CN1821314A - Process for preparing super fine cerium oxide for polishing - Google Patents
Process for preparing super fine cerium oxide for polishing Download PDFInfo
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- CN1821314A CN1821314A CN 200510132522 CN200510132522A CN1821314A CN 1821314 A CN1821314 A CN 1821314A CN 200510132522 CN200510132522 CN 200510132522 CN 200510132522 A CN200510132522 A CN 200510132522A CN 1821314 A CN1821314 A CN 1821314A
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Abstract
The present invention relates to preparation process of superfine cerium oxide powder, and belongs to the field of the preparing technology of RE compound. The preparation process of superfine cerium oxide powder includes the following steps: preparing salt solution containing cerium ion, adding surfactant into the solution, contacting the solution with alkali matter to control the pH value of the reaction suspension and produce precipitate; converting the suspension with oxalic acid and controlling the pH value in the reaction end point; filtering, washing and drying the precipitate, scalding at 600-1000 deg.cto obtain the superfine cerium oxide powder of grain size 10 nm to 3 micron and specific surface area smaller than 50 sq m/g. The superfine cerium oxide powder is used as polishing material, especially for optical mask.
Description
One, technical field
The present invention relates to a kind of preparation method who polishes with fine cerium oxide, belong to the preparing technical field of rare earth compound.
Two, background technology
In industrial circle, be extensive use of polishing powder.The use of polishing powder from rare earth can be traced back to the World War I, and the U.S. and Canada take the lead in using with the polishing powder from rare earth of cerium oxide as main component, are used for the grinding of accurate military equipment camera lens, have replaced the ferric oxide polishing powder.Cerium rouge has that polishing velocity height, operation pollute less, the quality of finish advantages of higher.Just because of the exploitation of polishing powder from rare earth, make the precision on glass grinding surface obtain improving significantly, thereby polishing powder from rare earth is utilized in the world widely.The application of cerium oxide on polishing powder now accounted for the whole application quantity of cerium oxide near half, become the maximum field that cerium oxide is used.
The market that polishing powder from rare earth is increasing is the application on field of photomasks, and photomask (claiming photomask again) is made with special glass such as silicate glass, and this glass need grind and polish, and technical requirements is extremely strict.Glass surface chromium plating after the polishing, reverse printed circuit in the above then is on the last semi-conductor chip with circuit projection surface spraying plating shading layer again.The polishing of photomask requires will to polish with the fine cerium oxide of even particle size distribution, shape high conformity than higher.
The preparation of polishing powder generally is divided into solid reaction process and precipitation-calcination method.Precipitation-calcination method is adopted in the preparation of fine cerium oxide polishing powder more.
United States Patent (USP) 5543126 discloses a kind of method of synthetic cerium oxide particle, it is that to be adjusted to the pH value be 8～11 for the aqueous medium that utilizes alkaline matter will contain cerous hydroxide (IV) and nitrate, and under pressure and temperature be controlled at 100～200 ℃ the heating these hydrous matters, the granularity that obtains cerium oxide is between 0.03 to 5 micron.The presoma of this method is a cerous hydroxide, and broad particle distribution, and polishing effect is bad.
TaiWan, China patent 328068 discloses mixed nitrate cerium (III) and has quickly heated up to 70～100 ℃, and regulating the pH value is between 5～10, and is incubated 0.2～20 hour under this temperature, obtains the cerium oxide powder of 10 to 80 nanometers.The presoma of this method also is a cerous hydroxide, and granularity is too thin, is not suitable for doing polishing powder and uses.
Aforesaid method has needs high-temperature high-pressure apparatus, costs an arm and a leg, and does not have economies of mass production to be worth; What have is not suitable for scale operation.And particle diameter is between 10nm～3 μ m, and specific surface area is less than 50m
2The preparation of the fine cerium oxide polishing powder of/g is not also reported.
Three, summary of the invention
The objective of the invention is to be to provide a kind of preparation specific surface area little even particle size distribution, shape high conformity, the lower-cost polishing method of fine cerium oxide.
Purpose of the present invention is realized by following technical scheme:
(1). dissolve the carbonate or the oxide compound of cerium with a kind of acid, or make the salts solution, particularly nitrate solution A of cerium with nitrate, muriate or the vitriol of water dissolution cerium;
(2). among this cerium solution A, the concentration of cerium ion is 0.1～2.0mol/l, and hydrogen ion concentration is 0.001～1mol/l;
(3). in this cerium solution, add dispersion agent G, form solution B;
(4). get a kind of alkaline matter H wiring solution-forming C;
(5). solution B mixed with solution C carry out chemical reaction, the reaction times is 10～180 minutes, and the pH value of control reaction end is 5～10, and the throw out that generates behind the chemical reaction is again through stirring formation suspension D 10～100 minutes;
(6). get oxalic acid, ammonium oxalate or basic metal oxalate and be made into the solution E that contains oxalic acid;
(7). suspension D and oxalic acid solution E fully contacted carry out chemical reaction, the reaction times is 20～200 minutes, and the pH value of control reaction end is 1～5, and the throw out that generates behind the chemical reaction through stirring 5～100 minutes, obtains throw out again;
(8). this throw out after filtration, washing, drying, obtain the presoma F of cerium oxide;
(9). this presoma F promptly obtains polishing fine cerium oxide product 600～1000 ℃ of following calcinations 2～10 hours.
Dispersion agent G is at least a organic surface-active substance.
The add-on of dispersion agent G is: 1～12% of cerium oxide weight.
Alkaline matter H is ammoniacal liquor, urea, bicarbonate of ammonia, volatile salt, alkali metal hydroxide, alkali-metal carbonate or alkali-metal acid carbonate.
The concentration that alkaline matter H is mixed with aqueous solution C, particularly C is 0.15～8mol/l.
The concentration of oxalic acid solution E is 0.1～2mol/l.
The presoma F of cerium oxide was 600～1000 ℃ of following calcinations 2～10 hours, and its heat-up rate is 50～500 ℃.
Advantage of the present invention is: contain the salts solution A of cerium ion by preparation, add dispersion agent G then in this solution, form solution B.Get a kind of alkaline matter H wiring solution-forming C.Solution B mixed with solution C carry out chemical reaction, the reaction times is 10～180 minutes, and the pH value of control reaction end is 5～10, and the throw out that generates behind the chemical reaction is again through stirring formation suspension D 10～100 minutes.Get, ammonium oxalate or basic metal oxalate oxalic acid is made into the solution E that contains oxalic acid.Suspension D and oxalic acid solution E fully contacted carry out chemical reaction, the reaction times is 20～200 minutes, and the pH value of control reaction end is 1～5, and the throw out that generates behind the chemical reaction is again through stirring 5～100 minutes.Filter then, wash, dry this throw out, 600～1000 ℃ of following calcinations 2～10 hours, its heat-up rate was 50～500 ℃ at last, can obtain particle diameter between 10nm～3 μ m, specific surface area is less than 50m
2The fine cerium oxide of/g.
The present invention adopts coprecipitation method capable of being industrialized to precipitate, prepare fine cerium oxide through steps such as precipitation, filtration, drying, roastings, precipitate with alkaline matters such as ammoniacal liquor, bicarbonate of ammonia earlier, obtain short grained throw out, make the transition with oxalic acid then, can control the crystal formation of fine cerium oxide product, make it be suitable for polishing.The present invention simultaneously prepares polishing and uses fine cerium oxide, and specific surface area is little, even particle size distribution, shape high conformity, and cost is lower.Also available industrial carbonic acid cerium, industrial carbon ammonium, industrial ammonia, industrial ethanedioic acid etc. are raw material, are fit to suitability for industrialized production, and the cost of this method is lower.
Four, description of drawings
Fig. 1 prepares the laser particle size figure of cerium oxide for the inventive method;
Fig. 2 prepares the sem photograph that reaches of cerium oxide for the inventive method:
Five, concrete embodiment
Embodiment 1:
With 2.2kg cerous carbonate (CeO
2〉=45%) uses 1.23LHNO
3Dissolving, and add the 5.48L deionized water and make solution A, add the 29.7g polyoxyethylene glycol therein and form solution B.Get the NH of 6.76L2.5mol/L
4HCO
3Become solution C.Under condition of stirring, solution C is added drop-wise in the solution B then, in the dropping process, the pH value of solution constantly raises, treat that solution C drips off after, the pH value of reaction system is 6.5; Generate white precipitate this moment, restir should precipitate 0.2 hour, became suspension D.Get 2.86kg oxalic acid 19.1L deionized water wiring solution-forming E.Then E is added drop-wise among the suspension D, in the dropping process, the pH value of solution constantly reduces, after treating that solution E drips off, the pH value of reaction system is 2.2, continues to stir 0.1 hour, with sedimentation and filtration, and with deionized water wash 3～4 times, then precipitation was placed 100 ℃ of still airs dry 8 hours, again 650 ℃ of roastings 2 hours, heat-up rate is 100 ℃/hour, product is a cerium oxide, and specific surface area is 35.6m
2/ g (U.S. Coulter SA3100 specific surface area analysis instrument records), its granularity D
50Be 0.355 μ m (U.S.'s Coulter LS230 laser particle analyzer records).
Embodiment 2:
With 2.5kg Ce (NO
3)
36H
2O and 4.80L deionized water are made solution A, add the 31.9g polyoxyethylene glycol therein and form solution B.Get the NaHCO of 8.13L1.5mol/L
3Become solution C.Under condition of stirring, solution C is added drop-wise in the solution B then, in the dropping process, the pH value of solution constantly raises, treat that solution C drips off after, the pH value of reaction system is 5.8; Generate white precipitate this moment, restir should precipitate 0.5 hour, became suspension D.Get 3.125kg oxalic acid 25L deionized water wiring solution-forming E.Then E is added drop-wise among the suspension D, in the dropping process, the pH value of solution constantly reduces, after treating that solution E drips off, the pH value of reaction system is 2.5, continues to stir 0.2 hour, with sedimentation and filtration, and with deionized water wash 3～4 times, then precipitation was placed 800 ℃ of still airs dry 12 hours, again 600 ℃ of roastings 2 hours, heat-up rate is 150 ℃/hour, product is a cerium oxide, and specific surface area is 42.3m
2/ g (U.S. Coulter SA3100 specific surface area analysis instrument records), its granularity D
50Be 0.336 μ m (U.S.'s Coulter LS230 laser particle analyzer records).
Embodiment 3:
With 0.8kg cerium oxide (CeO
2〉=99%) uses 1.00LHNO
3Dissolving, and add the 4.65L deionized water and make solution A, add the 28g polyoxyethylene glycol therein and form solution B.The ammoniacal liquor of getting 4.67L3.0mol/L becomes solution C.Under condition of stirring, solution C is added drop-wise in the solution B then, in the dropping process, the pH value of solution constantly raises, treat that solution C drips off after, the pH value of reaction system is 7.5; Generate brown precipitate this moment, restir should precipitate 0.2 hour, became suspension D.Get 1.08kg oxalic acid 5.4L deionized water wiring solution-forming E.Then E is added drop-wise among the suspension D, in the dropping process, the pH value of solution constantly reduces, after treating that solution E drips off, the pH value of reaction system is 1.5, continues to stir 0.2 hour, with sedimentation and filtration, and with deionized water wash 3～4 times, then precipitation was placed 120 ℃ of still airs dry 10 hours, again 700 ℃ of roastings 2 hours, heat-up rate is 200 ℃/hour, product is a cerium oxide, and specific surface area is 28.2m
2/ g (U.S. Coulter SA3100 specific surface area analysis instrument records), its granularity D
50Be 0.149 μ m (U.S.'s CoulterLS230 laser particle analyzer records), see accompanying drawing 1, accompanying drawing 2.
Claims (7)
1, a kind of preparation method who polishes with fine cerium oxide is characterized in that:
(1). dissolve the carbonate or the oxide compound of cerium with a kind of acid, or make the salts solution, particularly nitrate solution A of cerium with nitrate, muriate or the vitriol of water dissolution cerium;
(2). among this cerium solution A, the concentration of cerium ion is 0.1～2.0mol/l, and hydrogen ion concentration is 0.001～1mol/l;
(3). in this cerium solution, add dispersion agent G, form solution B;
(4). get a kind of alkaline matter H wiring solution-forming C;
(5). solution B mixed with solution C carry out chemical reaction, the reaction times is 10～180 minutes, and the pH value of control reaction end is 5～10, and the throw out that generates behind the chemical reaction is again through stirring formation suspension D 10～100 minutes;
(6). get oxalic acid, ammonium oxalate or basic metal oxalate and be made into the solution E that contains oxalic acid;
(7). suspension D and oxalic acid solution E fully contacted carry out chemical reaction, the reaction times is 20～200 minutes, and the pH value of control reaction end is 1～5, and the throw out that generates behind the chemical reaction through stirring 5～100 minutes, obtains throw out again;
(8). this throw out after filtration, washing, drying, obtain the presoma F of cerium oxide;
(9). this presoma F promptly obtains polishing fine cerium oxide product 600～1000 ℃ of following calcinations 2～10 hours.
2, a kind of preparation method who polishes with fine cerium oxide according to claim 1, it is characterized in that: dispersion agent G is at least a organic surface-active substance.
3, the polishing according to claim 2 preparation method of fine cerium oxide, it is characterized in that: the add-on of dispersion agent G is: 1～12% of cerium oxide weight.
4, a kind of preparation method who polishes with fine cerium oxide according to claim 1, it is characterized in that: alkaline matter H is ammoniacal liquor, urea, bicarbonate of ammonia, volatile salt, alkali metal hydroxide, alkali-metal carbonate or alkali-metal acid carbonate.
5, a kind of preparation method who polishes with fine cerium oxide according to claim 1, it is characterized in that: the concentration that alkaline matter H is mixed with aqueous solution C, particularly C is 0.15～8mol/l.
6, a kind of preparation method who polishes with fine cerium oxide according to claim 1, it is characterized in that: the concentration of oxalic acid, ammonium oxalate or basic metal oxalate solution E is 0.1～2mol/l.
7, a kind of preparation method who polishes with fine cerium oxide according to claim 1, its feature is being: the presoma F of cerium oxide was 600～1000 ℃ of following calcinations 2～10 hours, and its heat-up rate is 50～500 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541912B (en) * | 2006-11-20 | 2012-12-12 | Lg化学株式会社 | Method for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same |
| CN103059737A (en) * | 2013-01-25 | 2013-04-24 | 湖南皓志新材料股份有限公司 | Preparation method of high-polishing-rate rare-earth polishing powder |
| CN103754923A (en) * | 2014-01-28 | 2014-04-30 | 内蒙古科技大学 | Method for preparing superfine cerium oxide |
| CN106029572A (en) * | 2013-12-16 | 2016-10-12 | 罗地亚经营管理公司 | Liquid suspension of cerium oxide particles |
| CN108017082A (en) * | 2018-01-19 | 2018-05-11 | 常州市卓群纳米新材料有限公司 | A kind of preparation method for being conducive to stablize nano-cerium oxide color and state |
| CN108161582A (en) * | 2017-12-27 | 2018-06-15 | 重庆市华阳光学仪器有限公司 | A kind of telescope disk fine-processing technique |
| CN108408757A (en) * | 2018-03-15 | 2018-08-17 | 益阳鸿源稀土有限责任公司 | A kind of preparation method of high pure and ultra-fine scandium oxide powder |
| CN115403064A (en) * | 2022-09-20 | 2022-11-29 | 中国科学院长春应用化学研究所 | Cerium oxide and preparation method thereof |
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| DD154010A1 (en) * | 1980-11-03 | 1982-02-17 | Adolf Kaller | PROCESS FOR PRODUCING COARSE-BROKEN COMPOUNDS OF FINE-CRYSTALLINE CERDIOXIDE HYDRATES |
| TW311905B (en) * | 1994-07-11 | 1997-08-01 | Nissan Chemical Ind Ltd | |
| US6596042B1 (en) * | 2001-11-16 | 2003-07-22 | Ferro Corporation | Method of forming particles for use in chemical-mechanical polishing slurries and the particles formed by the process |
| CN100337926C (en) * | 2002-10-28 | 2007-09-19 | 日产化学工业株式会社 | Cerium oxide particles and process for the production thereof |
| DE10337199A1 (en) * | 2003-08-13 | 2005-03-10 | Degussa | cerium oxide powder |
| CN1321896C (en) * | 2004-04-14 | 2007-06-20 | 北京方正稀土科技研究所有限公司 | Process for preparing nano cerium dioxide |
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2005
- 2005-12-26 CN CNB2005101325228A patent/CN100357362C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541912B (en) * | 2006-11-20 | 2012-12-12 | Lg化学株式会社 | Method for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same |
| CN103059737A (en) * | 2013-01-25 | 2013-04-24 | 湖南皓志新材料股份有限公司 | Preparation method of high-polishing-rate rare-earth polishing powder |
| CN106029572A (en) * | 2013-12-16 | 2016-10-12 | 罗地亚经营管理公司 | Liquid suspension of cerium oxide particles |
| CN103754923A (en) * | 2014-01-28 | 2014-04-30 | 内蒙古科技大学 | Method for preparing superfine cerium oxide |
| CN103754923B (en) * | 2014-01-28 | 2016-08-17 | 内蒙古科技大学 | The preparation method of fine cerium oxide |
| CN108161582A (en) * | 2017-12-27 | 2018-06-15 | 重庆市华阳光学仪器有限公司 | A kind of telescope disk fine-processing technique |
| CN108017082A (en) * | 2018-01-19 | 2018-05-11 | 常州市卓群纳米新材料有限公司 | A kind of preparation method for being conducive to stablize nano-cerium oxide color and state |
| CN108408757A (en) * | 2018-03-15 | 2018-08-17 | 益阳鸿源稀土有限责任公司 | A kind of preparation method of high pure and ultra-fine scandium oxide powder |
| CN115403064A (en) * | 2022-09-20 | 2022-11-29 | 中国科学院长春应用化学研究所 | Cerium oxide and preparation method thereof |
| CN115403064B (en) * | 2022-09-20 | 2023-10-13 | 中国科学院长春应用化学研究所 | Cerium oxide and preparation method thereof |
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