CN105177538B - A kind of preparation method of nanometer of copper clad monocrystalline sapphire fiber - Google Patents
A kind of preparation method of nanometer of copper clad monocrystalline sapphire fiber Download PDFInfo
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- CN105177538B CN105177538B CN201510588770.7A CN201510588770A CN105177538B CN 105177538 B CN105177538 B CN 105177538B CN 201510588770 A CN201510588770 A CN 201510588770A CN 105177538 B CN105177538 B CN 105177538B
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- monocrystalline sapphire
- copper clad
- whisker
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- monocrystalline
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- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 119
- 239000010980 sapphire Substances 0.000 title claims abstract description 119
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 72
- 239000010949 copper Substances 0.000 title claims abstract description 72
- 239000000835 fiber Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 26
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 26
- -1 copper complex ion Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 7
- 239000010437 gem Substances 0.000 claims description 6
- 229910001751 gemstone Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011157 advanced composite material Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention provides the preparation method of a kind of nanometer of copper clad monocrystalline sapphire fiber, including：A, alkaline sodium borohydride reduction solution is prepared at room temperature；B, the reproducibility mixed liquor of monocrystalline sapphire whisker is prepared；C, the navy blue solution containing ammoniacal copper complex ion is prepared；D, blended liquid phase made from mixed liquor made from b and c is mixed to prepare the monocrystalline sapphire mixed liquor of nanometer copper clad；E, it filters, washing obtains the monocrystalline sapphire whisker of wet nanometer copper clad；F, the monocrystalline sapphire whisker of wet nanometer copper clad is dried, the monocrystalline sapphire whisker that nanometer copper clad is contained on surface can be obtained.The methods experiment process of the modified monocrystalline sapphire whisker of copper clad of the invention is easy to operate, which easily realizes industrialization, has a good application prospect.
Description
Technical field
The invention belongs to field of compound material, in particular to the preparation sides of a kind of nanometer copper clad monocrystalline sapphire fiber
Method.
Background technique
Monocrystalline sapphire fiber is a kind of signle crystal alumina fiber (whisker) with certain draw ratio, it and semiconductor serve as a contrast
Bottom sapphire wafer material applications and preparation method are entirely different.High-melting-point, high intensity, high-modulus, to be able to bear strong corrosion be to third
For the composite request of advanced composite material.And monocrystalline sapphire fiber is the optimal selection for meeting composite request at present.
Metal-base composites is that both had by selection optimum organization metallic matrix or alloy substrate and reinforcer
There are metallic character, and the material of the comprehensive performance with high specific strength, high ratio modulus, heat-resisting, wear-resisting etc..Monocrystalline sapphire whisker
(Single crystal sapphire Whisker) is the high-purity monocrystal for cultivating growth under controlled conditions, crystal
Structure is near-complete, without containing crystal defects such as boundary or grain, dislocation, cavities, small, high-intensitive, high-melting-point, high abrasion with specific gravity
The physical property of amount and highly corrosion resistant, can significantly improve the specific strength and specific modulus of composite material.Monocrystalline sapphire whisker
Optimal selection as third generation advanced composite material.
After monocrystalline sapphire whisker is added in a metal, can significantly improve the bending elastic modulus of product, tensile strength,
Dimensional stability and thermal distoftion temperature.The component quality made of high specific strength, specific modulus composite material is small, the good, intensity of rigidity
Height is ideal structural material in aerospace field.It can be used as aircraft turbine engine and rocket engine hot-zone and Supersonic
The surfacing of fast aircraft.After metal material is added in inorganic crystal whisker, the properties of metal material, aluminium borate whisker can be improved
Enhancing metallic composite has succeeded application in metal alloy industry, resulting materials can used in engine piston, connecting rod,
On the heat-resistant parts such as compresser cylinder（Application [J] the chemical industry mine of Dai Jing, Wang Min, Zhang Jincai aluminium borate whisker in the composite
Object and processing, 2005, (10):36-38）.Whisker alloy filter, compressor blade and in terms of application also very
Extensively.
Matrix accounts for very at high proportion in metal-base composites, and generally 60% or more, good thermal conductivity can be passed effectively
Heat reduces the gradient generated after component is heated, radiates rapidly, this is particularly important to the component that dimensionally stable is high.It is good simultaneously
Electric conductivity can be effectively prevented aircraft component and lead to the problem of static focus.
It is bad with the wetability of metal since monocrystalline sapphire whisker is thermally conductive, poorly conductive, it cannot be formed with metal function
Firm bonding, limits the application of monocrystalline sapphire whisker reinforced metal matrix composites.
Summary of the invention
The purpose of the present invention is to provide a kind of method using the modified monocrystalline sapphire whisker of coated copper, the present invention can be with
Wellability when monocrystalline sapphire whisker and metal composite is effectively improved, solves the problems, such as that electrical and thermal conductivity is poor.
In order to achieve the above object, the technical scheme is that：
A kind of preparation method of nanometer of copper clad monocrystalline sapphire fiber, including：A, at room temperature, sodium borohydride is added to
In weak aqua ammonia, 1 ~ 5min is stirred, alkaline sodium borohydride reduction solution is obtained；B, monocrystalline sapphire whisker is added to above-mentioned alkali
Property sodium borohydride solution reducing solution in, with ultrasonic washing instrument to containing monocrystalline sapphire whisker solution ultrasonic disperse handle,
Obtain the reproducibility mixed liquor containing monocrystalline sapphire whisker；C, weak aqua ammonia is gradually added dropwise in copper salt solution, then has light blue
Precipitating generate, continue ammonium hydroxide to precipitating is added dropwise being completely dissolved, at this time up to the navy blue solution containing ammoniacal copper complex ion；d,
It is stirred using magnetic agitation instrument, with 5 drops/min ~ 10 drops/min speed to the reproducibility mixed liquor containing monocrystalline sapphire whisker
Middle solution of the addition containing ammoniacal copper complex ion stops stirring, obtains Nanometer Copper until monocrystalline sapphire whisker becomes red
The monocrystalline sapphire mixed liquor of cladding；E, the monocrystalline sapphire mixed liquor after reaction is filtered, washing obtains wet nanometer copper-clad
The monocrystalline sapphire whisker covered；F, the monocrystalline sapphire whisker of wet nanometer copper clad is dried, surface can be obtained and contain
The monocrystalline sapphire whisker of nanometer copper clad.
The mass ratio of sodium borohydride and weak aqua ammonia is 1 in the step a:1 ~ 50, dilute ammonia concn is 1~30% (w/
v)。
The temperature of ultrasonic washing instrument described in step b is 40 ~ 60 DEG C, and the processing time is 5 ~ 10min.
The mass ratio of monocrystalline sapphire whisker and sodium borohydride is 1 ~ 1 in step b:10.
Mantoquita is copper sulphate, copper nitrate, copper chloride, copper acetate or their combination in step c.
The concentration of the mantoquita be 1~30% (w/v), dilute ammonia concn be 1~30% (w/v), and mantoquita used with
The mass ratio of monocrystalline sapphire whisker is 1~100: 1.
The revolving speed of magnetic agitation instrument is the r/min of 250 r/min ~ 500 in step d, to going back containing monocrystalline sapphire whisker
The speed that the solution containing ammoniacal copper complex ion is added in originality mixed liquor is 5 drops/min ~ 10 drops/min.
It is by the method washed after the monocrystalline sapphire mixed liquor filtering after reaction in step e：Deionized water washing 2 ~ 5
It is secondary；Drying means in step f is：By the monocrystalline sapphire whisker of wet nanometer copper clad temperature be 60 ~ 100 DEG C at into
Row drying, drying time are 3 ~ 9h.
A kind of metallic composite, including Nanometer Copper coating modification monocrystalline sapphire made from method of the present invention are brilliant
Palpus.
The beneficial effects of the invention are as follows：
（1）The present invention is intended to provide the method for a kind of nanometer of copper clad monocrystalline sapphire whisker, it is blue precious to can achieve monocrystalline
The clad ratio on stone crystal whisker surface 98%, the monocrystalline sapphire whisker after copper clad not only keep original excellent performance, also have with
The good wellability of metal composite, electric conductivity thermal conductivity are good.The modified monocrystalline sapphire whisker of resulting copper clad can be used as gold
The toughening body of metal-matrix composite material.
（2）The method of the modified monocrystalline sapphire whisker of copper clad of the invention, experimentation is easy to operate, and the technique is easy
It realizes industrialization, has a good application prospect.
（3）The method of the modified monocrystalline sapphire whisker of copper clad of the invention, raw material is cheap, from a wealth of sources, and has
Good environmental benefit and economic benefit.
Specific embodiment
The present invention is described in further detail by embodiment.
Embodiment 1
（1）At room temperature, 10g sodium borohydride is added in the weak aqua ammonia that 20g concentration is 1~30% (w/v), stirring 1 ~
5min obtains alkaline sodium borohydride reduction solution.
（2）10g monocrystalline sapphire whisker is added in above-mentioned alkaline sodium borohydride solution reducing solution.Temperature be 40 ~
5 ~ 10min is handled to the solution ultrasonic disperse containing monocrystalline sapphire whisker in 60 DEG C of ultrasonic washing instrument, is obtained containing single
The reproducibility mixed liquor of brilliant sapphire whisker.
（3）Weak aqua ammonia is gradually added dropwise in the sulfuric acid solution of 40g20%, then has precipitating azury to generate, continues that ammonia is added dropwise
Water to precipitating is completely dissolved, at this time up to the navy blue solution containing ammoniacal copper complex ion.
（4）Using magnetic agitation instrument revolving speed be 250 r/min ~ 500 r/min mixing speed under, with 5 drop/
Min ~ 10 drops/min speed is added into the reproducibility mixed liquor containing monocrystalline sapphire whisker contains the molten of ammoniacal copper complex ion
Liquid stops stirring, obtains the monocrystalline sapphire mixed liquor of nanometer copper clad until monocrystalline sapphire whisker becomes red.
（5）By the mixed liquor filtering after reaction, deionized water is washed 2 ~ 3 times, and the monocrystalline for obtaining wet nanometer copper clad is blue
Jewel whisker.
（6）It is dried at being 60 ~ 100 DEG C in temperature by the monocrystalline sapphire whisker of wet nanometer copper clad, when dry
Between be 3 ~ 9h, the monocrystalline sapphire whisker that nanometer copper clad is contained on surface can be obtained.Through measuring, for yield up to 85%, monocrystalline is blue precious
The metallic copper of 17.8% mass is contained on stone crystal whisker surface, and monocrystalline sapphire whisker surface copper clad rate is 88%.
Embodiment 2
（1）At room temperature, 20g sodium borohydride is added in the weak aqua ammonia that 30g concentration is 1~30% (w/v), stirring 1 ~
5min obtains alkaline sodium borohydride reduction solution.
（2）10g monocrystalline sapphire whisker is added in above-mentioned alkaline sodium borohydride solution reducing solution.Temperature be 40 ~
5 ~ 10min is handled to the solution ultrasonic disperse containing monocrystalline sapphire whisker in 60 DEG C of ultrasonic washing instrument, is obtained containing single
The reproducibility mixed liquor of brilliant sapphire whisker.
（3）Weak aqua ammonia is gradually added dropwise in the sulfuric acid solution of 40g10%, then has precipitating azury to generate, continues that ammonia is added dropwise
Water to precipitating is completely dissolved, at this time up to the navy blue solution containing ammoniacal copper complex ion.
（4）Using magnetic agitation instrument revolving speed be 250 r/min ~ 500 r/min mixing speed under, with 5 drop/
Min ~ 10 drops/min speed is added into the reproducibility mixed liquor containing monocrystalline sapphire whisker contains the molten of ammoniacal copper complex ion
Liquid stops stirring, obtains the monocrystalline sapphire mixed liquor of nanometer copper clad until monocrystalline sapphire whisker becomes red.
（5）By the mixed liquor filtering after reaction, deionized water is washed 2 ~ 3 times, and the monocrystalline for obtaining wet nanometer copper clad is blue
Jewel whisker.
（6）It is dried at being 60 ~ 100 DEG C in temperature by the monocrystalline sapphire whisker of wet nanometer copper clad, when dry
Between be 3 ~ 9h, the monocrystalline sapphire whisker that nanometer copper clad is contained on surface can be obtained.Through measuring, for yield up to 90%, monocrystalline is blue precious
The metallic copper of 19% mass is contained on stone crystal whisker surface, and monocrystalline sapphire whisker surface copper clad rate is 92%.
Embodiment 3
（1）At room temperature, 30g sodium borohydride is added in the weak aqua ammonia that 50g concentration is 1~30% (w/v), stirring 1 ~
5min obtains alkaline sodium borohydride reduction solution.
（2）10g monocrystalline sapphire whisker is added in above-mentioned alkaline sodium borohydride solution reducing solution.Temperature be 40 ~
5 ~ 10min is handled to the solution ultrasonic disperse containing monocrystalline sapphire whisker in 60 DEG C of ultrasonic washing instrument, is obtained containing single
The reproducibility mixed liquor of brilliant sapphire whisker.
（3）Weak aqua ammonia is gradually added dropwise in the sulfuric acid solution of 50g20%, then has precipitating azury to generate, continues that ammonia is added dropwise
Water to precipitating is completely dissolved, at this time up to the navy blue solution containing ammoniacal copper complex ion.
（4）Using magnetic agitation instrument revolving speed be 250 r/min ~ 500 r/min mixing speed under, with 5 drop/
Min ~ 10 drops/min speed is added into the reproducibility mixed liquor containing monocrystalline sapphire whisker contains the molten of ammoniacal copper complex ion
Liquid stops stirring, obtains the monocrystalline sapphire mixed liquor of nanometer copper clad until monocrystalline sapphire whisker becomes red.
（5）By the mixed liquor filtering after reaction, deionized water is washed 2 ~ 3 times, and the monocrystalline for obtaining wet nanometer copper clad is blue
Jewel whisker.
（6）It is dried at being 60 ~ 100 DEG C in temperature by the monocrystalline sapphire whisker of wet nanometer copper clad, when dry
Between be 3 ~ 9h, the monocrystalline sapphire whisker that nanometer copper clad is contained on surface can be obtained.Through measuring, for yield up to 90%, monocrystalline is blue precious
The metallic copper of 25% mass is contained on stone crystal whisker surface, and monocrystalline sapphire whisker surface copper clad rate is 94%.
Embodiment 4
（1）At room temperature, 40g sodium borohydride is added in the weak aqua ammonia that 60g concentration is 1~30% (w/v), stirring 1 ~
5min obtains alkaline sodium borohydride reduction solution.
（2）10g monocrystalline sapphire whisker is added in above-mentioned alkaline sodium borohydride solution reducing solution.Temperature be 40 ~
5 ~ 10min is handled to the solution ultrasonic disperse containing monocrystalline sapphire whisker in 60 DEG C of ultrasonic washing instrument, is obtained containing single
The reproducibility mixed liquor of brilliant sapphire whisker.
（3）Weak aqua ammonia is gradually added dropwise in the sulfuric acid solution of 50g30%, then has precipitating azury to generate, continues that ammonia is added dropwise
Water to precipitating is completely dissolved, at this time up to the navy blue solution containing ammoniacal copper complex ion.
（4）Using magnetic agitation instrument revolving speed be 250 r/min ~ 500 r/min mixing speed under, with 5 drop/
Min ~ 10 drops/min speed is added into the reproducibility mixed liquor containing monocrystalline sapphire whisker contains the molten of ammoniacal copper complex ion
Liquid stops stirring, obtains the monocrystalline sapphire mixed liquor of nanometer copper clad until monocrystalline sapphire whisker becomes red.
（5）By the mixed liquor filtering after reaction, deionized water is washed 2 ~ 3 times, and the monocrystalline for obtaining wet nanometer copper clad is blue
Jewel whisker.
（6）It is dried at being 60 ~ 100 DEG C in temperature by the monocrystalline sapphire whisker of wet nanometer copper clad, when dry
Between be 3 ~ 9h, the monocrystalline sapphire whisker that nanometer copper clad is contained on surface can be obtained.Through measuring, for yield up to 93%, monocrystalline is blue precious
The metallic copper of 28% mass is contained on stone crystal whisker surface, and monocrystalline sapphire whisker surface copper clad rate is 96%.
Embodiment 5
（1）At room temperature, 100g sodium borohydride is added in the weak aqua ammonia that 80g concentration is 1~30% (w/v), stirring 1 ~
5min obtains alkaline sodium borohydride reduction solution.
（2）10g monocrystalline sapphire whisker is added in above-mentioned alkaline sodium borohydride solution reducing solution.Temperature be 40 ~
5 ~ 10min is handled to the solution ultrasonic disperse containing monocrystalline sapphire whisker in 60 DEG C of ultrasonic washing instrument, is obtained containing single
The reproducibility mixed liquor of brilliant sapphire whisker.
（3）Weak aqua ammonia is gradually added dropwise in the sulfuric acid solution of 60g30%, then has precipitating azury to generate, continues that ammonia is added dropwise
Water to precipitating is completely dissolved, at this time up to the navy blue solution containing ammoniacal copper complex ion.
（4）Using magnetic agitation instrument revolving speed be 250 r/min ~ 500 r/min mixing speed under, with 5 drop/
Min ~ 10 drops/min speed is added into the reproducibility mixed liquor containing monocrystalline sapphire whisker contains the molten of ammoniacal copper complex ion
Liquid stops stirring, obtains the monocrystalline sapphire mixed liquor of nanometer copper clad until monocrystalline sapphire whisker becomes red.
（5）By the mixed liquor filtering after reaction, deionized water is washed 2 ~ 3 times, and the monocrystalline for obtaining wet nanometer copper clad is blue
Jewel whisker.
（6）It is dried at being 60 ~ 100 DEG C in temperature by the monocrystalline sapphire whisker of wet nanometer copper clad, when dry
Between be 3 ~ 9h, the monocrystalline sapphire whisker that nanometer copper clad is contained on surface can be obtained.Through measuring, for yield up to 95%, monocrystalline is blue precious
The metallic copper of 30% mass is contained on stone crystal whisker surface, and monocrystalline sapphire whisker surface copper clad rate is 98%.
The processed monocrystalline sapphire whisker of Examples 1 to 5 is subjected to coating content, clad ratio, electric conductivity and thermal conductivity
Test, to cladding monocrystalline sapphire whisker characterize（0 represents the monocrystalline sapphire whisker of not copper clad）, test knot
Fruit is as shown in table 1：
Table 1
Case study on implementation monocrystalline sapphire whisker surface copper content wt% monocrystalline sapphire whisker surface copper clad rate copper-clad
Cover monocrystalline sapphire crystal whisker conductive (s/m) copper clad monocrystalline sapphire crystal whisker conductive (w/mK)
| Implement Case | Monocrystalline sapphire whisker table Face copper content wt% | Monocrystalline sapphire whisker Surface copper clad rate | Copper clad monocrystalline sapphire is brilliant It must electric conductivity (s/m) | Copper clad monocrystalline sapphire is brilliant It must electric conductivity (w/mK) |
| 0 | 0 | 0 | 1×10-14 | 36 |
| 1 | 17.8% | 88 % | 2.42×106 | 115 |
| 2 | 19% | 92 % | 5.93×106 | 126 |
| 3 | 25% | 94% | 7.89×106 | 132 |
| 4 | 28% | 96% | 8.65×106 | 138 |
| 5 | 30% | 98% | 9.15×106 | 140 |
Note：Two parameters use power spectrum constituent content analysis method, x-ray photoelectron spectroscopy analytic approach, ampere respectively in table
Table, thermal conductivity measuring apparatus.
Embodiment described above is merely illustrative of the invention's technical idea and feature, and the description thereof is more specific and detailed,
Its object is to make those skilled in the art can understand the content of the present invention and implement it accordingly, therefore cannot be only with this
To limit the scope of the patents of the invention, it is noted that for those of ordinary skill in the art, do not departing from this hair
Under the premise of bright design, various modifications and improvements can be made, i.e., all any modifications made according to an embodiment of the present invention, etc.
With variation and modification, in the range of still falling within technical solution of the present invention.
Claims (7)
1. the preparation method of a kind of nanometer of copper clad monocrystalline sapphire fiber, including：A, at room temperature, sodium borohydride is added to dilute
In ammonium hydroxide, 1~5min is stirred, alkaline sodium borohydride reduction solution is obtained；B, monocrystalline sapphire whisker is added to above-mentioned alkalinity
In sodium borohydride solution reducing solution, the solution ultrasonic disperse containing monocrystalline sapphire whisker is handled with ultrasonic washing instrument, is obtained
To the reproducibility mixed liquor containing monocrystalline sapphire whisker；C, weak aqua ammonia is gradually added dropwise in copper salt solution, then has azury
Precipitating generates, and continues dropwise addition ammonium hydroxide to precipitating and is completely dissolved, at this time up to the navy blue solution containing ammoniacal copper complex ion；D, benefit
It is stirred with magnetic agitation instrument, is added at the uniform velocity into the reproducibility mixed liquor containing monocrystalline sapphire whisker and contains ammoniacal copper complex ion
Solution stops stirring until monocrystalline sapphire whisker becomes red, obtains the monocrystalline sapphire mixing of nanometer copper clad
Liquid；E, the monocrystalline sapphire mixed liquor after reaction is filtered, washing obtains the monocrystalline sapphire whisker of wet nanometer copper clad；
F, the monocrystalline sapphire whisker of wet nanometer copper clad is dried, it is blue precious that the monocrystalline for containing nanometer copper clad in surface can be obtained
Stone crystal whisker；The mass ratio of sodium borohydride and weak aqua ammonia is 1 in the step a:1~50, dilute ammonia concn is 1~30% (w/
v)；The revolving speed of magnetic agitation instrument is 250r/min~500r/min in step d, mixed to the reproducibility containing monocrystalline sapphire whisker
Closing and the speed of the solution containing ammoniacal copper complex ion is added in liquid is 5 drops/min~10 drops/min.
2. the preparation method of according to claim 1 nanometer of copper clad monocrystalline sapphire fiber, ultrasonic wave described in step b
The temperature of cleaning device is 40~60 DEG C, and the processing time is 5~10min.
3. the preparation method of according to claim 1 nanometer of copper clad monocrystalline sapphire fiber, monocrystalline sapphire in step b
The mass ratio of whisker and sodium borohydride is 1~1:10.
4. the preparation method of according to claim 1 nanometer of copper clad monocrystalline sapphire fiber, mantoquita is sulfuric acid in step c
Copper, copper nitrate, copper chloride, copper acetate or their combination.
5. the preparation method of according to claim 1 nanometer of copper clad monocrystalline sapphire fiber, the concentration of the mantoquita is 1
~30% (w/v), dilute ammonia concn is 1~30% (w/v), and the mass ratio of mantoquita used and monocrystalline sapphire whisker is 1
~100:1.
It, will be after reaction in step e 6. the preparation method of according to claim 1 nanometer of copper clad monocrystalline sapphire fiber
The method washed is after the filtering of monocrystalline sapphire mixed liquor：Deionized water is washed 2~5 times；Drying means in step f is：It will
The monocrystalline sapphire whisker of wet nanometer copper clad is dried at being 60~100 DEG C in temperature, and drying time is 3~9h.
7. a kind of metallic composite, including the modified monocrystalline of copper clad made from method described in any one of claims 1-6 are blue
Jewel whisker.
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| CN102124142A (en) * | 2008-09-25 | 2011-07-13 | 宇部日东化成株式会社 | Method for forming metal coating film, and electrically conductive particle |
| CN103060779A (en) * | 2012-12-04 | 2013-04-24 | 复旦大学 | Preparation method of copper/modal fiber composite material |
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| CN102124142A (en) * | 2008-09-25 | 2011-07-13 | 宇部日东化成株式会社 | Method for forming metal coating film, and electrically conductive particle |
| CN103060779A (en) * | 2012-12-04 | 2013-04-24 | 复旦大学 | Preparation method of copper/modal fiber composite material |
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