CN104671248A - Method for directly preparing high-purity silica sol with large particle size by using silicon powder method - Google Patents
Method for directly preparing high-purity silica sol with large particle size by using silicon powder method Download PDFInfo
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- CN104671248A CN104671248A CN201310622550.2A CN201310622550A CN104671248A CN 104671248 A CN104671248 A CN 104671248A CN 201310622550 A CN201310622550 A CN 201310622550A CN 104671248 A CN104671248 A CN 104671248A
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Abstract
The invention aims to solve the problems that conventional special silica sol with a large particle size for chemical mechanical polishing is poor in grinding production stability, small in particle size, wide in particle size distribution range and the like and discloses a method for directly preparing high-purity silica sol with a large particle size from silicon powder at certain high pressure. By controlling the reaction temperature and the reaction pressure, precise control over the particle size of the silica sol can be achieved. The process of the method is simplified, the conversion rate of the raw material silicon powder is high, the particle size dispersity of the silica sol is low, and the prepared silica sol with a large particle size can be applied to chemical mechanical polishing and grinding.
Description
Technical field
The present invention relates to the method preparing high-purity silicasol.Particularly relating to comprise uses organic amine as catalyzer, utilizes the method for silica flour direct preparative chemistry mechanical polishing special high purity Large stone silicon sol under a certain pressure.
Background technology
Since the nineties in last century, Large stone silicon sol sharply increases as the raw materials requirement amount of silicon wafer polishing liquid.Large stone silicon sol abrasive material due to particle large and evenly, good dispersity, good fluidity, easy to clean, concentrated shape can be made, Transport Package problem is easy to solve, polishing velocity is fast, quality of finish good, high quality chemically machinery polished (CMP) can be met, considerably improve glazed surface quality and the geometric accuracy of all kinds of silicon chip.
Combine " bulletin about progressively forbidding selling ordinary lighting incandescent lamp " printed and distributed according to National Development and Reform Committee, Department of Commerce, General Administration of Customs, State Administration for Industry & Commerce, State General Administration for Quality Supervision, on October 1st, 2012 rises, and forbids selling and import 100 watts and above general lighting incandescent light.Under the guide of this policy, domesticly emerge in large numbers a large amount of LED manufacturing enterprise.As the important foundation that LED produces, the polishing technology of LED Sapphire Substrate requires very strict, all adopt the silicon sol abrasive material of Large stone, high density and be equipped with suitable adjuvants both at home and abroad at present, polishing is carried out to sapphire single-crystal, can effectively improve sapphire working (machining) efficiency and surface finish.
Large stone silicon sol, as the chemical mechanical polishing liquid abrasive material of alloy surface, can make alloy surface not damaged, improves the roughness of alloy surface to nano level.At present, the CMP Ultra-precision Turning of the electronic product aluminum alloy casings such as mobile phone, panel computer, laptop computer, greatly facilitate the development of Large stone silicon sol as aluminium alloy polishing fluid abrasive material, become one of necessary raw material of electronic product casing nanometer-level ultra-precise processing.In the polishing process that aluminium alloy wheel hub of vehicle is produced, the artificial polishing of the many employings of manufacturing enterprise, occupy the time of about 35% of whole wheel hub production and a large amount of labor forces, and need to rely on skilled manual polisher (1-3 pcs/day), its extremely low production efficiency and high labour intensity seriously constrain the development of Automobile Enterprises.And with the aluminium alloy CMP processing mode that Large stone silicon sol is abrasive material, for raising aluminium alloy wheel hub production efficiency and quality, there is important pushing effect.
Visible, Large stone, high-concentration silicon sol are widely used in the industries such as microelectronics, photoelectron, alloy manufacture.The Large stone silicon sol of industrial preparation because of its particle diameter little, dispersity is uneven, limits its application in silicon substrate, LED substrate, alloy processing and other fields.From the beginning of this century, the demand of electronic industry to Large stone silicon sol constantly increases, and for meeting the need of market, research and development Large stone silicon sol also seems particularly urgent and necessary, has very important meaning and far-reaching influence to China's industrial development.
Have and much patent reports the method for silica flour legal system for silicon sol.Patent CN1830777A discloses a kind of preparation method of silicon sol, basic catalyst is added in silica aqueous dispersion, being attached on silica seeds particle by the active silicic acid micropartical of silica flour hydrolysis makes seed particles increase rapidly, directly obtain the Large stone silicon sol that median size is 5-500nm, temperature of reaction is 60-100 DEG C.CN101397139A discloses the preparation method of high-purity silicasol, common lower concentration, the silicon sol prepared by water glass or silica flour are processed with highly purified siloxanes in the basic conditions, change the surface chemical composition of silicon-dioxide in silicon sol, by inorganic or organic catalyst, high-purity silicasol all stable under obtained alkalescence, neutrality, acidic conditions in a heated condition, metals content impurity is at below 1ppm, and silicon sol particle diameter is about 30nm.CN101585541A discloses a kind of preparation method of electronic-grade silica sol, is that raw material carries out in two steps: first under catalytic condition, prepare high-purity silicasol with silica flour with silica flour; Then select particle diameter by particle diameter selector switch, spent ion exchange resin, by controlling to exchange flow velocity imurity-removal, finally adding stablizer and obtaining the electronic-grade silica sol that particle diameter is 10-20nm, can be used in each technical field of electronic industry.CN102101674A discloses a kind of method preparing silicon sol, adds in mixing tank by metallic silicon power, alkali and deionized water, passes into hot steam and carries out material mixing and heating, obtain silicon dioxide gel seed; With the silicon dioxide gel seed of preparation for mother liquor, add reaction mass in batches, pass into hot steam and carry out the heating of material mixing machine; After having reacted, remove the metallic silicon power of micro-reaction, obtain silicon sol.This invention mainly adopts hot steam from heat supply bottom reactor, by hot gas flow, hot steam heat rapidly, is evenly delivered to whole reaction system, overcomes the defect of chuck heating, is conducive to the even generation of silicon sol seed and the even growth of grain diameter.CN102417185A discloses a kind of preparation method of novel superlarge-particle-high-concentration high-concentration silicon sol.Raw material choose silica flour, sodium hydroxide and ceric ammonium nitrate and pure water.Activation silica flour, sodium hydroxide and the ceric ammonium nitrate aqueous solution is added at 80 DEG C, reaction 30min, after this every 30min adds a silica flour sodium hydroxide and the ceric ammonium nitrate aqueous solution, and total reaction time is 30h, and finally obtained Large stone silicon sol median size is at more than 150nm.Patent CN102849748A discloses a kind of method that elemental silicon single stage method prepares silicon sol.Elemental silicon is placed in dissolve medium, add appropriate sodium hydroxide or potassium hydroxide catalyst, be heated to 90-95 DEG C, reaction 8-10h, can obtain the rare finished product of silicon sol and mother liquor, mother liquid evaporation anhydrates, can obtain the silicon sol finished product of 3-100nm, the silicon sol cost prepared is low, good stability, quality is good, and product yield is high.
Patent CN1830777A, CN102101674A, CN102417185A, CN102849748A etc. disclose the method preparing Large stone silicon sol, and patent CN101397139A, CN101585541A etc. disclose the method preparing high-purity silicasol.Above-mentioned patent is the method that silicon sol prepared by silica flour, but is all react at ambient pressure, and the unexposed special method directly preparing Large stone silicon sol for the silica flour under certain high pressure.The present invention is then under certain high pressure, disposable various raw material, catalyzer is added reactor, and by the reaction conditions such as control temperature, pressure, obtain transformation efficiency more than 96%, median size reaches the Large stone silicon sol of 40-150nm.Although this preparation method employs pressure reaction still, higher to preparation method disclosed in the more above-mentioned patent of the requirement of equipment, but also having work simplification is easy to the features such as stability contorting, raw material silica flour transformation efficiency is high, silicon sol grain size dispersity is low, has good market outlook simultaneously.
Summary of the invention
The present invention is to solve the problems such as current chemically machinery polished special Large stone silicon sol abrasive material production stability is poor, particle diameter is little, particle size distribution range is wide, and disclose a kind of under certain high pressure, the method for Large stone silicon sol directly prepared by silica flour.By controlling temperature of reaction, reaction pressure, achieve the accurate control of silicon sol size, work simplification, raw material silica flour transformation efficiency is high, and silicon sol grain size dispersity is low.
The invention provides a kind of method of silica flour method direct preparation of high-purity degree Large stone silicon sol, adopt following technical scheme:
The method comprises the following steps:
(1) metallic silicon power, organic amine catalyst and deionized water are joined in autoclave according to a certain ratio mix; Sealed reactor, open and stir and heating, be rapidly heated certain temperature A, reaction 25-35min; Continue to be warming up to temperature B, and control reaction pressure C, terminate after reaction certain hour.Lower the temperature gradually, obtained high purity Large stone silicon sol;
(2), in step (1), metallic silicon power purity is more than 99%;
(3), in step (1), organic amine catalyst is the combination of any one or they in thanomin, diethanolamine, trolamine, hydroxyethylethylene diamine;
(4) in step (1), the ultrapure water of deionized water to be resistivity be 18.2 M Ω .cm;
(4), in step (1), the mass ratio of metallic silicon power and organic amine is (50-200): 1;
(5), in step (1), A temperature is 60-95 DEG C, preferred 80-90 DEG C;
(6), in step (1), B temperature is 105-200 DEG C, preferred 140-170 DEG C;
(7), in step (1), C pressure is 0.1-5MPa.
Large stone silicon sol prepared by the present invention can be applied to CMP art after ultrafiltration and concentration.
According to the requirement to product concentration, can concentrate or be diluted to respective concentration.
Gained silicon sol particle diameter can at 40-150nm, and mass percentage can regulate between 1-20%.
Compared with prior art, the technical characterstic of this preparation method and excellent results as follows:
(1) the present invention adopts silica flour method direct preparation of high-purity degree Large stone silicon sol, and work simplification is easy to stability contorting quality product, easy to operate, economical and efficient.
(2) raw material silica flour transformation efficiency of the present invention is high, and the Large stone silicon sol purity of preparation is high.
(3) the Large stone silicon sol size prepared of the present invention is controlled, and grain size dispersity is low, is applicable to the requirement of chemically machinery polished to abrasive material.
embodiment
Below in conjunction with embodiment, the present invention is described in detail:
embodiment 1
Get metallic silicon power (400 orders, purity is 99.5wt%) 1kg, 0.005kg hydroxyethylethylene diamine, 0.005kg trolamine, ultrapure water 20kg puts into autoclave, sealed reactor, opens and stirs and heating, be rapidly heated 80 DEG C, reaction 30min; Continue to be warming up to 150 DEG C, and control reaction pressure react end after 1.0MPa, 15h, lower the temperature gradually, obtained median size is 62.8nm, Large stone silicon sol that dispersity is 1.15, see Fig. 1.
embodiment 2
Get metallic silicon power (600 orders, purity is 99.5wt%) 1kg, 0.01kg hydroxyethylethylene diamine, ultrapure water 25kg puts into autoclave, sealed reactor, opens and stirs and heating, be rapidly heated 90 DEG C, reaction 30min; Continue to be warming up to 160 DEG C, and control reaction pressure react end after 1.5MPa, 20h, lower the temperature gradually, obtained median size is 105nm, Large stone silicon sol that dispersity is 1.12, see Fig. 2.
embodiment 3
Get metallic silicon power (500 orders, purity is 99.5wt%) 1kg, 0.01kg hydroxyethylethylene diamine and 0.002kg thanomin, ultrapure water 30kg puts into autoclave, sealed reactor, opens and stirs and heating, be rapidly heated 90 DEG C, reaction 30min; Continue to be warming up to 180 DEG C, and control reaction pressure react end after 2MPa, 20h, lower the temperature gradually, obtained median size is 98.5nm, Large stone silicon sol that dispersity is 1.10, see Fig. 3.
Accompanying drawing explanation
Fig. 1 high quality Gaussian distribution figure
Fig. 2 high quality Gaussian distribution figure
Fig. 3 high quality Gaussian distribution figure.
Claims (1)
1. the invention provides a kind of method of silica flour method direct preparation of high-purity degree Large stone silicon sol, adopt following technical scheme:
The method comprises the following steps:
Metallic silicon power, organic amine catalyst and deionized water are joined in autoclave according to a certain ratio and mixes; Sealed reactor, open and stir and heating, be rapidly heated certain temperature A, reaction 25-35min; Continue to be warming up to temperature B, and control reaction pressure C, terminate after reaction certain hour;
lower the temperature gradually, obtained high purity Large stone silicon sol;
Method according to claim 1, is characterized in that: metallic silicon power purity is more than 99%;
Method according to claim 1, is characterized in that: organic amine catalyst is the composition of any one or they in thanomin, diethanolamine, trolamine, hydroxyethylethylene diamine;
Method according to claim 1, is characterized in that: the ultrapure water of deionized water to be resistivity be 18.2 M Ω .cm;
Method according to claim 1, is characterized in that: the mass ratio of metallic silicon power and organic amine is (50-200): 1;
Method according to claim 1, is characterized in that: A temperature is 60-95 DEG C, preferred 80-90 DEG C;
Method according to claim 1, is characterized in that: B temperature is 105-200 DEG C, preferred 140-170 DEG C;
Method according to claim 1, is characterized in that: C pressure is 0.1-5MPa.
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| CN201310622550.2A CN104671248A (en) | 2013-11-30 | 2013-11-30 | Method for directly preparing high-purity silica sol with large particle size by using silicon powder method |
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| CN201310622550.2A CN104671248A (en) | 2013-11-30 | 2013-11-30 | Method for directly preparing high-purity silica sol with large particle size by using silicon powder method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112678832A (en) * | 2021-01-19 | 2021-04-20 | 德阳展源新材料科技有限公司 | Method for preparing electronic-grade silica sol based on bipolar membrane electroosmosis technology |
| CN114804122A (en) * | 2022-05-16 | 2022-07-29 | 山东科翰硅源新材料有限公司 | Preparation method of ultra-pure silica sol and product thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112678832A (en) * | 2021-01-19 | 2021-04-20 | 德阳展源新材料科技有限公司 | Method for preparing electronic-grade silica sol based on bipolar membrane electroosmosis technology |
| CN112678832B (en) * | 2021-01-19 | 2023-06-23 | 德阳展源新材料科技有限公司 | Method for preparing electronic grade silica sol based on bipolar membrane electroosmosis technology |
| CN114804122A (en) * | 2022-05-16 | 2022-07-29 | 山东科翰硅源新材料有限公司 | Preparation method of ultra-pure silica sol and product thereof |
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Application publication date: 20150603 |