CN102030479B - 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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- CN102030479B CN102030479B CN200910190282.5A CN200910190282A CN102030479B CN 102030479 B CN102030479 B CN 102030479B CN 200910190282 A CN200910190282 A CN 200910190282A CN 102030479 B CN102030479 B CN 102030479B
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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 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
Doped with the matrix material of metallics, in fields such as optics, electronics, antibacterial and catalysis, have a wide range of applications, especially doped with the glass material of metallics, at optics, electronic applications, have important application.When metal nanoparticle is impregnated in glass, glass matrix is isolated from each other particle, forms quantum dot, and the locality of electronics and coherency are strengthened, and causes quantum confined effect.Meanwhile, when the size of metal nanoparticle is during much smaller than light field wavelength, the electric field acting on particle is also obviously different from medium macroscopic field around, and its polarization process will change the specific inductivity of local, thereby produce Dielectric confinement effect.These effects all can cause the significantly improving of non-linear optical property of glass, make the matrix material with non-linear optical property have important application advantage in fields such as optical storage, transmission and switches, for example: compare with electronic switching device, full light photon switch device has the advantages such as short, energy-conservation and life-span switching time is long, will become the important composition parts of following optoelectronic device.
At present, conventional preparation has doped with the method for metal nanoparticle glass: scorification, ion implantation and sol-gel method etc., these techniques are relatively ripe.For example, but these methods also all exist some shortcomings part: scorification at high temperature carries out melting after metal-salt need to being mixed with frit, because the viscosity of glass system is larger, metallic particles is not easy to realize dispersed in glass matrix.Ion implantation is that metal is injected in glass matrix with ionic species, by thermal treatment, obtain metal nanoparticle again, this method need to be used expensive ion implantation device, and it is limited to inject the degree of depth, and metal nanoparticle can only be distributed in glass matrix surface.Also having a kind of method is to utilize sol-gel method to prepare glass, during preparation, the solution that contains metal-salt is mixed with glass colloidal sol simultaneously, by aftertreatment, obtain the glass that contains metal nanoparticle, 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, do not reach practical requirement.
Summary of the invention
The technical problem to be solved in the present invention is, glass for existing doping metals particle exists metallics to disperse the problem inhomogeneous, 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, copper nano-particle particle diameter is even, physical strength is large is provided.
The technical problem that the present invention further will solve is, in prior art---scorification exists metallics in glass, to disperse metal nanoparticle prepared by inhomogeneous problem, ion implantation can only be distributed in the problem on glass matrix surface, the longer problem of complex process production cycle of sol-gel method, the preparation method of the sintered glass of the copper doped nanoparticle of provide a kind of and can copper metal nanoparticle is dispersed in glass, technique 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 the sintered glass that is evenly distributed with UNICOM's micropore be base material, 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 is mainly grouped into by the one-tenth of following parts 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 preparation method for the sintered glass of copper doped nanoparticle, comprises the following steps:
(1), prepare respectively copper ion solution and for reducing the reductant solution of cupric ion;
(2), select the sintered glass that is evenly distributed with UNICOM's micropore, sintered glass is placed in respectively to copper ion solution and reductant solution, and each at least soaks once, 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.
In the preparation method of the sintered glass of copper doped nanoparticle, in described step (1), described copper ion solution is that copper-containing compound is dissolved in solvent and is made, and described copper ion solution concentration is 1mol/L～1 * 10
-6mol/L.
In 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.
In the preparation method of the sintered glass of copper doped nanoparticle, in described step (1), the concentration of described reductant solution is 1 * 10
-2mol/L～1 * 10
-6mol/L, described reductant solution is the reductive agent for cupric ion reduction to be dissolved in to solvent make.
In 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.
In the preparation method of the sintered glass of copper doped nanoparticle, in described step (2), when sintered glass is placed in copper ion solution and soaks, soak time is no less than 0.5h, then sintered glass is taken out, and rinses; Preferably soak time is 0.5h～12h.
In the preparation method of the sintered glass of copper doped nanoparticle, in described step (2), when sintered glass is placed in reductant solution and soaks, soak time is no less than 0.5h, then sintered glass is taken out, and rinses; Preferably soak time is 0.5h～12h.
In the preparation method of the sintered glass of copper doped nanoparticle, described sintered glass is mainly grouped into by the one-tenth of following parts 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 the sintered glass that is evenly distributed with mutual UNICOM microvoid structure as copper metal particle substrate material, makes copper metal particle in glass, have sufficient amount, and disperses well.And the advantages such as the sintered glass of making 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 short, can effectively save production cost; Copper nano-particle in prepared glass is evenly distributed, and can make the non-linear optical property of glass significantly improve.
Embodiment
The sintered glass that the embodiment of the present invention is selected, can adopt existing glass manufacturing technology to make.
Embodiment 1: the sintered glass of copper doped nanoparticle: select parts by weight to be respectively SiO
294.0, B
2o
33.0, Al
2o
33.0 sintered glass is base material, and the volume of micropore accounts for 25% of sintered glass cumulative volume, and micropore size is 10～20nm, in the micropore of sintered glass, is uniformly distributed copper nano-particle.
Preparation method: the cupric chloride ethanolic soln that compound concentration is 1mol/L and concentration are 1 * 10
-2each 10mL of POTASSIUM BOROHYDRIDE ethanolic soln of mol/L.Sintered glass is put in cupric chloride ethanolic soln and soaks 0.5h; Take out sintered glass, use alcohol flushing 3 times; Sintered glass is put in POTASSIUM BOROHYDRIDE ethanolic soln and soaks reaction 0.5h, then take out sintered glass, with distilled water, clean and be dried, prepare the sintered glass of copper doped nanoparticle.
Embodiment 2: the sintered glass of copper doped nanoparticle: select 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 base material, and the volume of micropore accounts for 28% of sintered glass cumulative volume, and micropore size is 50～100nm, in the micropore of sintered glass, is uniformly distributed copper nano-particle.
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 and in copper sulfate solution, soaks 1h; Take out sintered glass, use distilled water flushing 3 times; Sintered glass is put in POTASSIUM BOROHYDRIDE ethanolic soln and soaks reaction 2h, then take out sintered glass, with distilled water, clean and be dried, prepare the sintered glass of copper doped nanoparticle.
Embodiment 3: the sintered glass of copper doped nanoparticle: select 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 is base material, and the volume of micropore accounts for 35% of sintered glass cumulative volume, and micropore size is 10～50nm, in the micropore of sintered glass, is uniformly distributed copper nano-particle.
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 cupric nitrate ethanolic soln and soaks 4h; Take out sintered glass, use alcohol flushing 3 times; Sintered glass is put in ethanol solution of sodium borohydride and soaks reaction 6h, then take out sintered glass, with distilled water, clean and be dried, prepare the sintered glass of copper doped nanoparticle.
Embodiment 4: the sintered glass of copper doped nanoparticle: select parts by weight to be respectively SiO
297.0, B
2o
31.5, Al
2o
32.6, ZrO
21.0 sintered glass is base material, and the volume of micropore accounts for 30% of sintered glass cumulative volume, and micropore size is 4～20nm, in the micropore of sintered glass, is uniformly distributed copper nano-particle.
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 cupric chloride methanol solution and soaks 5h; Take out sintered glass, use washed with methanol 3 times; Sintered glass is put in ethanol solution of sodium borohydride and soaks reaction 5h, then take out sintered glass, with distilled water, clean and be dried, prepare the sintered glass of copper doped nanoparticle.
Embodiment 5: the sintered glass of copper doped nanoparticle: select 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 is base material, and the volume of micropore accounts for 40% of sintered glass cumulative volume, and micropore size is 30～60nm, in the micropore of sintered glass, is uniformly distributed copper nano-particle.
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 and in ethanol solution of sodium borohydride, soaks 5h; Take out sintered glass, use alcohol flushing 3 times; Sintered glass is put in cupric nitrate ethanolic soln and soaks reaction 8h, then take out sintered glass, with distilled water, clean and be dried; Repeat aforesaid operations 2 times, prepare the sintered glass of copper doped nanoparticle.
Embodiment 6: the sintered glass of copper doped nanoparticle: select 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 is base material, and the volume of micropore accounts for 38% of sintered glass cumulative volume, and micropore size is 10～30nm, in the micropore of sintered glass, is uniformly distributed copper nano-particle.
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 and soaks 8h; Take out sintered glass, use distilled water flushing 3 times; Sintered glass is put in cupric nitrate ethanolic soln and soaks reaction 12h, then take out sintered glass, with distilled water, clean and be dried; Repeat aforesaid operations 4 times, prepare the sintered glass of copper doped nanoparticle.
Embodiment 7: the sintered glass of copper doped nanoparticle: select parts by weight to be respectively SiO
294.8, B
2o
31.3, Al
2o
32.8 sintered glass is base material, and the volume of micropore accounts for 28% of sintered glass cumulative volume, and micropore size is 70～100nm, in the micropore of sintered glass, is uniformly distributed copper nano-particle.
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.First sintered glass is put in cupric chloride methanol solution and soaks 5h; Take out sintered glass, use distilled water flushing 3 times; Again sintered glass is put in sodium borohydride methanol solution and soaks reaction 12h, then take out sintered glass, with distilled water, clean and be dried; Repeat aforesaid operations 3 times, prepare the sintered glass of copper doped nanoparticle.
The above embodiment of the present invention is to select sintered glass as copper metal particle substrate material, microvoid structure due to the special equally distributed mutual UNICOM of sintered glass, micropore is uniformly distributed and refers to 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 micropore effectively, by micropore, makes the metallics of nano-scale, and micropore is evenly distributed in sintered glass simultaneously, and due to the isolation of micropore, metallics has good dispersiveness in glass.And because micro pore volume accounts for 25～40% of sintered glass cumulative volume, having guaranteed like this can have the copper metal particle of sufficient amount in micropore.
Owing to selecting SiO in sintered glass base material
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,, physical strength high and low thermal expansivity good such as chemical stability, heat shock resistance etc.These premium propertiess can be used in many special fields glass of the present invention, are especially applied in some severe environment, for example, under high temperature, high pressure, high vibration and wet environment.
Preparation method of the present invention is immersed in respectively copper ion solution by sintered glass and for reducing the reductant solution of cupric ion, cupric ion reduction is become to the particle of metallic copper in the micropore of sintered glass, because sintered glass has even UNICOM micropore, cupric ion can be disperseed well in micropore, and because the aperture of micropore is nano-scale, also make the copper metal particle of reduction also there is nano-scale.
In order to guarantee to generate in the micropore of sintered glass the metallic copper nano particle of q.s, sintered glass is all no less than 0.5h at copper ion solution and reductant solution soak time, and can adopt repeatedly and at copper ion solution or reductant solution, soak separately, or repeatedly at copper ion solution and reductant solution, replace the method for soaking, increase the quantity of the metallic copper nano particle generating in the micropore of sintered glass.Say on the other hand, by control, soak number of times, can control the quantity of the metallic copper nano particle generating in micropore, make the sintered glass of the different copper doped nanoparticles that require.
Preparation technology of the present invention is simple, preparation cycle is short, can effectively save production cost; Copper nano-particle in prepared glass is evenly distributed, and can make the non-linear optical property of glass significantly improve.
Claims (6)
1. the sintered glass of a copper doped nanoparticle, it is characterized in that, be the sintered glass that is evenly distributed with UNICOM's micropore be base material, 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 is mainly grouped into by the one-tenth of following parts by weight:
3. a preparation method for the sintered glass of copper doped nanoparticle, is characterized in that, comprises the following steps:
(1), prepare respectively copper ion solution and for reducing the reductant solution of cupric ion;
(2), select the sintered glass that is evenly distributed with UNICOM's micropore, sintered glass is placed in respectively to copper ion solution and reductant solution, and each at least soaks once, 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;
In described step (1), described copper ion solution is that copper-containing compound is dissolved in solvent and is made, and described copper ion solution concentration is 1mol/L～1 * 10
-6mol/L; Described copper-containing compound is cupric chloride, cupric nitrate or copper sulfate, and described solvent is water or ethanol;
In described step (1), described reductant solution is the reductive agent for cupric ion reduction to be dissolved in to solvent make, and the concentration of described reductant solution is 1 * 10
-2mol/L～1 * 10
-6mol/L; Described reductive agent is POTASSIUM BOROHYDRIDE or sodium borohydride, and described solvent is water or ethanol.
4. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3, is characterized in that, in described step (2), when described sintered glass is placed in copper ion solution and soaks, soak time is no less than 0.5h, then sintered glass is taken out, and rinses.
5. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3, is characterized in that, in described step (2), when described sintered glass is placed in reductant solution and soaks, soak time is no less than 0.5h, then sintered glass is taken out, and rinses.
6. the preparation method of the sintered glass of copper doped nanoparticle as claimed in claim 3, is characterized in that, described sintered glass is mainly grouped into by the one-tenth of following parts by weight:
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| CN102030479B true CN102030479B (en) | 2014-04-09 |
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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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736920A (en) * | 2005-07-15 | 2006-02-22 | 中国科学院上海光学精密机械研究所 | The manufacture method of the vagcor of green light |
| EP1436445B1 (en) * | 2001-08-30 | 2006-05-17 | Atkina Limited | Process for making thin film porous ceramic-metal composites and composites obtained by this process |
| CN1785873A (en) * | 2005-10-21 | 2006-06-14 | 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 |
| US7149395B1 (en) * | 2005-08-09 | 2006-12-12 | Instrument Technology Research Center | Light-enhancing component and fabrication method thereof |
-
2009
- 2009-09-24 CN CN200910190282.5A patent/CN102030479B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1436445B1 (en) * | 2001-08-30 | 2006-05-17 | Atkina Limited | Process for making thin film porous ceramic-metal composites and composites obtained by this process |
| CN1736920A (en) * | 2005-07-15 | 2006-02-22 | 中国科学院上海光学精密机械研究所 | The manufacture method of the vagcor of green light |
| US7149395B1 (en) * | 2005-08-09 | 2006-12-12 | Instrument Technology Research Center | Light-enhancing component and fabrication method thereof |
| CN1785873A (en) * | 2005-10-21 | 2006-06-14 | 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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