CN102030479A - Copper nanoparticle-doped porous glass and preparation method thereof - Google Patents
Copper nanoparticle-doped porous glass and preparation method thereof Download PDFInfo
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- CN102030479A CN102030479A CN 200910190282 CN200910190282A CN102030479A CN 102030479 A CN102030479 A CN 102030479A CN 200910190282 CN200910190282 CN 200910190282 CN 200910190282 A CN200910190282 A CN 200910190282A CN 102030479 A CN102030479 A CN 102030479A
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Abstract
The invention discloses a copper nanoparticle-doped porous glass and a preparation method thereof. Porous glass, on which communicated micropores are uniformly distributed, is used as a substrate, and copper nanoparticles are uniformly distributed in the micropores, wherein the pore diameters of the micropores are 4-100nm, and the micropores account for 25-40% of the porous glass by volume. The preparation method comprises the following steps: respectively preparing a copper ion solution and a reducer solution for reducing copper ions; and selecting the porous glass on which communicated micropores are uniformly distributed, and respectively soaking the porous glass in the copper ion solution and the reducer solution for at least one time to prepare the copper nanoparticle-doped porous glass. The porous glass has the characteristics of uniform dispersion, uniform particle size and high mechanical strength for metallic copper nanoparticles; and by using the preparation method, the metallic copper nanoparticles can be uniformly dispersed in the glass, thus the preparation method has the advantage of simple technique and facilitates the preparation.
Description
Technical field
The invention belongs to the photoelectric material technical field, relate to sintered glass of a kind of doping metals particle and preparation method thereof, relate in particular to sintered glass of a kind of copper doped nanoparticle and preparation method thereof.
Background technology
The matrix material that is doped with metallics has a wide range of applications in fields such as optics, electronics, antibiotic and catalysis, especially is doped with the glass material of metallics, at optics, electronic applications important use is arranged.When metal nanoparticle was impregnated in glass, glass matrix was isolated from each other particle, formed quantum dot, made the locality of electronics and coherency strengthen, and caused quantum confined effect.Simultaneously, when the size of metal nanoparticle during much smaller than the light field wavelength, act on electric field on the particle medium macroscopic field around also obviously being different from, its polarization process will change the specific inductivity of local, thus generation dielectric confinement effect.These effects all can cause the significantly improving of non-linear optical property of glass, make matrix material the important use advantage be arranged in fields such as optical storage, transmission and switches with non-linear optical property, for example: compare with electronic switching device, full light photon switch device has short, energy-conservation and life-span switching time and advantage such as grows, and will become the important composition parts of following optoelectronic device.
At present, the Chang Yong preparation method that is doped with metal nanoparticle glass has: scorification, ion implantation and sol-gel method etc., these technologies are relatively ripe.But these methods also all exist the some shortcomings part, for example: scorification need with metal-salt with at high temperature carry out fusion after frit mixes because the viscosity of glass system is bigger, metallic particles is not easy to realize homodisperse in glass matrix.Ion implantation is that metal is injected in the glass matrix with ionic species, obtain metal nanoparticle by thermal treatment again, this method need be used expensive ion implantation device, and it is limited to inject the degree of depth, and metal nanoparticle can only be distributed in the glass matrix surface.Also having a kind of method is to utilize Prepared by Sol Gel Method glass, during preparation, the solution that will contain metal-salt simultaneously mixes with glass colloidal sol, obtain containing the glass of metal nanoparticle by aftertreatment, the dispersion of metal nanoparticle is also relatively even, but this method prepares glass, and complex process, production cycle are longer, and the intensity of glasswork is lower, does not reach practical requirement.
Summary of the invention
The technical problem to be solved in the present invention is, glass at existing doping metals particle exists metallics to disperse the problem inhomogeneous, that glasswork intensity is low, and the sintered glass of the copper doped nanoparticle that a kind of copper nano-particle is uniformly dispersed in glass, the copper nano-particle particle diameter is even, physical strength is big is provided.
The technical problem that the present invention further will solve is, in prior art---scorification exists metallics to disperse the metal nanoparticle of uneven problem, ion implantation preparation can only be distributed in the problem on glass matrix surface, the long problem of complex process production cycle of sol-gel method in glass, the preparation method of the sintered glass of the copper doped nanoparticle of provide a kind of and can be dispersed in the copper metal nanoparticle in the glass, technology is simple, easy to prepare.
The technical solution adopted for the present invention to solve the technical problems is: a kind of sintered glass of copper doped nanoparticle, be to be base material with the sintered glass that is evenly distributed with UNICOM's micropore, in the micropore of sintered glass, be evenly distributed with copper nano-particle, the aperture of described micropore is 4～100nm, and the volume of micropore accounts for 25～40% of sintered glass cumulative volume.
In the sintered glass of copper doped nanoparticle, described sintered glass mainly is made up of following compositions in portion by weight:
SiO
2 94.0～98.0
B
2O
3 1.0～3.0
Al
2O
3 1.0～3.0
Na
2O 0～1.0
ZrO
2 0～1.0。
A kind of preparation method of sintered glass of copper doped nanoparticle may further comprise the steps:
(1), prepares copper ion solution and being used to respectively and reduce the reductant solution of cupric ion;
(2), select the sintered glass that is evenly distributed with UNICOM's micropore for use, sintered glass is placed copper ion solution and reductant solution respectively, and each soaks once at least, promptly prepares the sintered glass of copper doped nanoparticle; The aperture of described micropore is 4～100nm, and the volume of micropore accounts for 25～40% of sintered glass cumulative volume.
Among the preparation method of the sintered glass of copper doped nanoparticle, in the described step (1), described copper ion solution is copper-containing compound to be dissolved in the solvent make, and described copper ion solution concentration is 1mol/L～1 * 10
-6Mol/L.
Among the preparation method of the sintered glass of copper doped nanoparticle, described copper-containing compound is cupric chloride, cupric nitrate or copper sulfate, and described solvent is water, methyl alcohol or ethanol.
Among the preparation method of the sintered glass of copper doped nanoparticle, in the described step (1), the concentration of described reductant solution is 1 * 10
-2Mol/L～1 * 10
-6Mol/L, described reductant solution are dissolved in solvent and make being used for cupric ion reductive reductive agent.
Among the preparation method of the sintered glass of copper doped nanoparticle, described reductive agent is POTASSIUM BOROHYDRIDE or sodium borohydride, and described solvent is water, methyl alcohol or ethanol.
Among the preparation method of the sintered glass of copper doped nanoparticle, in the described step (2), when sintered glass placed copper ion solution to soak, soak time was no less than 0.5h, then sintered glass was taken out flushing; Preferred soak time is 0.5h～12h.
Among the preparation method of the sintered glass of copper doped nanoparticle, in the described step (2), when sintered glass placed reductant solution to soak, soak time was no less than 0.5h, then sintered glass was taken out flushing; Preferred soak time is 0.5h～12h.
Among the preparation method of the sintered glass of copper doped nanoparticle, described sintered glass mainly is made up of following compositions in portion by weight:
SiO
2 94.0～98.0
B
2O
3 1.0～3.0
Al
2O
3 1.0～3.0
Na
2O 0～1.0
ZrO
2 0～1.0。
The present invention selects for use the sintered glass that is evenly distributed with mutual UNICOM microvoid structure as the copper metal particle substrate material, makes copper metal particle have sufficient amount in glass, and disperses well.And advantages such as the sintered glass of making the copper doped nanoparticle has, and chemical stability is good, the high and low thermal expansivity of physical strength, heat shock resistance.
Preparation technology of the present invention is simple, preparation cycle is lacked, can effectively be saved production cost; Copper nano-particle in the prepared glass is evenly distributed, and the non-linear optical property of glass is significantly improved.
Embodiment
The sintered glass that the embodiment of the invention is selected for use can adopt existing glass to make fabrication techniques.
Embodiment 1: the sintered glass of copper doped nanoparticle: select for use parts by weight to be respectively SiO
294.0, B
2O
33.0, Al
2O
33.0 sintered glass be base material, the volume of micropore accounts for 25% of sintered glass cumulative volume, micropore size is 10～20nm, uniform distribution copper nano-particle in the micropore of sintered glass.
The preparation method: compound concentration is that cupric chloride ethanolic soln and the concentration of 1mol/L is 1 * 10
-2Each 10mL of POTASSIUM BOROHYDRIDE ethanolic soln of mol/L.Sintered glass is put in the cupric chloride ethanolic soln soaks 0.5h; Take out sintered glass, use alcohol flushing 3 times; Sintered glass is put into immersion reaction 0.5h in the POTASSIUM BOROHYDRIDE ethanolic soln, takes out sintered glass then, clean and drying, promptly prepare the sintered glass of copper doped nanoparticle with distilled water.
Embodiment 2: the sintered glass of copper doped nanoparticle: select for use parts by weight to be respectively SiO
295.0, B
2O
32.0, Al
2O
33.0, Na
2The sintered glass of O 1.0 is a base material, and the volume of micropore accounts for 28% of sintered glass cumulative volume, and micropore size is 50～100nm, uniform distribution copper nano-particle in the micropore of sintered glass.
The preparation method: compound concentration is 1 * 10
-1The copper sulfate solution of mol/L and concentration are 1 * 10
-3Each 10mL of POTASSIUM BOROHYDRIDE ethanolic soln of mol/L.Sintered glass is put into soaks 1h in the copper sulfate solution; Take out sintered glass, use distilled water flushing 3 times; Sintered glass is put into immersion reaction 2h in the POTASSIUM BOROHYDRIDE ethanolic soln, takes out sintered glass then, clean and drying, promptly prepare the sintered glass of copper doped nanoparticle with distilled water.
Embodiment 3: the sintered glass of copper doped nanoparticle: select for use parts by weight to be respectively SiO
296.0, B
2O
31.0, Al
2O
31.0, Na
2O 0.5, ZrO
20.6 sintered glass be base material, the volume of micropore accounts for 35% of sintered glass cumulative volume, micropore size is 10～50nm, uniform distribution copper nano-particle in the micropore of sintered glass.
The preparation method: compound concentration is 1 * 10
-3The cupric nitrate ethanolic soln of mol/L and concentration are 1 * 10
-4Each 10mL of the ethanol solution of sodium borohydride of mol/L.Sintered glass is put in the cupric nitrate ethanolic soln soaks 4h; Take out sintered glass, use alcohol flushing 3 times; Sintered glass is put into immersion reaction 6h in the ethanol solution of sodium borohydride, takes out sintered glass then, clean and drying, promptly prepare the sintered glass of copper doped nanoparticle with distilled water.
Embodiment 4: the sintered glass of copper doped nanoparticle: select for use parts by weight to be respectively SiO
297.0, B
2O
31.5, Al
2O
32.6, ZrO
21.0 sintered glass be base material, the volume of micropore accounts for 30% of sintered glass cumulative volume, micropore size is 4～20nm, uniform distribution copper nano-particle in the micropore of sintered glass.
The preparation method: compound concentration is 1 * 10
-5The cupric chloride methanol solution of mol/L and concentration are 1 * 10
-3Each 10mL of the ethanol solution of sodium borohydride of mol/L.Sintered glass is put in the cupric chloride methanol solution soaks 5h; Take out sintered glass, use washed with methanol 3 times; Sintered glass is put into immersion reaction 5h in the ethanol solution of sodium borohydride, takes out sintered glass then, clean and drying, promptly prepare the sintered glass of copper doped nanoparticle with distilled water.
Embodiment 5: the sintered glass of copper doped nanoparticle: select for use parts by weight to be respectively SiO
298.0, B
2O
33.0, Al
2O
31.0, Na
2O 1.0, ZrO
20.8 sintered glass be base material, the volume of micropore accounts for 40% of sintered glass cumulative volume, micropore size is 30～60nm, uniform distribution copper nano-particle in the micropore of sintered glass.
The preparation method: compound concentration is 1 * 10
-5The cupric nitrate ethanolic soln of mol/L and concentration are 1 * 10
-5Each 10mL of the ethanol solution of sodium borohydride of mol/L.Sintered glass is put into soaks 5h in the ethanol solution of sodium borohydride; Take out sintered glass, use alcohol flushing 3 times; Sintered glass is put into immersion reaction 8h in the cupric nitrate ethanolic soln, takes out sintered glass then, clean and drying with distilled water; Repeat aforesaid operations 2 times, promptly prepare the sintered glass of copper doped nanoparticle.
Embodiment 6: the sintered glass of copper doped nanoparticle: select for use parts by weight to be respectively SiO
295.5, B
2O
32.4, Al
2O
32.0, Na
2O 0.4, ZrO
20.2 sintered glass be base material, the volume of micropore accounts for 38% of sintered glass cumulative volume, micropore size is 10～30nm, uniform distribution copper nano-particle in the micropore of sintered glass.
The preparation method: compound concentration is 1 * 10
-6The cupric nitrate ethanolic soln of mol/L and concentration are 1 * 10
-6Each 10mL of the POTASSIUM BOROHYDRIDE aqueous solution of mol/L.Sintered glass is put in the POTASSIUM BOROHYDRIDE aqueous solution soaks 8h; Take out sintered glass, use distilled water flushing 3 times; Sintered glass is put into immersion reaction 12h in the cupric nitrate ethanolic soln, takes out sintered glass then, clean and drying with distilled water; Repeat aforesaid operations 4 times, promptly prepare the sintered glass of copper doped nanoparticle.
Embodiment 7: the sintered glass of copper doped nanoparticle: select for use parts by weight to be respectively SiO
294.8, B
2O
31.3, Al
2O
32.8 sintered glass be base material, the volume of micropore accounts for 28% of sintered glass cumulative volume, micropore size is 70～100nm, uniform distribution copper nano-particle in the micropore of sintered glass.
The preparation method: compound concentration is 1 * 10
-5The cupric chloride methanol solution of mol/L and concentration are 1 * 10
-3Each 10mL of POTASSIUM BOROHYDRIDE methanol solution of mol/L.Earlier sintered glass is put in the cupric chloride methanol solution and soaks 5h; Take out sintered glass, use distilled water flushing 3 times; Again sintered glass is put into and soaks reaction 12h in the sodium borohydride methanol solution, take out sintered glass then, clean and drying with distilled water; Repeat aforesaid operations 3 times, promptly prepare the sintered glass of copper doped nanoparticle.
The above embodiment of the present invention is to select for use sintered glass as the copper metal particle substrate material, because the microvoid structure of the equally distributed mutual UNICOM that sintered glass is special, the micropore uniform distribution is meant micropore distributing equilibrium on sintered glass, does not have local micropore to concentrate or the phenomenon of local pore-free.Micropore can limit metal particle size in the micropore effectively, promptly makes the metallics of nano-scale by micropore, and micropore is evenly distributed in sintered glass simultaneously, because the isolation of micropore, metallics has good dispersiveness in glass.And, guaranteed to have in the micropore copper metal particle of sufficient amount like this because micro pore volume accounts for 25～40% of sintered glass cumulative volume.
Owing to select SiO in the sintered glass base material for use
2Weight percentage be not less than 90%, therefore its constituent class is similar to silica glass, has excellent physical and the chemical property that is similar to silica glass, for example chemical stability is good, the high and low thermal expansivity of physical strength, heat shock resistance etc.These premium propertiess make glass of the present invention can be used in many special fields, especially are applied in some severe environment, for example under high temperature, high pressure, high vibration and the wet environment.
Preparation method of the present invention is immersed in copper ion solution and being used for respectively with sintered glass to reduce the reductant solution of cupric ion, in the micropore of sintered glass, cupric ion reduction is become the particle of metallic copper, because sintered glass has even UNICOM micropore, cupric ion can be disperseed in micropore well, and, also make the reductive copper metal particle also have nano-scale because the aperture of micropore is a nano-scale.
In order to generate the metallic copper nano particle of q.s in the micropore that guarantees sintered glass, sintered glass all is no less than 0.5h at copper ion solution and reductant solution soak time, and can adopt repeatedly and soak at copper ion solution or reductant solution separately, or repeatedly replace the method for soaking at copper ion solution and reductant solution, increase the quantity of the metallic copper nano particle that generates in the micropore of sintered glass.Say on the other hand, soak number of times, can control the quantity of the metallic copper nano particle that generates in the micropore, make the sintered glass of the different copper doped nanoparticles that require by control.
Preparation technology of the present invention is simple, preparation cycle is lacked, can effectively be saved production cost; Copper nano-particle in the prepared glass is evenly distributed, and the non-linear optical property of glass is significantly improved.
Claims (10)
1. the sintered glass of a copper doped nanoparticle, it is characterized in that, be to be base material with the sintered glass that is evenly distributed with UNICOM's micropore, in the micropore of sintered glass, be evenly distributed with copper nano-particle, the aperture of described micropore is 4～100nm, and the volume of micropore accounts for 25～40% of sintered glass cumulative volume.
2. the sintered glass of copper doped nanoparticle as claimed in claim 1 is characterized in that, described sintered glass mainly is made up of following compositions in portion by weight:
SiO
2 94.0～98.0
B
2O
3 1.0～3.0
Al
2O
3 1.0～3.0
Na
2O 0～1.0
ZrO
2 0～1.0。
3. the preparation method of the sintered glass of a copper doped nanoparticle is characterized in that, may further comprise the steps:
(1), prepares copper ion solution and being used to respectively and reduce the reductant solution of cupric ion;
(2), select the sintered glass that is evenly distributed with UNICOM's micropore for use, sintered glass is placed described copper ion solution and reductant solution respectively, and each soaks once at least, promptly prepares the sintered glass of copper doped nanoparticle; The aperture of described micropore is 4～100nm, and the volume of micropore accounts for 25～40% of sintered glass cumulative volume.
4. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3 is characterized in that, in the described step (1), described copper ion solution is copper-containing compound to be dissolved in the solvent make, and described copper ion solution concentration is lmol/L～1 * 10
-6Mol/L.
5. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 4 is characterized in that, described copper-containing compound is cupric chloride, cupric nitrate or copper sulfate, and described solvent is water, methyl alcohol or ethanol.
6. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3 is characterized in that, in the described step (1), the concentration of described reductant solution is 1 * 10
-2Mol/L～1 * 10
-6Mol/L, described reductant solution are dissolved in solvent and make being used for cupric ion reductive reductive agent.
7. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 6 is characterized in that, described reductive agent is POTASSIUM BOROHYDRIDE or sodium borohydride, and described solvent is water, methyl alcohol or ethanol.
8. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3 is characterized in that, in the described step (2), when described sintered glass placed copper ion solution to soak, soak time was no less than 0.5h, then sintered glass is taken out flushing.
9. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3 is characterized in that, in the described step (2), when described sintered glass placed reductant solution to soak, soak time was no less than 0.5h, then sintered glass is taken out flushing.
10. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3 is characterized in that, described sintered glass mainly is made up of following compositions in portion by weight:
SiO
2 94.0～98.0
B
2O
3 1.0～3.0
Al
2O
3 1.0～3.0
Na
2O 0～1.0
ZrO
2 0～1.0。
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910190282.5A CN102030479B (en) | 2009-09-24 | 2009-09-24 | Copper nanoparticle-doped porous glass and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603215A (en) * | 2017-09-22 | 2018-01-19 | 安庆市虹泰新材料有限责任公司 | A kind of preparation method of polyamide copper composite membrane |
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| DE60211543T2 (en) * | 2001-08-30 | 2007-05-10 | Aktina Ltd. | METHOD FOR PRODUCING POROUS CERAMIC METAL COMPOSITE MATERIALS AND COMPOSITE MATERIALS THUS OBTAINED THEREFOR |
| CN100484896C (en) * | 2005-07-15 | 2009-05-06 | 中国科学院上海光学精密机械研究所 | Geen light emitting vycor glass production method |
| US7149395B1 (en) * | 2005-08-09 | 2006-12-12 | Instrument Technology Research Center | Light-enhancing component and fabrication method thereof |
| CN1308255C (en) * | 2005-10-21 | 2007-04-04 | 中国科学院上海光学精密机械研究所 | Manufacturing method of erbium doped high silicon oxygen infrared luminous glass |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107603215A (en) * | 2017-09-22 | 2018-01-19 | 安庆市虹泰新材料有限责任公司 | A kind of preparation method of polyamide copper composite membrane |
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