CN102659124A - Method for preparing nanometer silicon powder by sol-microemulsion-hydro-thermal system - Google Patents
Method for preparing nanometer silicon powder by sol-microemulsion-hydro-thermal system Download PDFInfo
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- CN102659124A CN102659124A CN2012101063085A CN201210106308A CN102659124A CN 102659124 A CN102659124 A CN 102659124A CN 2012101063085 A CN2012101063085 A CN 2012101063085A CN 201210106308 A CN201210106308 A CN 201210106308A CN 102659124 A CN102659124 A CN 102659124A
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Abstract
A method for preparing a nanometer silicon powder by a sol-microemulsion-hydro-thermal system comprises technological processes of: preparation of sodium silicate, preparation of a silicic acid sol system, preparation of a four-phase microemulsion system, hydro-thermal system reaction, washing treatment and the like. The method provided by the invention has a simple technology, requires no special equipment, is convenient to operate and easy to control, and requires low production cost and low reaction temperature, and can be popularized for the preparation of nanometer silicon powder with natural powder quartz as a raw material.
Description
Technical field
The invention belongs to inorganic materials science and technology field, relate to a kind of preparation method of nano silicon micronization.
Background technology
Good physics, chemical property such as that silicon-dioxide has is nontoxic, tasteless, pollution-free, resistance to elevated temperatures is good, acid-alkali-corrosive-resisting, thermal expansivity is low, thermal conductivity is little, high-insulativity, hardness are big, aboundresources, piezoelectric effect and resonance effect.Therefore, silicon powder (SiO
2Micro mist, Silica Fine Powder) all has vast application prospect in electron and electrician fields such as chemical fields such as plastics, high-grade paint, senior paint, rubber, epoxy resin, advanced ceramic and computer chip, photoconductive fiber, unicircuit, solar cells.The quality of silicon powder product is not only relevant with its purity, and its globule size also is the essential factor of its performance of decision and application.Nano silicon micronization (nanometer SiO
2Micro mist) quantum size effect that causes owing to nano-scale, surface and interface effect, dielectric confinement effect etc.; Make it show the character of many uniquenesses; Like special light, electrical property and high magnetic resistance phenomenon, the high-strength and high ductility under thyrite phenomenon and the high temperature, high heat-resisting moisture-proof, high dielectric, high filler loading capacity and high stability etc.Nano silicon micronization also shows anti-ultraviolet optical property, and has the effect of adsorpting pigment ion, the decay of reduction pigment, has widened the range of application of silicon powder greatly.Therefore, nano silicon micronization can be widely used in support of the catalyst, polymer composite, electronic package material, precision casting and other relate to nearly all industry of applying silicon micro mist.
At present, the method for preparing nano silicon micronization mainly still is a chemical method, divides two kinds of gas phase and liquid phases.Vapor phase process is many to be basic raw material with the silicon tetrachloride, and hydrolysis makes smoke-like nanometer SiO under hydrogen-oxygen air-flow high temperature
2Micro mist.The product purity that these class methods make is higher, and good dispersion degree and surface hydroxyl are few, but expensive raw materials, energy consumption is high, technical sophistication, and equipment requirements is high; The liquid phase rule is main with the precipitator method and sol-gel method, is basic raw material with inorganic silicate (like water glass) or organosilicon source (like silicic acid fat) usually.The precipitator method with alkalimetal silicate through acidifying obtain to loosen, nanometer SiO finely divided, that be precipitated out with flocculent structure
2, the common purity of its resultant is not good, and nanoparticle exists with aggregated forms usually; Sol-gel method is in silicic acid fat, to add acid its basicity is reduced; Thereby bring out the polyreaction of silicate; Make the height that exists with the colloidal particle form in the system gather attitude silicate ion particle diameter and constantly increase the formation silicon sol; Along with the further reduction of pH value becomes the silicon gel, make nanometer SiO after the dehydration
2This method complex process, the production cycle is long, the difficult control of parameter, and product size is bigger than normal.The disadvantage that liquid phase method prepares nano silicon micronization also is its product cut size distribution range broad, because the hydrolysis rate of raw material can't keep highly even, thereby makes prepared SiO
2The nano particle size is uneven, and this may bring negative impact in practical application.
Summary of the invention
The problem of the wide and easy reunion of size distribution when preparing nano silicon micronization for solving the precipitator method, the present invention proposes the uniform torispherical nano silicon micronization of a kind of colloidal sol-micro emulsion-hydro-thermal compound system preparation size.Advantages such as this method need not complex apparatus, and it is simple to have processing condition, and easy handling is controlled, and production cost is low.
The present invention realizes through following technical scheme.
1) preparation of water glass.The mixed of 1:2.5 ~ 3.5 is even in molar ratio with molten silicon micro mist and yellow soda ash, carries out frit reaction under 900 ~ 1000 ℃ of the constant temperature, be cooled to after the room temperature the water glass solid, and pulverize.
2) preparation of silicic acid sol system.Take by weighing water glass powder prepared in a certain amount of step 1) and place container, add less water, fully stirring is dissolved water glass fully, forms sodium silicate solution, and its concentration is about 0.1 ~ 0.4M.Mol ratio by hydrochloric acid and water glass is the amount of 2 ~ 2.5:1, and slowly dripping hydrochloric acid also keeps stirring fast to make silicic acid sol in sodium silicate solution.
3) preparation of four phase microemulsion systems.At first; To step 2) in add oil phase in the prepared silicic acid sol (water-sol phase); Stir score layer solution, add tensio-active agent then, the continuation stirring is fully dissolved tensio-active agent or is mixed; Dropwise drip cosurfactant and keep continuing vigorous stirring, up to the microemulsion system that forms homogeneous.
Described oil phase is C
6~ C
8Alkane, naphthenic hydrocarbon or aromatic hydrocarbon etc.
Described tensio-active agent is one or more in AS, cats product or the nonionogenic tenside.AS such as X 2073, sodium laurylsulfonate, sodium lauryl sulphate etc.; Cats product such as cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride etc.; Nonionogenic tenside such as Vinylpyrrolidone polymer, all kinds of Soxylat A 25-7, polyoxyethylene glycol, tween (Tween), sapn (Span), Triton (Triton) etc.
Described cosurfactant is C
2~ C
8Alcohols.
Wherein, silicic acid sol (water-sol) is 1:1 ~ 4 with the volume ratio of oil phase, and the oil phase ratio is big more, and the water-in-oil-type micro emulsion is obvious more.Surfactant concentrations is about 0.02 ~ 0.2M, and it has considerable influence to the product size.
4) hydrothermal system reaction.Silicon sol-the microemulsion that is disposed in the step 3) is transferred in the hydrothermal reaction kettle, 100 ~ 150 ℃ of constant temperature sealed reaction some hrs, reaction finishes postcooling to room temperature.
5) carrying out washing treatment.Hydro-thermal reaction product in the step 4) is alternately washed for several times with a large amount of hot water and ethanol, be washed till and use AgNO
3Inspection does not have cl ions, makes nano silicon micronization after the suction filtration drying.
The product prepared with above-mentioned steps is the pure phase of amorphous structure silicon-dioxide through the X-ray diffraction Analysis and Identification, is the torispherical nano particle about particle diameter 50nm through scanning electron microscope analysis gained silicon powder.
Technological method involved in the present invention has following obvious advantage: though 1. the present invention is a raw material with the molten silicon micro mist, can extend to the natural powdery quartz is that (its composition is all SiO to raw material
2), because the initial thing of real reaction is actually water glass; 2. technology is simple, and no especial equipment requirements is easy to operate, is easy to control, and production cost is low; 3. temperature of reaction is low.
Embodiment
In order to understand the present invention better, below in conjunction with concrete embodiment the present invention is further specified, but protection content of the present invention is not limited to the following example.
Embodiment 1.
Present embodiment is to be raw material with industrial molten silicon micro mist, utilizes silicic acid sol-micro emulsion-hydrothermal system to prepare nano silicon micronization, and concrete technological process is following.
1) mixed of 1:3 is even in molar ratio with dihedral molten silicon micro mist and yellow soda ash, 1000 ℃ of following frit reaction half a hour, obtains the water glass solid after being cooled to room temperature, and pulverizes.
2) take by weighing 0.43g (3.5mmol) water glass powder, stirring and dissolving forms clarifying sodium silicate solution in 20mL water in beaker.Under the stirring that continues fast, slowly drip about 1.8mL hydrochloric acid (4M) preparation silicic acid sol.
3) in silicic acid sol, add the 15mL normal hexane; Mix and form profit layering solution, add the 0.6mmol cetyl trimethylammonium bromide, continue stirring it is fully dissolved; Solution becomes is muddy; In mixing solutions, dropwise drip n-hexyl alcohol while stirring,, make the silicic acid sol-microemulsion of homogeneous up to the solution becomes clarification.
4) silicic acid sol-microemulsion is transferred to 60mL hydro-thermal autoclave, sealing places thermostatic drying chamber, and 120 ℃ of isothermal reactions 8 ~ 12 hours, reaction finish postcooling to room temperature.
5) in order to reduce cl ions in the product, sodium ion and organic content as far as possible, hydro-thermal reaction product suction filtration is precipitated, and alternately wash repeatedly, be washed till and use AgNO with a large amount of 70 ~ 90 ℃ of hot water and absolute ethyl alcohol
3Check does not have a cl ions, and 60 ~ 70 ℃ of dryings 6 ~ 8 hours make white nano silicon micronization.
Embodiment 2.
Present embodiment is to be raw material with industrial molten silicon micro mist, utilizes silicic acid sol-micro emulsion-hydrothermal system to prepare nano silicon micronization, and concrete technological process is following.
1) mixed of 1:3 is even in molar ratio with molten silicon micro mist and yellow soda ash, 1000 ℃ of following frit reaction half a hour, obtains the water glass solid after being cooled to room temperature, and pulverizes.
2) take by weighing 0.43g (3.5mmol) water glass powder, stirring and dissolving forms clarifying sodium silicate solution in 20mL water in beaker.Under the stirring that continues fast, slowly drip about 1.8mL hydrochloric acid (4M) preparation silicic acid sol.
3) in silicic acid sol, add the 15mL normal hexane; Mix and form profit layering solution, add 16mL polyoxyethylene glycol-400, continue stirring and make its thorough mixing even; In mixing solutions, dropwise drip n-hexyl alcohol while stirring, become the silicic acid sol-microemulsion system of clarification, homogeneous up to solution.
4) gained silicic acid sol-microemulsion is transferred to 60mL hydro-thermal autoclave, sealing places thermostatic drying chamber, and 100 ℃ of isothermal reactions 8 ~ 12 hours, reaction finish postcooling to room temperature.
5) in order to reduce cl ions in the product, sodium ion and organic content as far as possible, hydro-thermal reaction product suction filtration is precipitated, and alternately wash repeatedly, be washed till and use AgNO with a large amount of 70 ~ 90 ℃ of hot water and absolute ethyl alcohol
3Titration does not have cl ions, and 60 ~ 70 ℃ of dryings 6 ~ 8 hours make nano silicon micronization.
Embodiment 3.
Present embodiment is to be raw material with industrial molten silicon micro mist, utilizes silicic acid sol-micro emulsion-hydrothermal system to prepare nano silicon micronization, and concrete technological process is following.
1) mixed of 1:3 is even in molar ratio with industrial molten silicon micro mist and yellow soda ash, 1000 ℃ of following frit reaction half a hour, obtains the water glass solid after being cooled to room temperature, and pulverizes.
2) take by weighing 0.43g (3.5mmol) water glass powder, stirring and dissolving forms clarifying sodium silicate solution in 10mL water in beaker.Under the stirring that continues fast, slowly drip about 1.8mL hydrochloric acid (4M) preparation silicic acid sol.
3) in silicic acid sol, add the 20mL normal hexane; Mix and form profit layering solution, add the 6mL tween-80, continue stirring and make its thorough mixing even; In mixing solutions, dropwise drip terepthaloyl moietie while stirring, up to the silicic acid sol-microemulsion system of solution becomes clarification, homogeneous.
4) gained silicic acid sol-microemulsion is transferred to 60mL hydro-thermal autoclave, sealing places thermostatic drying chamber, and 120 ℃ of isothermal reactions 8 ~ 12 hours, reaction finish postcooling to room temperature.
5) in order to reduce cl ions in the product, sodium ion and organic content as far as possible, hydro-thermal reaction product suction filtration is precipitated, and alternately wash repeatedly, be washed till and use AgNO with a large amount of 70 ~ 90 ℃ of hot water and absolute ethyl alcohol
3Inspection does not have a cl ions, and 60 ~ 70 ℃ of dryings 6 ~ 8 hours make nano silicon micronization.
Claims (4)
- , a kind of colloidal sol-micro emulsion-hydrothermal system prepares the method for nano silicon micronization, it is characterized in that according to the following steps:1) mixed of 1:2.5 ~ 3.5 is even in molar ratio with molten silicon micro mist and yellow soda ash, carries out frit reaction under 900 ~ 1000 ℃ of the constant temperature, be cooled to after the room temperature the water glass solid, and pulverize;2) take by weighing water glass powder prepared in a certain amount of step 1) and place container, add less water, fully stirring is dissolved water glass fully, forms sodium silicate solution, and its concentration is about 0.1 ~ 0.4M;Mol ratio by hydrochloric acid and water glass is the amount of 2 ~ 2.5:1, and slowly dripping hydrochloric acid also keeps stirring fast to make silicic acid sol in sodium silicate solution;3) to step 2) in add oil phase in the prepared silicic acid sol; Stir score layer solution, add tensio-active agent then, the continuation stirring is fully dissolved tensio-active agent or is mixed; Dropwise drip cosurfactant and keep continuing vigorous stirring, up to the microemulsion system that forms homogeneous;Described oil phase is C 6~ C 8Alkane, naphthenic hydrocarbon or aromatic hydrocarbon; Described tensio-active agent is one or more in AS, cats product or the nonionogenic tenside; Described cosurfactant is C 2~ C 8Alcohols;Wherein, the volume ratio of silicic acid sol and oil phase is 1:1 ~ 4; Surfactant concentrations is about 0.02 ~ 0.2M;4) silicon sol-microemulsion that is disposed in the step 3) is transferred in the hydrothermal reaction kettle, 100 ~ 150 ℃ of constant temperature sealed reaction some hrs, reaction finishes postcooling to room temperature;5) the hydro-thermal reaction product in the step 4) is alternately washed for several times with a large amount of hot water and ethanol, be washed till and use AgNO 3Inspection does not have cl ions, makes nano silicon micronization after the suction filtration drying.
- 2. the method for preparing nano silicon micronization according to claim 1 is characterized in that the AS described in the step 3) is X 2073, sodium laurylsulfonate, sodium lauryl sulphate.
- 3. the method for preparing nano silicon micronization according to claim 1 is characterized in that the cats product described in the step 3) is cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride.
- 4. the method for preparing nano silicon micronization according to claim 1 is characterized in that the nonionogenic tenside described in the step 3) is Vinylpyrrolidone polymer, all kinds of Soxylat A 25-7, polyoxyethylene glycol, tween, sapn, Triton.
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Cited By (6)
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| CN104332620A (en) * | 2014-08-26 | 2015-02-04 | 中国科学技术大学先进技术研究院 | Method for synthesizing silicon nano powder through hydrothermal reactions and applications of silicon nano powder |
| CN106904978A (en) * | 2017-02-28 | 2017-06-30 | 景德镇陶瓷大学 | A kind of method and its obtained product that spherical ceramic powder is prepared based on hard microemulsion method |
| WO2021248897A1 (en) * | 2020-06-12 | 2021-12-16 | 三达膜科技（厦门）有限公司 | Preparation method for zirconia ceramic ultrafiltration membrane |
| CN114538997A (en) * | 2022-02-25 | 2022-05-27 | 大连环球矿产股份有限公司 | Preparation method of composite silicate nitrogen fertilizer |
| CN114853498A (en) * | 2022-04-22 | 2022-08-05 | 胜利油田新海兴达实业集团有限责任公司 | Micron ceramic ball material and preparation method and application thereof |
| CN115784245A (en) * | 2022-12-29 | 2023-03-14 | 苏州西丽卡电子材料有限公司 | Preparation method of hydrophobic high-purity micron-sized spherical silicon dioxide powder |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332620A (en) * | 2014-08-26 | 2015-02-04 | 中国科学技术大学先进技术研究院 | Method for synthesizing silicon nano powder through hydrothermal reactions and applications of silicon nano powder |
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| WO2021248897A1 (en) * | 2020-06-12 | 2021-12-16 | 三达膜科技（厦门）有限公司 | Preparation method for zirconia ceramic ultrafiltration membrane |
| CN114538997A (en) * | 2022-02-25 | 2022-05-27 | 大连环球矿产股份有限公司 | Preparation method of composite silicate nitrogen fertilizer |
| CN114538997B (en) * | 2022-02-25 | 2023-03-14 | 大连环球矿产股份有限公司 | Preparation method of composite silicate nitrogen fertilizer |
| CN114853498A (en) * | 2022-04-22 | 2022-08-05 | 胜利油田新海兴达实业集团有限责任公司 | Micron ceramic ball material and preparation method and application thereof |
| CN115784245A (en) * | 2022-12-29 | 2023-03-14 | 苏州西丽卡电子材料有限公司 | Preparation method of hydrophobic high-purity micron-sized spherical silicon dioxide powder |
| CN115784245B (en) * | 2022-12-29 | 2024-01-16 | 苏州西丽卡电子材料有限公司 | Preparation method of hydrophobic high-purity micron-sized spherical silicon dioxide powder |
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Application publication date: 20120912 |