer exists during hydrogen thermal reduction, collosol stability is poor, heat-treatment temperature range
The problems such as narrower, film layer is easily cracked, therefore the method that urgent need finds solution.
The content of the invention
The purpose of the present invention be in view of the shortcomings of the prior art there is provided it is a kind of coat tungsten nanometer film layer diamond and its
Preparation method.
To achieve these goals, technical scheme is as follows：
A kind of diamond for coating tungsten nanometer film layer, its structure is that diamond body Surface coating has tungsten nanometer film
, there is the transition zone that micro carbonic acid tungsten and carbonic acid molybdenum are constituted between diamond body and tungsten nanometer film layer in layer；Tungsten nanometer film
Mo, W mol ratio are 0.01~1 in layer:1.
The thickness of above-mentioned tungsten nanometer film layer is 20nm~1000nm.
Above-mentioned diamond body can be 0 to the granular, fibrous of 3-dimensional, rope form, tabular, sheet or film-form diamond.
The preparation method of the diamond of above-mentioned cladding tungsten nanometer film layer, specific preparation method comprises the following steps：
（1）Feedstock treating：Diamond is added in acid with strong oxidizing property, 0.5-2h is boiled in heating, diamond surface is carried out
Roughening treatment；
（2）Colloidal sol is configured：According to Mo:W=0.01~1:Molybdenum powder and tungsten powder are well mixed by 1 mol ratio, and tungsten is mixed
Powder adds H2O2In and be stirred continuously, W and Mo total moles content and H2O2The ratio between molar content be 1:0.5~4,0~
10 DEG C of progress oxidation reactions；The total moles of glacial acetic acid and organic solvent, W and Mo are sequentially added in the completely backward mixed solution of reaction
The ratio between content and glacial acetic acid, the molar content of organic solvent are 0.2-0.5:1:2~4；Stirred after well mixed at 60 DEG C~90 DEG C
0.5-72h is mixed, precipitation is removed, obtains the complex sol of tungsten oxide and molybdenum oxide；
Or, according to Mo:W=0.01~1:1 mol ratio mixes sodium tungstate and sodium molybdate solution, through highly acid sun from
After sub- resin column processing, molybdenum oxide and tungsten oxide mixed solution are obtained, H is sequentially added into mixed solution2O2With organic solvent, W
With Mo total moles content and H2O2, organic solvent the ratio between molar content be 0.5-1:1:2~4, add catalyst chlorine platinum
Acid, 0.5-72h is stirred after being well mixed at 60 DEG C~90 DEG C, is removed precipitation, is obtained tungsten oxide and molybdenum oxide complex sol；
（3）Impregnation and drying：Diamond after roughening is put into tungsten oxide and molybdenum oxide complex sol, to diamond table
Face carries out impregnation, then dries；
（4）Hydrogen thermal reduction：Dried product exhibited is put into tube furnace, under the flowing atmosphere of vapor and hydrogen, is warming up to
700 DEG C~1000 DEG C, 0.1~5h is incubated, the diamond of Surface coating tungsten nanometer film layer is obtained.
A kind of preparation method of the diamond of preferred cladding tungsten nanometer film layer, in step（2）The oxidation prepared
In the complex sol of tungsten and molybdenum oxide, stabilizer is added；The stabilizer is in sodium metasilicate, silica, titanium oxide, boron oxide
It is a kind of；Si, Ti or B molar content are 0.001~0.02 with the ratio between W and Mo total moles content in stabilizer:1.
By the waterglass introducing that modulus 2.1~3.4, concentration 40wt% are added into tungsten oxide and molybdenum oxide complex sol
Sodium metasilicate；Silica is introduced by the tetraethyl orthosilicate that 28wt% is added into tungsten oxide and molybdenum oxide complex sol；Titanium oxide
Butyl titanate for purity more than 99% is obtained through hydrolysis；By being with adding purity in molybdenum oxide complex sol to tungsten oxide
More than 99% boric acid introduces boron oxide.
Step（1）In acid with strong oxidizing property be concentrated nitric acid, the mixed acid of one or two kinds of compositions of sulfuric acid, concentrated nitric acid.
Step（2）In molybdenum powder and tungsten powder granularity be 250 mesh, H2O2Volume fraction be 30%, organic solvent is ethanol
Or acetone.
Step（2）The concentration of middle chloroplatinic acid is 0.10g/L, and addition is the 0.5% of mixed liquor volume.
Step（3）Described in impregnation temperature be 20 DEG C~80 DEG C；Dry temperature is 50 DEG C~90 DEG C, and drying time is
0.5h~10h；It can regulate and control the thickness of diamond surface tungsten nanometer film layer by repeating impregnation and drying steps.
Step（4）Described in vapor and hydrogen flowing atmosphere in vapor and hydrogen volume ratio be 5~10:90~
95, hydrogen flowing quantity 0.05L/min~10L/min.
Beneficial effects of the present invention are：The diamond of the cladding tungsten nanometer film layer of the present invention, its thicknesses of layers is only 20-
1000nm, compared to prior art, even film layer, without exposed flawless；The preparation method of the present invention, uses pure tungsten powder and molybdenum powder
Oxidation prepares mixed sols, there are raw material powder wide material sources, cost advantage clear advantage；And use sodium tungstate and sodium molybdate molten
The colloidal sol that liquid is prepared with ion-exchange is more uniformly distributed；In addition, the addition of stabilizer can be effectively improved the viscosity, stably of colloidal sol
Property and dip-coating performance, the problem of glued membrane is easy to crack when can improve hydrogen thermal reduction；The present invention enters to nanometer film according to actual needs
Row is modified, and is increased it into film uniformity and is solved hydrogen thermal reduction stage glued membrane performance easy to crack, and buffered film layer with
Stress problem between diamond surface.
Embodiment
Below by way of specific embodiment, the present invention will be described in detail, but not thereby limiting the invention interior
Hold.
Following embodiments use material to reach from commercial channels, wherein adding HAc for direct 99wt% glacial acetic acid
Non- acetum, addition EtOH is directly addition 99.7wt% absolute ethyl alcohol rather than ethanol water.
Comparative example one
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid solution；Tungsten powder used is 250 mesh, 0.01mol tungsten powders is weighed, by powder
In the hydrogen peroxide solution for being slowly added into 30% volume fraction, H in the solution2O2Content be 0.05mol, carry out in a water bath anti-
Should, temperature control is stirred continuously until that dissolving is complete, 0.02mol HAc is then added dropwise thereto, adds at 0 DEG C~10 DEG C
0.02mol EtOH, stirs 24h at 80 DEG C after being well mixed, the white precipitate of container bottom is filtered, aoxidized accordingly
The faint yellow colloidal sol of tungsten；By the diamond after roughening in 20 DEG C of above-mentioned colloidal sol of immersion, 50 DEG C of air drying 0.5h after taking-up；Hydrogen
First risen to during thermal reduction after 250 DEG C of insulations and rise to 700 DEG C of progress insulation 30min, vapor and hydrogen stream are taken offence vapor in atmosphere
Volume ratio with hydrogen is 5:95, hydrogen flowing quantity 0.05L/min, obtain carrying tungsten nanometer with tungsten carbide transition zone after processing
The diamond product of clad.Coating thickness 200nm, but there is crackle, cracking in clad.
Comparative example two
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid solution；Molybdenum powder used is 250 mesh, 0.01mol molybdenum powders is weighed, by powder
It is slowly added into the hydrogen peroxide solution that concentration is 30% volume fraction, H in the solution2O2Content be 0.05mol, in a water bath
Reacted, temperature control is stirred continuously until that dissolving is complete, 0.02mol HAc is then added dropwise thereto at 0 DEG C~10 DEG C,
0.02mol EtOH is added, 24h is stirred at 80 DEG C after being well mixed, the white precipitate of container bottom is filtered, obtains corresponding
Molybdenum oxide pale red colloidal sol；By the diamond after roughening in 20 DEG C of above-mentioned colloidal sol of immersion, 50 DEG C of air dryings after taking-up
0.5h；First risen to during hydrogen thermal reduction after 250 DEG C of insulations and rise to 700 DEG C of progress insulation 30min, vapor is taken offence with hydrogen stream in atmosphere
The volume ratio of vapor and hydrogen is 5:95, hydrogen flowing quantity 0.05L/min, obtain carrying with molybdenum carbide transition zone after processing
The diamond product of molybdenum nanometer clad.Coating thickness 232nm, but clad has local exposed, became uneven and cracking
The problem of.
Comparative example three
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid solution；Tungsten powder used is 250 mesh, 0.01mol tungsten powders is weighed, by powder
It is slowly added into the hydrogen peroxide that concentration is 30% volume fraction, H in the solution2O2Content be 0.05mol, carry out in a water bath
Reaction, temperature control is stirred continuously until that dissolving is complete at 0 DEG C~10 DEG C, 0.02mol HAc is then added dropwise thereto, then add
Enter 0.02mol EtOH, stir 24h at 80 DEG C after being well mixed, the white precipitate of container bottom is filtered, corresponding oxygen is obtained
Change the faint yellow colloidal sol of tungsten；Ti in molar ratio:W=1:1, which weighs the TiO 2 sol obtained by butyl titanate aquation, adds oxygen
Change in tungsten colloidal sol and obtain tungsten oxide-titanium oxide mixed sols；By the diamond after roughening in 20 DEG C of above-mentioned colloidal sol of immersion, take out
50 DEG C of air drying 0.5h afterwards；First risen to during hydrogen thermal reduction after 250 DEG C of insulations and rise to 700 DEG C of progress insulation 30min, vapor
It is 5 with the hydrogen stream volume ratio of vapor and hydrogen in atmosphere of taking offence:95, hydrogen flowing quantity 0.05L/min, are obtained with carbon after processing
Change the diamond product with tungsten nanometer clad of tungsten transition zone.Coating thickness 235nm, but there is cracking, knot in clad
Close situation loosely.
Embodiment one
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid solution；Tungsten powder and molybdenum powder used are 250 mesh, weigh 0.001mol tungsten
Powder and 0.00001mol molybdenum powders be sufficiently mixed uniformly, in the hydrogen peroxide solution that powder is slowly added into 30% volume fraction,
H in the solution2O2Content 0.005mol, reacted in a water bath, temperature control is stirred continuously until molten at 0 DEG C~10 DEG C
Solution is complete, and 0.002mol HAc is then added dropwise thereto, 0.02mol EtOH is added, in 80 DEG C of stirrings after being well mixed
24h, the white precipitate of container bottom is filtered, and obtains corresponding tungsten oxide and the faint yellow complex sol of molybdenum oxide；After being roughened
Diamond in 20 DEG C of above-mentioned colloidal sol of immersion, 50 DEG C of air drying 0.5h after taking-up；250 DEG C of guarantors are first risen to during hydrogen thermal reduction
Rise to 700 DEG C of progress insulation 30min after temperature, vapor and the hydrogen stream volume ratio of vapor and hydrogen in atmosphere of taking offence are 5:95,
The diamond with tungsten nanometer clad with tungsten tungsten carbide transition zone is obtained after hydrogen flowing quantity 0.05L/min, processing
Product.Coating thickness 20nm, thickness is uniform, without exposed flawless.
Embodiment two
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
Acid solution boils 30min for heating in 98.4% sulfuric acid mixture liquid with concentration and carries out surface coarsening processing；Tungsten powder and molybdenum powder used
It is 250 mesh, weighs 0.01mol tungsten powders and 0.01mol molybdenum powders be sufficiently mixed uniformly, powder is slowly added into concentration is
In the hydrogen peroxide solution of 30% volume fraction, H in the solution2O2Content be 0.08mol, reacted in a water bath, temperature control
System is stirred continuously until that dissolving is complete, 0.1mol HAc is then added dropwise thereto, 0.4mol is added at 0 DEG C~10 DEG C
EtOH, stirs 72h at 20 DEG C after being well mixed, the white precipitate of container bottom is filtered, and obtains corresponding tungsten oxide and oxidation
The faint yellow complex sol of molybdenum；By the diamond after roughening in 20 DEG C of above-mentioned colloidal sol of immersion, 90 DEG C of air dryings after taking-up
10h；First risen to during hydrogen thermal reduction after 250 DEG C of insulations and rise to 1000 DEG C of progress insulation 5h, vapor and hydrogen stream are taken offence atmosphere reclaimed water
The volume ratio of steam and hydrogen is 10:90, hydrogen flowing quantity 10L/min, obtain the band with tungsten tungsten carbide transition zone after processing
There is the diamond product of tungsten nanometer clad.Coating thickness 242nm, thickness is uniform, without exposed flawless.
Embodiment three
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
Acid solution boils 2h for heating in 36% hydrochloric acid mixed solution with concentration and carries out surface coarsening processing；Tungsten powder and molybdenum powder used are
250 mesh, weigh 0.01mol tungsten powders and 0.005mol molybdenum powders be sufficiently mixed uniformly, and it is 30% that powder is slowly added into concentration
In the hydrogen peroxide solution of volume fraction, H in the solution2O2Content be 0.06mol, reacted in a water bath, temperature control exists
0 DEG C~10 DEG C, it is stirred continuously until that dissolving is complete, 0.075mol HAc is then added dropwise thereto, 0.3mol EtOH are added,
72h is stirred at 60 DEG C after well mixed, the white precipitate of container bottom is filtered, corresponding tungsten oxide is obtained yellowish with molybdenum oxide
Color complex sol；By the diamond after roughening in 80 DEG C of above-mentioned colloidal sol of immersion, 80 DEG C of air drying 2h after taking-up；Hydrogen heat is also
First risen to when former after 250 DEG C of insulations and rise to 1000 DEG C of progress insulation 1h, vapor and hydrogen stream are taken offence vapor and hydrogen in atmosphere
Volume ratio be 8:92, hydrogen flowing quantity 5L/min, obtain being wrapped with tungsten nanometer with tungsten tungsten carbide transition zone after processing
The diamond product of coating.Coating thickness 255nm, thickness is uniform, without exposed flawless.
Example IV
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
Acid solution boils 2h for heating in 36% hydrochloric acid mixed solution with concentration and carries out surface coarsening processing；Tungsten powder and molybdenum powder used are
250 mesh, weigh 0.01mol tungsten powders and 0.005mol molybdenum powders be sufficiently mixed uniformly, and it is 30% that powder is slowly added into concentration
In the hydrogen peroxide solution of volume fraction, H in the solution2O2Content be 0.06mol, reacted in a water bath, temperature control exists
0 DEG C~10 DEG C, it is stirred continuously until that dissolving is complete, 0.075mol HAc is then added dropwise thereto, 0.3mol EtOH are added,
72h is stirred at 60 DEG C after well mixed, the white precipitate of container bottom is filtered, corresponding tungsten oxide is obtained yellowish with molybdenum oxide
Color complex sol；By the diamond after roughening in 20 DEG C of above-mentioned colloidal sol of immersion, 80 DEG C of air drying 2h after taking-up, impregnation-
Drying process is repeated 10 times；First risen to during hydrogen thermal reduction 250 DEG C insulation after rise to 1000 DEG C progress insulation 1h, vapor with
The hydrogen stream volume ratio of vapor and hydrogen in atmosphere of taking offence is 5:95, hydrogen flowing quantity 0.05L/min, obtained after processing with tungsten
The diamond product with tungsten nanometer clad of molybdenum tungsten carbide transition zone.Coating thickness 1000nm, thickness is uniform, without naked
Reveal flawless.
Embodiment five
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
Acid solution boils 2h for heating in 36% hydrochloric acid mixed solution with concentration and carries out surface coarsening processing；Tungsten powder and molybdenum powder used are
250 mesh, weigh 0.01mol tungsten powders and 0.005mol molybdenum powders be sufficiently mixed uniformly, and it is 30% that powder is slowly added into concentration
In the hydrogen peroxide solution of volume fraction, H in the solution2O2Content be 0.06mol, reacted in a water bath, temperature control exists
0 DEG C~10 DEG C, it is stirred continuously until that dissolving is complete, 0.075mol HAc is then added dropwise thereto, 0.3mol EtOH are added,
72h is stirred at 60 DEG C after well mixed, the white precipitate of container bottom is filtered, corresponding tungsten oxide is obtained yellowish with molybdenum oxide
Color complex sol；Ratio according to B molar content, W and Mo total moles content is 0.001:1,0.1wt% is added thereto
Boric acid be stirred uniformly, add after boric acid the boron oxide that is formed as stabilizer；By the diamond after roughening in 20 DEG C of leachings
Enter in above-mentioned colloidal sol, 80 DEG C of air drying 2h after taking-up, impregnation-drying process is repeated 8 times；First risen to during hydrogen thermal reduction
Rise to 1000 DEG C of progress insulation 1h after 250 DEG C of insulations, vapor and the hydrogen stream volume ratio of vapor and hydrogen in atmosphere of taking offence are
5:95, hydrogen flowing quantity 0.05L/min, obtain the gold with tungsten nanometer clad with tungsten tungsten carbide transition zone after processing
Hard rock product.Coating thickness 800nm, thickness is uniform, without exposed flawless.
Embodiment six
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
Acid solution boils 2h for heating in 36% hydrochloric acid mixed solution with concentration and carries out surface coarsening processing；Tungsten powder and molybdenum powder used are
250 mesh, weigh 0.01mol tungsten powders and 0.005mol molybdenum powders be sufficiently mixed uniformly, and it is 30% that powder is slowly added into concentration
In the hydrogen peroxide solution of volume fraction, H in the solution2O2Content be 0.06mol, reacted in a water bath, temperature control exists
0 DEG C~10 DEG C, it is stirred continuously until that dissolving is complete, 0.075mol HAc is then added dropwise thereto, 0.3mol EtOH are added,
72h is stirred at 60 DEG C after well mixed, the white precipitate of container bottom is filtered, corresponding tungsten oxide is obtained yellowish with molybdenum oxide
Color complex sol.Ratio according to Ti molar content, W and Mo total moles content is 0.02:1, oxygen is added thereto
Change titanium colloidal sol, titanium oxide sol is obtained by butyl titanate aquation, be stirred uniform.By the diamond after roughening at 60 DEG C
Immerse in above-mentioned colloidal sol, 80 DEG C of air drying 2h after taking-up, impregnation-drying process is repeated 5 times；First risen during hydrogen thermal reduction
Rise to 1000 DEG C of progress insulation 1h after to 250 DEG C of insulations, vapor and hydrogen stream are taken offence the volume ratio of vapor and hydrogen in atmosphere
For 5:95, hydrogen flowing quantity 0.05L/min, obtained after processing with tungsten tungsten carbide transition zone with tungsten nanometer clad
Diamond product.Coating thickness 900nm, thickness is uniform, without exposed flawless.
Embodiment seven
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid and concentrated hydrochloric acid solution；0.0001mol sodium molybdates and 0.01mol sodium tungstates
Wiring solution-forming mixed liquor, mixed liquor flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and tungsten oxide mixed solution,
The hydrogen peroxide containing 30% volume fraction is added into mixed sols, makes H in solution2O2Content be 0.0101mol, add
0.0202mol acetone, adds the catalyst chloroplatinic acid that concentration is 0.10g/L, and its volume is that molybdenum oxide and tungsten oxide are mixed
The 0.5% of solution.Prepare rear 60 DEG C of heating water baths and be sufficiently stirred for 24h, the precipitation of container bottom is filtered, corresponding oxygen is obtained
Change tungsten and the faint yellow complex sol of molybdenum oxide；Diamond after roughening is immersed into above-mentioned colloidal sol and carries out impregnation, impregnation temperature is 80
DEG C, 60 DEG C of dry 2h after taking-up；First risen to during hydrogen thermal reduction after 250 DEG C of insulations and rise to 700 DEG C of progress insulation 30min, vapor
It is 5 with the hydrogen stream volume ratio of vapor and hydrogen in atmosphere of taking offence:95, hydrogen flowing quantity 10L/min, are obtained with tungsten after processing
The diamond product with tungsten nanometer clad of tungsten carbide transition zone.Coating thickness 230nm, clad is uniform, intact.
Embodiment eight
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid and concentrated hydrochloric acid solution；0.01mol sodium molybdates and 0.01mol sodium tungstates are matched somebody with somebody
Into solution mixed liquor, mixed liquor flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and tungsten oxide mixed solution, to
The hydrogen peroxide of 30% volume fraction is added in mixed sols, makes H in solution2O2Content be 0.04mol, add 0.16mol's
Acetone, adds the catalyst chloroplatinic acid that concentration is 0.10g/L, and its volume is the 0.5% of molybdenum oxide and tungsten oxide mixed solution.
Prepare rear 60 DEG C of heating water baths and be sufficiently stirred for 24h, the precipitation of container bottom is filtered, corresponding tungsten oxide and molybdenum oxide is obtained
Faint yellow complex sol；Diamond after roughening is immersed into above-mentioned colloidal sol and carries out impregnation, impregnation temperature 60 C is done for 60 DEG C after taking-up
Dry 2h, repeatedly impregnation-drying 2 times；First risen to during hydrogen thermal reduction after 250 DEG C of insulations and rise to 1000 DEG C of progress insulation 30min, water steams
Gas and the hydrogen stream volume ratio of vapor and hydrogen in atmosphere of taking offence are 10:90, hydrogen flowing quantity 5L/min, are obtained with tungsten after processing
The diamond product with tungsten nanometer clad of molybdenum tungsten carbide transition zone.Coating thickness 350nm, clad is uniform, complete
It is good.
Embodiment nine
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid and concentrated hydrochloric acid solution；0.01mol sodium molybdates and 0.02mol sodium tungstates are matched somebody with somebody
Into solution mixed liquor, mixed liquor flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and tungsten oxide mixed solution, to
The hydrogen peroxide of 30% volume fraction is added in mixed sols, makes H in solution2O2Content be 0.04mol, add 0.08mol's
Acetone, adds the catalyst chloroplatinic acid that concentration is 0.10g/L, and its volume is the 0.5% of molybdenum oxide and tungsten oxide mixed solution.
Prepare rear 60 DEG C of heating water baths and be sufficiently stirred for 24h, the precipitation of container bottom is filtered, corresponding tungsten oxide and molybdenum oxide is obtained
Faint yellow complex sol.Ratio according to Si molar content, W and Mo total moles content is 0.001:1, add thereto dense
The tetraethyl orthosilicate for 28wt% is spent, the titanium dioxide formed after tetraethyl orthosilicate is added as stabilizer.By the Buddha's warrior attendant after roughening
Stone immerses above-mentioned colloidal sol and carries out impregnation, 80 DEG C of impregnation temperature, 60 DEG C of dry 2h, repeatedly impregnation-drying 2 times after taking-up；Hydrogen heat is also
First risen to when former after 250 DEG C of insulations and rise to 1000 DEG C of progress insulation 30min, vapor and hydrogen stream are taken offence vapor and hydrogen in atmosphere
The volume ratio of gas is 10:90, hydrogen flowing quantity 5L/min, obtain carrying tungsten nanometer with tungsten tungsten carbide transition zone after processing
The diamond product of clad.Coating thickness 400nm, clad is uniform, intact.
Embodiment ten
Using graininess diamond, its granularity is 140/170 mesh, takes 10g diamond particles to be put into the dense nitre that concentration is 65%
30min progress surface coarsening processing is boiled in heating in acid and concentrated hydrochloric acid solution；0.01mol sodium molybdates and 0.02mol sodium tungstates are matched somebody with somebody
Into solution mixed liquor, mixed liquor flows through strong acidic ion resin post and collects i.e. acquisition molybdenum oxide and tungsten oxide mixed solution, to
The hydrogen peroxide of 30% volume fraction is added in mixed sols, H in the solution2O2Content be 0.04mol, add 0.12mol's
Acetone, adds the catalyst chloroplatinic acid that concentration is 0.10g/L, and its volume is the 0.5% of molybdenum oxide and tungsten oxide mixed solution.
Prepare rear 60 DEG C of heating water baths and be sufficiently stirred for 24h, the precipitation of container bottom is filtered, corresponding tungsten oxide and molybdenum oxide is obtained
Faint yellow complex sol.According to the ratio between Si molar content, W and Mo total moles contents 0.02:1, modulus is added thereto is
2.1, concentration is 40wt% waterglass, and the sodium metasilicate that addition waterglass is formed is as stabilizer.By the diamond after roughening
Immerse above-mentioned colloidal sol and carry out impregnation, 20 DEG C of impregnation temperature, 60 DEG C of dry 2h, repeatedly impregnation-drying 3 times after taking-up；Hydrogen thermal reduction
When first rise to after 250 DEG C of insulations and rise to 1000 DEG C of progress insulation 30min, vapor and hydrogen stream are taken offence vapor and hydrogen in atmosphere
Volume ratio be 10:90, hydrogen flowing quantity 5L/min, obtain being wrapped with tungsten nanometer with tungsten tungsten carbide transition zone after processing
The diamond product of coating.Coating thickness 600nm, clad is uniform, intact.
Although present disclosure has carried out introduction, above-mentioned reality in detail relatively by above-mentioned preferred embodiment
The limitation of the present invention should not be turned into by applying the description of example.Therefore, protection scope of the present invention should have appended claim to limit
It is fixed.
Claims (9)
1. a kind of diamond for coating tungsten nanometer film layer, it is characterised in that diamond body Surface coating has tungsten nanometer film
, there is the transition zone that micro tungsten carbide and molybdenum carbide are constituted between diamond body and tungsten nanometer film layer in layer；The tungsten is received
Mo, W mol ratio are 0.01~1 in rice film layer:1；Specific preparation method comprises the following steps：
(1) Feedstock treating：Diamond is added in acid with strong oxidizing property, 0.5-2h is boiled in heating, and diamond surface is roughened
Processing；
(2) colloidal sol is configured：According to Mo:W=0.01~1:Molybdenum powder and tungsten powder are well mixed by 1 mol ratio, by tungsten mixed powder
End adds H2O2In and be stirred continuously, W and Mo total moles content and H2O2The ratio between molar content be 1:0.5~4,0~10
DEG C carry out oxidation reaction；React and glacial acetic acid and organic solvent are sequentially added in completely backward mixed solution, W and Mo total moles contain
The ratio between amount and glacial acetic acid, the molar content of organic solvent are 0.2-0.5:1:2~4；In 60 DEG C~90 DEG C stirrings after well mixed
0.5-72h, removes precipitation, obtains the complex sol of tungsten oxide and molybdenum oxide；
Or, according to Mo:W=0.01~1:1 mol ratio mixes sodium tungstate and sodium molybdate solution, through highly acidic cation tree
After the processing of fat post, molybdenum oxide and tungsten oxide mixed solution are obtained, H is sequentially added into mixed solution2O2With organic solvent, W and Mo
Total moles content and H2O2, organic solvent the ratio between molar content be 0.5-1:1:2~4, catalyst chloroplatinic acid is added, is mixed
0.5-72h are stirred at 60 DEG C~90 DEG C after closing uniformly, precipitation is removed, obtains tungsten oxide and molybdenum oxide complex sol；
(3) impregnation and drying：Diamond after roughening is put into tungsten oxide with molybdenum oxide complex sol, entering to diamond surface
Row impregnation, is then dried；
(4) hydrogen thermal reduction：Dried product exhibited is put into tube furnace, under the flowing atmosphere of vapor and hydrogen, is warming up to 700 DEG C
~1000 DEG C, 0.1~5h is incubated, the diamond of Surface coating tungsten nanometer film layer is obtained.
2. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that the tungsten nanometer film layer
Thickness be 20nm~1000nm.
3. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that described in step (2)
Tungsten oxide in molybdenum oxide complex sol with adding stabilizer；The stabilizer is sodium metasilicate, silica, titanium oxide or boron oxide
In one kind；Si, Ti or B molar content are 0.001~0.02 with the ratio between W and Mo total moles content in stabilizer:1.
4. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that by tungsten oxide and oxygen
Change the waterglass introducing sodium metasilicate that modulus 2.1~3.4, concentration 40wt% are added in molybdenum complex sol；By to tungsten oxide and oxygen
Change the tetraethyl orthosilicate introducing silica that 28wt% is added in molybdenum complex sol；Titanium oxide is the metatitanic acid four of purity more than 99%
Butyl ester is obtained through hydrolysis；Aoxidized by adding purity into tungsten oxide and molybdenum oxide complex sol for more than 99% boric acid introducing
Boron.
5. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that strong described in step (1)
Oxidizing acid is concentrated nitric acid, the mixed acid of one or two kinds of compositions of sulfuric acid.
6. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that molybdenum described in step (2)
The granularity of powder and tungsten powder is 250 mesh, H2O2Volume fraction be 30%, organic solvent be ethanol or acetone.
7. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that chlorine described in step (2)
The concentration of platinic acid is 0.10g/L, and addition is the 0.5% of mixed liquor volume.
8. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that soaked described in step (3)
The temperature of glue is 20 DEG C~80 DEG C；Dry temperature is 50 DEG C~90 DEG C, and drying time is 0.5h~10h；By repeating impregnation
The thickness of diamond surface tungsten nanometer film layer can be regulated and controled with drying steps.
9. the diamond of cladding tungsten nanometer film layer according to claim 1, it is characterised in that water described in step (4)
The volume ratio of vapor and hydrogen is 5~10 in the flowing atmosphere of steam and hydrogen:90~95, hydrogen flowing quantity 0.05L/min~
10L/min。
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| CN1361077A (en) * | 2000-12-29 | 2002-07-31 | 中国科学院广州能源研究所 | Method of preparing gas-discoloration WO3 film on a substrate |
| CN1954042A (en) * | 2004-09-23 | 2007-04-25 | 六号元素(控股)公司 | Polycrystalline abrasive materials and method of manufacture |
| CN101664809A (en) * | 2009-10-09 | 2010-03-10 | 株洲硬质合金集团有限公司 | Uniform macromeritic tungsten powder and method for preparing tungsten carbide powder |
| CN102356138A (en) * | 2009-02-11 | 2012-02-15 | 六号元素（产品）（控股）公司 | Process for coating diamond with refractory metal carbide and methal |
| CN102560455A (en) * | 2012-01-10 | 2012-07-11 | 上海交通大学 | Preparation method of ultra-thin tungsten film-coated diamond |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361077A (en) * | 2000-12-29 | 2002-07-31 | 中国科学院广州能源研究所 | Method of preparing gas-discoloration WO3 film on a substrate |
| CN1954042A (en) * | 2004-09-23 | 2007-04-25 | 六号元素(控股)公司 | Polycrystalline abrasive materials and method of manufacture |
| CN102356138A (en) * | 2009-02-11 | 2012-02-15 | 六号元素（产品）（控股）公司 | Process for coating diamond with refractory metal carbide and methal |
| CN101664809A (en) * | 2009-10-09 | 2010-03-10 | 株洲硬质合金集团有限公司 | Uniform macromeritic tungsten powder and method for preparing tungsten carbide powder |
| CN102560455A (en) * | 2012-01-10 | 2012-07-11 | 上海交通大学 | Preparation method of ultra-thin tungsten film-coated diamond |
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