US20040154230A1 - Polishing formulations for SiO2-based substrates - Google Patents
Polishing formulations for SiO2-based substrates Download PDFInfo
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- US20040154230A1 US20040154230A1 US10/703,848 US70384803A US2004154230A1 US 20040154230 A1 US20040154230 A1 US 20040154230A1 US 70384803 A US70384803 A US 70384803A US 2004154230 A1 US2004154230 A1 US 2004154230A1
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- Prior art keywords
- ceria
- particles
- ceramic
- powder
- polishing
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- 238000005498 polishing Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 238000009472 formulation Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 52
- 239000000377 silicon dioxide Substances 0.000 title claims description 16
- 229910052681 coesite Inorganic materials 0.000 title description 10
- 229910052906 cristobalite Inorganic materials 0.000 title description 10
- 229910052682 stishovite Inorganic materials 0.000 title description 10
- 229910052905 tridymite Inorganic materials 0.000 title description 10
- 239000000758 substrate Substances 0.000 title description 5
- 235000012239 silicon dioxide Nutrition 0.000 title description 3
- 239000002245 particle Substances 0.000 claims abstract description 41
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000007771 core particle Substances 0.000 claims description 10
- 229910021485 fumed silica Inorganic materials 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 230000032683 aging Effects 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- 150000000703 Cerium Chemical class 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000012695 Ce precursor Substances 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012693 ceria precursor Substances 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
- C09K3/1445—Composite particles, e.g. coated particles the coating consisting exclusively of metals
Definitions
- This invention relates to materials used to polish SiO 2 -based substrates and specifically to abrasive particles used in such materials.
- ceria operates on glass in a chemical-mechanical polishing manner which is not available with the other abrasive oxides.
- Ceria with its properties largely dependent upon its defect structure, especially shows affinity to SiO 2 which is the basis for the chemical-mechanical polishing effect. It is also softer than SiO 2 or SiO 2 -based glass, which prevent the surface from rough scratches.
- commercial ceria polishing compositions may contain only 40 to 80% of ceria but the use of such materials is confined to polishing conventional glasses used for mirrors, TV screen surfaces, ordinary optical lenses and so on where the highest finish standards are not so critical. With the maximum chemical-mechanical effect, pure ceria is however still used for the most critical high precision surfaces.
- the present invention provides abrasive particles which comprise a ceramic core with a coating of ceria deposited thereon such that the ceria represents for 2 to 30%, and preferably from 3 to 15% of the weight of the particles.
- the inert core will provide mechanical action while the shell give chemical action during the polishing.
- the ceramic core can be any ceramic oxide but is preferably one on which ceria can readily precipitate and adhere as a thin layer.
- the interface between the core and shell ceria should be strong enough to ensure that the shell will not easily come off during processing and abrasion action in the course of polishing a substrate.
- the particle sizes are preferably those most useful in putting a polished surface on glass. Most preferably the particles do not contain a large volume of particles that are significantly larger than the average. Therefore with the particle sizes herein being the volume average particle size as measured by a Microtrac technique, the d 90 particle size should not be more than an order of magnitude larger than the d 50 particle size.
- the actual size of the coated particles is determined by the application intended and the practicalities of the process. Large sized particles give higher material removal rate but normally worse surface finishing than the small sized particles. Since a major objective is to reduce the cost of the polishing operation, the use of very fine ceramic core particles will lead to a high surface area and therefore a large amount of ceria will be required to place a coat thereon. In addition the coating process becomes more difficult to carry out. As a practical matter therefore the coated particles are commonly built on 20 to 2000 nanometer core particles and the shell deposited thereon has a thickness, estimate from the increase in weight of the particles, of from 1 to 20 and preferably from 2 to 10 nanometers.
- the invention further provides a polishing-formulation comprising an abrasive powder as described above dispersed in a carrier medium.
- the formulation can optionally also contain an adjuvant which aids in the dispersion of debris resulting from the polishing action such that it can be removed from the surface in suspension in the dispersion medium.
- the invention further provides a method making abrasive particles comprising a ceramic shell with a surface layer of ceria which comprises dispersing a ceramic powder in a dispersion medium such as water which contains in solution a ceria precursor and treating the dispersion to separate a powder comprising ceramic powder particles having a surface layer of ceria deposited thereon.
- a dispersion medium such as water which contains in solution a ceria precursor
- the preferred substrate ceramic materials are silica, silicon carbide and alumina.
- the silica option is more preferably fumed silica since this is readily available in the form of a very fine powder with relatively uniform particle sizes. It is also quite insoluble in water which is the preferred dispersion medium for the production of polishing slurries providing the pH is not excessively acidic or basic.
- the silica option can also be fused silica powder, which has larger size ( ⁇ 1-2 um) or colloidal silica, which has smaller size (10 nm ⁇ 100 nm) as compared with fumed silica.
- the alumina option can be particles of alpha alumina, gamma alumina, amorphous alumina or boehmite.
- Silicon Carbide can be in either the alpha or beta crystalline phase, but with the surface oxidized so that ceria can be more adherent than on SiC itself. References to “silicon carbide” in the following should be understood to refer to such surface-oxidized materials.
- a polishing slurry containing the novel powder according to the invention is preferably water-based and may contain water-soluble detergent materials such as phosphates, as long as no inhibiting effect upon the contact of ceria to the substrate surface.
- the pH of the polishing formulation can be kept from 3 to 11. Normally, higher pH leads to higher hydration rate or dissolution rate of SiO 2 which benefit the polishing action. However, low pH might be preferred in some cases where good stability of the slurry is required, as ceria can be better dispersed in acidic solution and the slurry will have longer shelf time. In either the cases, the isoelectric point (IEP) of ceria, normally around pH 7, should be avoided.
- IEP isoelectric point
- the production of the ceria-coated particles is preferably accomplished by a solution process.
- ceramic particles need to be mixed with water to make a good and stable dispersion.
- water soluble cerium salts can be added before or after the pH is raised to close to 10 at which point, cerium salts will completely precipitate as oxide or hydroxide. If addition occurs before the pH is raised, a mixture of cerium salt with ceramic particles in water will typically have an acid pH value and this can be adjusted by addition of a base that is effective to raise the pH, typically to about 10. At this pH the cerium salt deposits on the ceramic particles, probably in the form of the hydrated oxide.
- a straightforward way is to add NH 4 OH to the solution containing the cerium salts under vigorous stirring until a pH of 10 is reached.
- a basic chemical such as urea can be dissolved in the solution, followed by decomposition of urea into ammonia by heating the solution to an elevated temperature, preferably from about 75 to 90° C. and holding the solution at the temperature until ceria deposition is complete.
- pH is raised in-situ, and there is no abrupt local increase of pH in a local region as would occur when ammonia is added.
- Cerium salts can also be added after the pH is raised.
- an aqueous dispersion of ceramic particles can be first mixed with ammonia to a high pH of about 10, and an aqueous solution of a cerium salt can then be added drop-wise to the solution while under stirring.
- an aqueous solution of a cerium salt can then be added drop-wise to the solution while under stirring.
- the salt solution is added the pH falls so a certain amount of aqueous ammonia needs to be added to keep the solution around pH 10.
- the particles can be separated by sedimentation or by the use of a centrifuge and fired at from 600 to 1000° C. to form the ceria as a thin shell on the surfaces of the ceramic particles.
- This shell can represent any desired percentage of the weight of the powder, such as from 3 to 25% and most preferably from 3 to 15% of the weight of the particles.
- the precursors for the ceria can be any cerium salts that are water soluble, such as Ce(NO 3 ) 3 .6H 2 O, Ce(SO 4 ) 2 .4H 2 O, (NH 4 ) 2 .Ce(NO 3 ) 6 and the like. It is also possible to use a commercial CeO 2 sol, (for example Nyacol).
- a number of glass polishing slurries were produced with a pH of 10 and a 5 wt % solids content of the abrasive.
- the slurries differed only in the abrasive used as follows:
- PA-1 100% pure ceria. This is made from the same cerium nitrate salt via the same precipitation and firing process, except there was no silica powder used as cores.
- PA-2 “Opaline” which is a commercial ceria polishing powder containing about 100% of ceria obtained from Rhodia under that registered trademark.
- PA-3 100% fumed silica having a purity of about 96% and an average particle size, (d 50 ), of about 0.4 micrometers.
- INV-1 This illustrates the invention and was prepared using the above process based on the fumed silica in PA-3.
- the present invention provides a glass polishing formulation that removes material at a rate that is a little less than that achieved with the most pure ceria powders available, in about the same time and with a better surface finish. In all respects it performs better that the silica core powder at only a slightly elevated cost.
- the fumed silica used in Example 1, (200 g) was mixed with 1800 g of DI water. 2.12 g of ammonia was added to adjust the pH to 10 under vigorous stirring. In a separate beaker, 100 g of Ce(NO 3 ) 3 .6H 2 O was dissolved in 100 g of DI water. Under the vigorous stirring, the cerium nitrate solution is added drop wise to the fumed silica slurry slowly. At the same time, aqueous ammonia ( ⁇ 30%) is added to the slurry to keep the solution at pH ⁇ 10 and thus ensure that all cerium salt hydrolyzes completely. In total, 86.8 g of ammonia was added together with the cerium nitrate solution.
- solid material After finishing addition of the cerium nitrate solution, solid material is separated from solution by centrifuge and dried in oven for overnight. Thereafter, the material is fired at 800° C./2 hrs, followed by crushing into fine powder before being mixed with water to make a polishing slurry.
- Example 2 The above procedures in Example 2 were used to generate the core-shell structure on fused silica powder which is commercially available from Alfa Aesar, with 2 um average particle size; S.A., 2 m 2 /g; and 99.5% purity.
- the fused silica was first dispersed in water, with pH adjusted with ammonia.
- the slurry was poured through a metal screen #325 to remove any large particles, before the same treatment the same way as in Example 2.
- the product was pulverized into powder for polishing test.
- PA-4 Fused silica powder obtained from alfa Aesar that was used as cores in Example 3.
- cerium precursors other than cerium nitrate can also be used to process different type of core particles to achieve improved polishing performance. It is also noticeable that the larger silica core particles, while showing an impressive material removal rate, led to a rougher finish on account of the larger average particle size.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Composite Materials (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Powders of particles comprising a ceramic core and a coating of ceria deposited thereon provide an economical and effective abrasive for glass polishing formulations.
Description
- This invention relates to materials used to polish SiO2-based substrates and specifically to abrasive particles used in such materials.
- The most widely used abrasive for polishing SiO2 based materials, such as glass or quartz surfaces is ceria and this is because it gives the highest polishing rate combined with the best surface finish among all the alternative abrasives materials that have been tried such as silica, iron oxide, zirconia and various forms of alumina. However it is also very expensive when supplied as a pure material. To mitigate this factor, ceria has been used in admixture with other abrasives such as oxides of silicon, aluminum, rare earth metals or calcium. This saves money but carries a penalty since, in general terms and in the context of glass polishing, the higher the impurity level, the longer it takes to remove the required amount of surface and the worse the surface finish. In part this is because ceria operates on glass in a chemical-mechanical polishing manner which is not available with the other abrasive oxides. Ceria, with its properties largely dependent upon its defect structure, especially shows affinity to SiO2 which is the basis for the chemical-mechanical polishing effect. It is also softer than SiO2 or SiO2-based glass, which prevent the surface from rough scratches. Thus commercial ceria polishing compositions may contain only 40 to 80% of ceria but the use of such materials is confined to polishing conventional glasses used for mirrors, TV screen surfaces, ordinary optical lenses and so on where the highest finish standards are not so critical. With the maximum chemical-mechanical effect, pure ceria is however still used for the most critical high precision surfaces.
- There is therefore a need to supply high quality ceria polishing compositions at a more affordable price that are still adapted for use in producing very high precision polished glass surfaces.
- The present invention provides abrasive particles which comprise a ceramic core with a coating of ceria deposited thereon such that the ceria represents for 2 to 30%, and preferably from 3 to 15% of the weight of the particles. In such a core-shell structure, the inert core will provide mechanical action while the shell give chemical action during the polishing.
- The ceramic core can be any ceramic oxide but is preferably one on which ceria can readily precipitate and adhere as a thin layer. The interface between the core and shell ceria should be strong enough to ensure that the shell will not easily come off during processing and abrasion action in the course of polishing a substrate. Preferably, not only physical attachment on the cores but strong chemical bonding exists between the CeO2 coating and cores.
- The particle sizes are preferably those most useful in putting a polished surface on glass. Most preferably the particles do not contain a large volume of particles that are significantly larger than the average. Therefore with the particle sizes herein being the volume average particle size as measured by a Microtrac technique, the d90 particle size should not be more than an order of magnitude larger than the d50 particle size.
- The actual size of the coated particles is determined by the application intended and the practicalities of the process. Large sized particles give higher material removal rate but normally worse surface finishing than the small sized particles. Since a major objective is to reduce the cost of the polishing operation, the use of very fine ceramic core particles will lead to a high surface area and therefore a large amount of ceria will be required to place a coat thereon. In addition the coating process becomes more difficult to carry out. As a practical matter therefore the coated particles are commonly built on 20 to 2000 nanometer core particles and the shell deposited thereon has a thickness, estimate from the increase in weight of the particles, of from 1 to 20 and preferably from 2 to 10 nanometers.
- The invention further provides a polishing-formulation comprising an abrasive powder as described above dispersed in a carrier medium. The formulation can optionally also contain an adjuvant which aids in the dispersion of debris resulting from the polishing action such that it can be removed from the surface in suspension in the dispersion medium.
- The invention further provides a method making abrasive particles comprising a ceramic shell with a surface layer of ceria which comprises dispersing a ceramic powder in a dispersion medium such as water which contains in solution a ceria precursor and treating the dispersion to separate a powder comprising ceramic powder particles having a surface layer of ceria deposited thereon.
- The preferred substrate ceramic materials are silica, silicon carbide and alumina. The silica option is more preferably fumed silica since this is readily available in the form of a very fine powder with relatively uniform particle sizes. It is also quite insoluble in water which is the preferred dispersion medium for the production of polishing slurries providing the pH is not excessively acidic or basic. The silica option can also be fused silica powder, which has larger size (˜1-2 um) or colloidal silica, which has smaller size (10 nm˜100 nm) as compared with fumed silica. The alumina option can be particles of alpha alumina, gamma alumina, amorphous alumina or boehmite. Silicon Carbide can be in either the alpha or beta crystalline phase, but with the surface oxidized so that ceria can be more adherent than on SiC itself. References to “silicon carbide” in the following should be understood to refer to such surface-oxidized materials.
- A polishing slurry containing the novel powder according to the invention is preferably water-based and may contain water-soluble detergent materials such as phosphates, as long as no inhibiting effect upon the contact of ceria to the substrate surface. The pH of the polishing formulation can be kept from 3 to 11. Normally, higher pH leads to higher hydration rate or dissolution rate of SiO2 which benefit the polishing action. However, low pH might be preferred in some cases where good stability of the slurry is required, as ceria can be better dispersed in acidic solution and the slurry will have longer shelf time. In either the cases, the isoelectric point (IEP) of ceria, normally around pH 7, should be avoided.
- The production of the ceria-coated particles is preferably accomplished by a solution process. First, ceramic particles need to be mixed with water to make a good and stable dispersion. To the solution, water soluble cerium salts can be added before or after the pH is raised to close to 10 at which point, cerium salts will completely precipitate as oxide or hydroxide. If addition occurs before the pH is raised, a mixture of cerium salt with ceramic particles in water will typically have an acid pH value and this can be adjusted by addition of a base that is effective to raise the pH, typically to about 10. At this pH the cerium salt deposits on the ceramic particles, probably in the form of the hydrated oxide. A straightforward way is to add NH4OH to the solution containing the cerium salts under vigorous stirring until a pH of 10 is reached. Alternatively a basic chemical such as urea can be dissolved in the solution, followed by decomposition of urea into ammonia by heating the solution to an elevated temperature, preferably from about 75 to 90° C. and holding the solution at the temperature until ceria deposition is complete. In that way, pH is raised in-situ, and there is no abrupt local increase of pH in a local region as would occur when ammonia is added. Cerium salts can also be added after the pH is raised. For example an aqueous dispersion of ceramic particles, such as SiO2, can be first mixed with ammonia to a high pH of about 10, and an aqueous solution of a cerium salt can then be added drop-wise to the solution while under stirring. As the salt solution is added the pH falls so a certain amount of aqueous ammonia needs to be added to keep the solution around pH 10. Thereafter the particles can be separated by sedimentation or by the use of a centrifuge and fired at from 600 to 1000° C. to form the ceria as a thin shell on the surfaces of the ceramic particles. This shell can represent any desired percentage of the weight of the powder, such as from 3 to 25% and most preferably from 3 to 15% of the weight of the particles.
- The precursors for the ceria can be any cerium salts that are water soluble, such as Ce(NO3)3.6H2O, Ce(SO4)2.4H2O, (NH4)2.Ce(NO3)6 and the like. It is also possible to use a commercial CeO2 sol, (for example Nyacol).
- Production of Core-Shell Structured Particles
- A convenient way of producing the core-shell ceramic particles of the invention is exemplified by the following Examples.
- A fumed silica powder with a surface area of 15 m2/g, 300 g, which corresponds to an average particle size of about 300 nanometers, was dispersed in 2700 g of water. After 30 min. of sonication, 150 g of cerium nitrate hexahydrate is added which gives a solution at pH 2.7. The pH of the dispersion was adjusted using 500 g of urea and the mixture was aged at about 90° C. for a period of 16 hours. During this time the pH changed from about 3.64 to 8.3. After the pH had stabilized at this level, the solid material was separated by centrifuge and dried in an oven for overnight before being fired at 800° C. over a period of about 2 hours. The fumed silica powder showed a weight increase of 15% due to the formation of a ceria shell around the particles. After firing, this material is crushed and pulverized into powder to make a polishing slurry.
- A number of glass polishing slurries were produced with a pH of 10 and a 5 wt % solids content of the abrasive. The slurries differed only in the abrasive used as follows:
- PA-1 100% pure ceria. This is made from the same cerium nitrate salt via the same precipitation and firing process, except there was no silica powder used as cores.
- PA-2 “Opaline” which is a commercial ceria polishing powder containing about 100% of ceria obtained from Rhodia under that registered trademark.
- PA-3 100% fumed silica having a purity of about 96% and an average particle size, (d50), of about 0.4 micrometers.
- INV-1 This illustrates the invention and was prepared using the above process based on the fumed silica in PA-3.
- The above formulations were evaluated under identical conditions in the polishing of a fused SiO2 glass surface using a 5% slurry at pH=10. In each case the time taken to reach the final Ra level and the Ra after such period were both measured, along with the amount of glass removed from the surface in that time. The results are shown in Table 1 below.
TABLE 1 Density Time (min) Glass Removal Final Surface (g/cm3) to Final Ra Rate (μm/min) Finish Ra (A) PA-1 7.13 10 1.1 9 PA-2 7.13 10 1.94 9.2 PA-3 2.3 30 0.15 59.9 INV-1 2.6 10 0.87 7.4 - From the above data it is very clear that the present invention provides a glass polishing formulation that removes material at a rate that is a little less than that achieved with the most pure ceria powders available, in about the same time and with a better surface finish. In all respects it performs better that the silica core powder at only a slightly elevated cost.
- The fumed silica used in Example 1, (200 g) was mixed with 1800 g of DI water. 2.12 g of ammonia was added to adjust the pH to 10 under vigorous stirring. In a separate beaker, 100 g of Ce(NO3)3.6H2O was dissolved in 100 g of DI water. Under the vigorous stirring, the cerium nitrate solution is added drop wise to the fumed silica slurry slowly. At the same time, aqueous ammonia (˜30%) is added to the slurry to keep the solution at pH ˜10 and thus ensure that all cerium salt hydrolyzes completely. In total, 86.8 g of ammonia was added together with the cerium nitrate solution. After finishing addition of the cerium nitrate solution, solid material is separated from solution by centrifuge and dried in oven for overnight. Thereafter, the material is fired at 800° C./2 hrs, followed by crushing into fine powder before being mixed with water to make a polishing slurry.
- The above procedures in Example 2 were used to generate the core-shell structure on fused silica powder which is commercially available from Alfa Aesar, with 2 um average particle size; S.A., 2 m2/g; and 99.5% purity. The fused silica was first dispersed in water, with pH adjusted with ammonia. The slurry was poured through a metal screen #325 to remove any large particles, before the same treatment the same way as in Example 2. The product was pulverized into powder for polishing test.
- 80 g of the same fumed silica as in Example 1 was well dispersed in 4000 g DI water under stirring, to which, 7.6 g of Ce(SO4)2.xH2O.yH2SO4, 9.12 g of(NH4)2.Ce(NO3)6, and 64.4 g of H2SO4 were added. The solution was heated to 95° C. and aged at that temperature for 16 hours. In addition 250 g of urea were added to the solution which was then aged for 6 more hours. Thereafter, the solids were separated from the solution by centrifuge, dried in oven and then fired at 800° C./2 hrs. After calcinations, the material was pulverized into powder and provided for polishing test on SiO2 in the form of an aqueous dispersion with a pH 10 containing 5% solids. Table 2 summarizes the polishing results as compared with pure ceria either commercial product or according to the invention.
TABLE 2 Density Time (min) Glass Removal Final Surface (g/cm3) to Final Ra Rate (μm/min) Finish Ra (A) PA-1 7.13 10 1.1 9 PA-2 7.13 10 1.94 9.2 PA-4 2.2 30 0.45 122 INV-2 2.6 10 0.87 7.4 INV-3 2.6 10 1.40 30.1 INV-4 2.4 10 0.78 8.6 - PA-4 Fused silica powder obtained from alfa Aesar that was used as cores in Example 3.
- INV-2 Powder produced in Example 2
- INV-3 Powder produced in Example 3
- INV-4 Powder produced in Example 4
- From Table 2, it is clear, that cerium precursors other than cerium nitrate can also be used to process different type of core particles to achieve improved polishing performance. It is also noticeable that the larger silica core particles, while showing an impressive material removal rate, led to a rougher finish on account of the larger average particle size.
Claims (7)
1. Abrasive powder particles each comprising a core particle of a ceramic material with a shell of ceria deposited thereon such that the ceria represents from 2 to 40% of the particle weight.
2. Abrasive powder according to claim 1 in which the ceria represents from 3 to 20% of the particle weight.
3. Abrasive powder according to claim 1 in which the ceramic providing the core particles is selected from the group consisting of silica, alumina, zirconia, silicon carbide, calcium oxide, rare earth metal oxides and mixtures thereof.
4. Abrasive powder according to claim 4 in which the ceramic providing the core particles is fumed silica and colloidal silica.
5. A glass polishing formulation comprising a dispersion medium and abrasive powder particles each comprising a core particle of a ceramic material with a shell of ceria deposited thereon such that the ceria represents from 2 to 40% of the particle weight, the powder being present in then formulation in an amount of from 2 to 20% by weight.
6. A glass polishing formulation according to claim 5 in which the pH is adjusted to at least pH 8.
7. A process for the production of a glass polishing abrasive powder comprising ceramic core particles and a shell of ceria deposited thereon which comprises mixing a powder of the ceramic core particles with a solution of a soluble salt of cerium; adjusting the pH of the dispersion to at least a pH of 8; aging the dispersion at a temperature of from 60 to 95° C. until the pH has stabilized above 8; separating and drying the solids content of the dispersion; and firing the dried solids at a temperature of from 600 to 1000° C.
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US6645265B1 (en) | 2003-11-11 |
AU2003248899A1 (en) | 2004-02-09 |
MY145589A (en) | 2012-02-29 |
WO2004009726A1 (en) | 2004-01-29 |
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