CN102030478B - Iron nano particle doped porous glass and preparation method thereof - Google Patents
Iron nano particle doped porous glass and preparation method thereof Download PDFInfo
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- CN102030478B CN102030478B CN200910190281.0A CN200910190281A CN102030478B CN 102030478 B CN102030478 B CN 102030478B CN 200910190281 A CN200910190281 A CN 200910190281A CN 102030478 B CN102030478 B CN 102030478B
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Abstract
The invention discloses iron nano particle doped porous glass and a preparation method thereof. The base material of the glass is porous glass uniformly provided with communicated micropores, iron nano particles are uniformly distributed in the micropores, the diameter of the micropores is 4-100 nm, and the volume of the micropores accounts for 25-40% of the total volume of the porous glass. The preparation method comprises the following steps of: selecting the porous glass uniformly provided with communicated micropores; respectively preparing an iron ion solution and a reducing agent solution used for reducing iron ions; and respectively immersing the porous glass in the iron ion solution and the reducing agent solution for at least one time to prepare the porous glass doped with iron nano particles. The porous glass of the invention has the characteristics of uniform dispersion of iron nano particles, uniform particle size and great mechanical strength, and moreover, the preparation method can enable the iron nano particles to be uniformly dispersed in the glass. The porous glass has simple process and is convenient to prepare.
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 doping iron 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 doping iron nanoparticle that a kind of Fe nanometer particles is uniformly dispersed in glass, Fe nanometer particles 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 doping iron nanoparticle of provide a kind of and can ferrous metal nanoparticle is dispersed in glass, technique is simple, easy to prepare.
The present invention solves the technical scheme that its technical problem adopts: a kind of sintered glass of doping iron nanoparticle, the sintered glass that is evenly distributed with UNICOM's micropore of take is base material, in the micropore of sintered glass, be evenly distributed with Fe nanometer particles, 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 doping iron 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 doping iron nanoparticle, comprises the following steps:
(1), prepare respectively ferric ion solutions and for the reductant solution of reduced iron ion;
(2), select the sintered glass that is evenly distributed with UNICOM's micropore; Sintered glass is placed in respectively to ferric ion solutions and reductant solution, and each at least soaks once, prepares the sintered glass of doping iron 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 doping iron nanoparticle, in described step (1), described ferric ion solutions is that iron containing compounds is dissolved in solvent and is made, and described ferric ion solutions concentration is 1mol/L～1 * 10
-6mol/L.
In the preparation method of the sintered glass of doping iron nanoparticle, described iron containing compounds is iron(ic) chloride, iron nitrate or ferric sulfate, and described solvent is water or ethanol.
In the preparation method of the sintered glass of doping iron 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 iron ion reduction to be dissolved in to solvent make.
In the preparation method of the sintered glass of doping iron nanoparticle, described reductive agent is POTASSIUM BOROHYDRIDE or sodium borohydride, and described solvent is water or ethanol.
In the preparation method of the sintered glass of doping iron nanoparticle, in described step (2), when described sintered glass is placed in ferric ion solutions 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 doping iron nanoparticle, 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; Preferably soak time is 0.5h～12h.
In the preparation method of the sintered glass of doping iron 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 ferrous metal particle-based material, makes ferrous metal particle in glass, have sufficient amount, and disperses well.And the advantages such as the sintered glass of making doping iron 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; Fe nanometer particles 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 doping iron 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 Fe nanometer particles.
Preparation method: the iron(ic) 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 iron(ic) chloride ethanolic soln and soaks 0.5h; Take out sintered glass, use alcohol flushing 3 times; Again sintered glass is put in POTASSIUM BOROHYDRIDE ethanolic soln and soaks reaction 30min, then take out sintered glass, with distilled water, clean and be dried, prepare the sintered glass of doping iron nanoparticle.
Embodiment 2: the sintered glass of doping iron 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 Fe nanometer particles.
Preparation method: compound concentration is 1 * 10
-1the ferric sulfate aqueous 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 ferric sulfate aqueous solution, soaks 1h; Take out sintered glass, use distilled water flushing 3 times; Again 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 doping iron nanoparticle.
Embodiment 3: the sintered glass of doping iron 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 Fe nanometer particles.
Preparation method: compound concentration is 1 * 10
-3the iron 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 iron nitrate ethanolic soln and soaks 3h; Take out sintered glass, use alcohol flushing 3 times; Again 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 doping iron nanoparticle.
Embodiment 4: the sintered glass of doping iron 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 Fe nanometer particles.
Preparation method: compound concentration is 1 * 10
-5the ferric chloride in aqueous 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 into and in ferric chloride in aqueous solution, soaks 2h; Take out sintered glass, use distilled water flushing 3 times; Again 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, repeat aforesaid operations 4 times, prepare the sintered glass of doping iron nanoparticle.
Embodiment 5: the sintered glass of doping iron 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 Fe nanometer particles.
Preparation method: compound concentration is 1 * 10
-5the iron 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; Again sintered glass is put in iron nitrate ethanolic soln and soaks reaction 8h, then take out sintered glass, with distilled water, clean and be dried; Repeat aforesaid operations 3 times, prepare the sintered glass of doping iron nanoparticle.
Embodiment 6: the sintered glass of doping iron 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 Fe nanometer particles.
Preparation method: compound concentration is 1 * 10
-6the iron(ic) chloride 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; Again sintered glass is put in iron(ic) chloride ethanolic soln and soaks reaction 12h, then take out sintered glass, with distilled water, clean and be dried; Repeat aforesaid operations 5 times, prepare the sintered glass of doping iron nanoparticle.
Embodiment 7: the sintered glass of doping iron 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 Fe nanometer particles.
Preparation method: compound concentration is 1 * 10
-5the ferric sulfate ethanolic soln of mol/L and concentration are 1 * 10
-3each 10mL of POTASSIUM BOROHYDRIDE ethanolic soln of mol/L.First sintered glass is put in ferric sulfate ethanolic soln and soaks 5h; Take out sintered glass, use distilled water flushing 3 times; Again 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; Repeat aforesaid operations 3 times, prepare the sintered glass of doping iron nanoparticle.
The present invention selects sintered glass as ferrous metal particle-based 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, guaranteed like this can have in micropore the ferrous metal particle of sufficient amount.
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 ferric ion solutions by sintered glass and for the reductant solution of reduced iron ion, iron ion reduction is become to the particle of metallic iron in the micropore of sintered glass, because sintered glass has even UNICOM micropore, iron ion can be disperseed well in micropore, and because the aperture of micropore is nano-scale, also make the ferrous metal particle of reduction also there is nano-scale.
In order to guarantee to generate in the micropore of sintered glass the nano metallic nickel powder of q.s, sintered glass is all no less than 0.5 hour in ferric ion solutions and reductant solution soak time, and can adopt repeatedly and in ferric ion solutions or reductant solution, soak separately, or repeatedly in ferric ion solutions and reductant solution, replace the method for soaking, increase the quantity of the nano metallic nickel powder generating in the micropore of sintered glass.Say on the other hand, by control, soak number of times, can control the quantity of the nano metallic nickel powder generating in micropore, make the sintered glass of the different doping iron nanoparticles that require.
Preparation technology of the present invention is simple, preparation cycle is short, can effectively save production cost; Fe nanometer particles 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 doping iron 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 Fe nanometer particles, 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 doping iron 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 doping iron nanoparticle, is characterized in that, comprises the following steps:
(1), prepare respectively ferric ion solutions and for the reductant solution of reduced iron ion;
(2), select the sintered glass that is evenly distributed with UNICOM's micropore, sintered glass is placed in respectively to ferric ion solutions and reductant solution, and each at least soaks once, prepares the sintered glass of doping iron 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 ferric ion solutions is that iron containing compounds is dissolved in solvent and is made, and described ferric ion solutions concentration is 1mol/L～1 * 10
-6mol/L; Described iron containing compounds is iron(ic) chloride, iron nitrate or ferric sulfate, and described solvent is water or ethanol;
In described step (1), described reductant solution is the reductive agent for iron 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 doping iron nanoparticle as claimed in claim 3, is characterized in that, in described step (2), when described sintered glass is placed in ferric ion solutions 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 doping iron 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 doping iron 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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|---|---|---|---|
| CN200910190281.0A CN102030478B (en) | 2009-09-24 | 2009-09-24 | Iron nano particle doped porous glass and preparation method thereof |
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| CN102030478B true CN102030478B (en) | 2014-04-09 |
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| CN103833222B (en) * | 2014-01-14 | 2016-06-01 | 杭州电子科技大学 | The multi-functional quantum dot glass material that Fe is nano-particle doped and its preparation method |
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