CN102020421B - Method for preparing silver nanoparticles in cellular glass - Google Patents

Method for preparing silver nanoparticles in cellular glass Download PDF

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Publication number
CN102020421B
CN102020421B CN2009101901964A CN200910190196A CN102020421B CN 102020421 B CN102020421 B CN 102020421B CN 2009101901964 A CN2009101901964 A CN 2009101901964A CN 200910190196 A CN200910190196 A CN 200910190196A CN 102020421 B CN102020421 B CN 102020421B
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sintered glass
glass
nano silver
silver grain
cellular glass
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CN102020421A (en
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周明杰
马文波
陆树新
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Oceans King Lighting Science and Technology Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
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Abstract

The invention provides a method for preparing silver nanoparticles in cellular glass. The method comprises the following steps of: 1) selecting the cellular glass; 2) dissolving a silver compound into a solvent to prepare solution with the concentration range of between 1 and 1*10<-6>mol/L; 3) putting the cellular glass into the solution prepared in the step 2), and soaking for over 0.5 hour to ensure that the solution is fully infiltrated to micropores of the cellular glass; and 4) putting the cellular glass obtained in the step 3) into a heating furnace for heating, preserving heat for certain time, and then cooling to the room temperature to obtain the silver nanoparticles which are uniformly distributed in the cellular glass. By the method for preparing the silver nanoparticles in the cellular glass, which is provided by the invention, the size of the particles can be effectively limited; and the process parameters are set to ensure that the silver nanoparticles have high dispersibility and are distributed uniformly in glass.

Description

A kind of method that in sintered glass, prepares Nano silver grain
Technical field
The present invention relates to a kind of preparation method of Nano silver grain, relating in particular to a kind of is the method for preparing carriers Nano silver grain with the sintered glass.
Background technology
It is a kind of functional materials that vital role is arranged in fields such as optics, electronics, antibiotic and catalysis that gold doping belongs to matrix material that particle obtains.As far back as 4th century of Christian era, the Rome glazier has just understood at metallic particles such as glass doping gold and silver to have glasswork abundant, beautiful color to prepare.Nowadays, along with the development of nonlinear optics, especially after the third-order non-linear performance after nineteen eighty-three U.S. scientist Jian and Lind have studied the glass doped nanoparticle, people begin to bias toward its optical property aspect to the research that gold doping in the glass belongs to particle.When metal nanoparticle was impregnated in glass, glass matrix was isolated from each other particle, formed quantum dot, can make 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 material the important use advantage arranged in fields such as optical storage, transmission and switches with non-linear optical property; As comparing 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 be the important composition parts of following optoelectronic device.
At present, in vitreum, prepare the significant effort direction that equally distributed metal nanoparticle has become international physics, chemical boundary.Preparing method commonly used has: scorification, ion implantation and sol-gel method etc., these technologies are relatively ripe.But; These methods also all exist the some shortcomings part; As 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 will realize in glass matrix that homodisperse is not the easy thing of part; Ion implantation is that metal is injected in the glass matrix with ionic species; Obtain metal nanoparticle through 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 sol-gel method will contain metal-salt in preparation glass solution to mix with glass colloidal sol; Can access the glass that contains metal nanoparticle through aftertreatment; The dispersion of metal nanoparticle is also relatively even; It is longer that but this method prepares the cycle of glass, and the intensity of glass sample is lower, do not reach practical requirement.
Summary of the invention
The purpose of the embodiment of the invention is to provide a kind of method that in sintered glass, prepares Nano silver grain, and it is more even to distribute in the time of according to method provided by the invention Nano silver grain being prepared in vitreum.
The embodiment of the invention is achieved in that a kind of method that in sintered glass, prepares Nano silver grain, comprises the steps:
1) chooses sintered glass;
2) silver compound is dissolved in the solvent, is mixed with concentration range in 1mol/L～1 * 10 -6In the solution of mol/L;
3) sintered glass is put into step 2) solution of preparation, soak more than the 0.5h, utilize the balance quality of molecule, make solution evenly, disperse to penetrate in the micropore of sintered glass;
4) sintered glass that obtains in the step 3) is put into process furnace and heat, insulation for some time postcooling can make equally distributed Nano silver grain to room temperature in sintered glass.
Above-mentioned steps can repeat.
Preferably, sintered glass according to the invention is selected vagcor for use, and its predominant quantity per-cent is: SiO 294.0～98.0%, B 2O 31.0～3.0%, Al 2O 31.0～3.0%, also can select for use and be added with Na 2O 0～1%, ZrO 20～1% sintered glass, said sintered glass pore size is 4～100 nanometers, the volume of micropore accounts for 25～40% of glass TV, distributes uniformly on sintered glass to guarantee silver compound.
The compound of described silver is preferably Silver Nitrate;
Described solvent is preferably water of fine quality, inexpensive, that cost is low and ethanol.
Further; Behind the said soaking step, before the heating steps, also can be provided with and clean or/and drying program promptly soaks the back that finishes and takes out sintered glass; Compound to the sintered glass remained on surface cleans after drying; Avoiding issuable cracking phenomena in the follow-up heating process step, its drying temperature is 60 ℃～90 ℃, time of drying 2h～3h;
Further, the heating of said step 4) can also can be carried out under the reducing atmosphere environment under vacuum environment, said reducing atmosphere environment, CO that promptly in process furnace, exists or H 2Or N 2With H 2Gas mixture.This step is in order to guarantee that the high-temperature decomposition product of silver compound is reduced into simple substance.
Further, when said sintered glass heated in process furnace, speed that can 2 ℃～3 ℃/min was warmed up to 450 ℃～650 ℃, and insulation 0.5h～5h postcooling is to room temperature.The experiment proof; The present invention adopts equal difference speed incremental manner to heat up and adopts the regular hour insulation; Both can guarantee the abundant decomposition of the compound of silver; Nano silver grain stably is present in the micropore with solid phase, simultaneously can effectively avoids reaching too high temperature rapidly and the sintered glass cracking that causes and the defective of distortion.
To sum up; The invention provides a kind of is the method for preparing carriers Nano silver grain with the sintered glass; Because sintered glass has be isolated from each other nanometer level microporous, in micropore, prepares Nano silver grain, can limit the size of particle effectively; The setting of its processing parameter can make Nano silver grain in glass, have good dispersiveness, and it is more even to distribute.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1:
Compound concentration is the Silver Nitrate (AgNO of 1mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 294.0%, B 2O 33.0%, Al 2O 33.0%, pore size is 4 nanometers, the volume of micropore account for the glass TV 40%) be put into AgNO 3Soak 0.5h in the aqueous solution, then sintered glass is put in the vacuum electric furnace, vacuumize, vacuum tightness reaches 10 in stove -4During Pa, beginning is warmed up to 500 ℃ with the speed of 3 ℃/min, and insulation 1h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 2:
Compound concentration is the Silver Nitrate (AgNO of 0.5mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 298.0%, B 2O 31.0%, Al 2O 31.0%, pore size is 100 nanometers, the volume of micropore account for the glass TV 25%) be put into AgNO 3Soak 1h in the aqueous solution; Take out sintered glass, be put into 85 ℃ oven drying 2h, then sintered glass is put in the tube furnace, logical CO gas, and begin to be warmed up to 450 ℃ with the speed of 3 ℃/min, insulation 2h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 3:
Compound concentration is 1 * 10 -1Silver Nitrate (the AgNO of mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 295.0%, B 2O 32.5%, Al 2O 32.5%, pore size is 50 nanometers, the volume of micropore account for the glass TV 30%) be put into AgNO 3Soak 2h in the aqueous solution; Take out sintered glass,, then sintered glass is put in the tube furnace, lead to H with distilled water flushing 3 times 2Gas, and begin to be warmed up to 450 ℃ with the speed of 3 ℃/min, insulation 1h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 4:
Compound concentration is the Silver Nitrate (AgNO of 1mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 294.0%, B 2O 33.0%, Al 2O 33.0%, pore size is 4 nanometers, the volume of micropore account for the glass TV 40%) be put into AgNO 3Soak 0.5h in the aqueous solution; Take out sintered glass,, and be put into 90 ℃ oven drying 2h with distilled water flushing 3 times; Then sintered glass is put in the vacuum electric furnace, vacuumizes, vacuum tightness reaches 10 in stove -4During Pa, beginning is warmed up to 500 ℃ with the speed of 3 ℃/min, and insulation 1h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 5:
Compound concentration is the Silver Nitrate (AgNO of 0.5mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 298.0%, B 2O 31.0%, Al 2O 31.0%, pore size is 100 nanometers, the volume of micropore account for the glass TV 25%) be put into AgNO 3Soak 1h in the aqueous solution; Take out sintered glass,, and be put into 85 ℃ oven drying 2h with distilled water flushing 3 times; Then sintered glass is put in the tube furnace, logical CO gas, and begin to be warmed up to 450 ℃ with the speed of 3 ℃/min; Insulation 2h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 6:
Compound concentration is 1 * 10 -1Silver Nitrate (the AgNO of mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 295.0%, B 2O 32.5%, Al 2O 32.5%, pore size is 50 nanometers, the volume of micropore account for the glass TV 30%) be put into AgNO 3Soak 2h in the aqueous solution; Take out sintered glass,, and be put into 80 ℃ oven drying 2.5h with distilled water flushing 3 times; Then sintered glass is put in the tube furnace logical H 2Gas, and begin to be warmed up to 450 ℃ with the speed of 3 ℃/min, insulation 1h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 7:
Compound concentration is 1 * 10 -2Silver Nitrate (the AgNO of mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 296.0%, B 2O 32.0%, Al 2O 32.0%, pore size is 70 nanometers, the volume of micropore account for the glass TV 35%) be put into AgNO 3Soak 2h in the aqueous solution; Take out sintered glass,, and be put into 75 ℃ oven drying 3h with distilled water flushing 3 times; Then sintered glass is put in the tube furnace logical N 2And H 2Volume ratio is 95: 5 a mixed gas, and begins to be warmed up to 500 ℃ with the speed of 3 ℃/min, and insulation 4h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 8:
Compound concentration is 1 * 10 -3Silver Nitrate (the AgNO of mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 297.0%, B 2O 31.0%, Al 2O 31.0%, Na 2O 0.5%, ZrO 20.5%, pore size is 80 nanometers, the volume of micropore account for the glass TV 32%) be put into AgNO 3Soak 3h in the aqueous solution; Take out sintered glass,, and be put into 80 ℃ oven drying 3h with distilled water flushing 3 times; Then sintered glass is put in the tube furnace logical N 2And H 2Volume ratio is 95: 5 a mixed gas, and begins to be warmed up to 600 ℃ with the speed of 3 ℃/min, and insulation 0.5h postcooling is promptly prepared Nano silver grain to room temperature in sintered glass.
Embodiment 9:
Compound concentration is 1 * 10 -4Silver Nitrate (the AgNO of mol/L 3) aqueous solution 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 296.0%, B 2O 31.0%, Al 2O 31.0%, Na 2O 1.0%, ZrO 21.0%, pore size is 55 nanometers, the volume of micropore account for the glass TV 38%) be put into AgNO 3Soak 3h in the aqueous solution; Take out sintered glass,, and be put into 70 ℃ oven drying 2h with distilled water flushing 3 times; Then sintered glass is put in the vacuum electric furnace, vacuumizes, vacuum tightness reaches 10 in stove -3P aThe time, beginning is warmed up to 450 ℃ with the speed of 2 ℃/min, is incubated 5 postcooling to room temperature.The aforesaid operations step is repeated 2 times, promptly in sintered glass, prepare Nano silver grain.
Embodiment 10:
Compound concentration is 1 * 10 -5Silver Nitrate (the AgNO of mol/L 3) ethanolic soln 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 295.0%, B 2O 32.0%, Al 2O 32.0%, Na 2O 1.0%, and pore size is 20 nanometers, the volume of micropore account for the glass TV 35%) be put into AgNO 3Soak 3h in the ethanolic soln; Take out sintered glass,, and be put into 65 ℃ oven drying 2h with distilled water flushing 3 times; Then sintered glass is put in the tube furnace logical N 2And H 2Volume ratio is 95: 5 a mixed gas, and begins to be warmed up to 500 ℃ with the speed of 3 ℃/min, and insulation 2h postcooling is to room temperature.The aforesaid operations step is repeated 5 times, promptly in sintered glass, prepare Nano silver grain.
Embodiment 11:
Compound concentration is 1 * 10 -6Silver Nitrate (the AgNO of mol/L 3) ethanolic soln 10mL, and be kept in the brown narrow-mouthed bottle that has glass stopper.With porous borosilicate glass (predominant quantity per-cent: SiO 296.0%, B 2O 31.5%, Al 2O 32.5%, pore size is 10 nanometers, the volume of micropore account for the glass TV 40%) be put into AgNO 3Soak 3h in the ethanolic soln; Take out sintered glass,, and be put into 60 ℃ oven drying 2.5h with distilled water flushing 3 times; Then sintered glass is put in the tube furnace logical H 2Gas, and begin to be warmed up to 650 ℃ with the speed of 3 ℃/min, insulation 0.5h postcooling is to room temperature.The aforesaid operations step is repeated 8 times, promptly in sintered glass, prepare Nano silver grain.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (4)

1. a method that in sintered glass, prepares Nano silver grain is characterized in that, comprises the steps:
1) choose sintered glass, said sintered glass micropore diameter size is 4～100 nanometers, and the volume of micropore accounts for 25～40% of glass TV;
2) silver compound is dissolved in the solvent, is mixed with concentration range in 1mol/L～1 * 10 -6In the solution of mol/L;
3) sintered glass is put into step 2) solution of preparation, soak more than the 0.5h;
4) sintered glass that obtains in the step 3) is put into process furnace and heat, insulation for some time postcooling can make equally distributed Nano silver grain to room temperature in sintered glass, and said heating steps is at CO or H 2Or N 2With H 2The reducing atmosphere of gas mixture under carry out, when said sintered glass heats, be warmed up to 450 ℃～650 ℃ with the speed of 2 ℃～3 ℃/min in process furnace, insulation 0.5h～5h postcooling is to room temperature.
2. a kind of method that in sintered glass, prepares Nano silver grain according to claim 1 is characterized in that, said sintered glass predominant quantity per-cent is: SiO 294.0～98.0%, B 2O 31.0～3.0%, Al 2O 31.0～3.0%, Na 2O 0～1%, ZrO 20～1%.
3. a kind of method that in sintered glass, prepares Nano silver grain according to claim 1 is characterized in that the compound of described silver is preferably Silver Nitrate; Described solvent is preferably water and ethanol.
4. a kind of method that in sintered glass, prepares Nano silver grain according to claim 1; It is characterized in that, behind the soaking step of said step 3), before the heating steps of step 4), also comprise and cleaning or/and drying program; Said drying temperature is 60 ℃～90 ℃, time of drying 2h～3h.
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RU2540741C1 (en) * 2013-12-24 2015-02-10 Федеральное государственное бюджетное учреждение науки Институт физики прочности и материаловедения Сибирского отделения Российской академии наук (ИФПМ СО РАН) Method of making article from granular foam glass-ceramic
CN111940143A (en) * 2020-07-24 2020-11-17 合肥百诺金科技股份有限公司 Sterilizing, disinfecting and ozone-removing electrostatic adsorption electrode and preparation method thereof
CN112695407A (en) * 2020-12-28 2021-04-23 上海德福伦化纤有限公司 Glass silver-loaded antibacterial polyester fiber and preparation method thereof

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