WO2009097938A1 - Dispersion contenant des particules d'oxyde de cérium et son utilisation pour polir des verres - Google Patents

Dispersion contenant des particules d'oxyde de cérium et son utilisation pour polir des verres Download PDF

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Publication number
WO2009097938A1
WO2009097938A1 PCT/EP2008/067625 EP2008067625W WO2009097938A1 WO 2009097938 A1 WO2009097938 A1 WO 2009097938A1 EP 2008067625 W EP2008067625 W EP 2008067625W WO 2009097938 A1 WO2009097938 A1 WO 2009097938A1
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WO
WIPO (PCT)
Prior art keywords
cerium oxide
dispersion
oxide particles
dispersion according
particles
Prior art date
Application number
PCT/EP2008/067625
Other languages
English (en)
Inventor
Michael KRÖLL
Stefan Heberer
Stipan Katusic
Michael Krämer
Original Assignee
Evonik Degussa Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa Gmbh filed Critical Evonik Degussa Gmbh
Publication of WO2009097938A1 publication Critical patent/WO2009097938A1/fr

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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
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions

Definitions

  • the invention relates to a dispersion which contains cerium oxide particles and polyacrylates, and the use of this dispersion for polishing glasses.
  • Cerium oxide is considered to be the most efficient agent for polishing glass surfaces. As a rule, the cerium oxide is used in the form of a dispersion. With the increase in requirements regarding the quality of glass surfaces, improved polishing compositions are required.
  • US6221119 discloses a dispersion which contains sodium polyacrylate in addition to cerium oxide particles. This additive is intended to increase the stability of the dispersion and the polishing rate.
  • a disadvantage of this dispersion is that the quality of the surfaces treated therewith still has uneven areas which cannot be tolerated, particularly in precision optics .
  • the invention relates to a dispersion which contains cerium oxide particles and one or more polymeric, anionic dispersing additives which are soluble in the liquid phase of the dispersion, wherein
  • the dispersion has a pH in the range from 6 to 8, preferably from 6.5 to 7.5, and - the cerium oxide particles are positively charged in this range and are present in a proportion of 0.01 to 10% by weight, preferably 0.1 to 2% by weight, in the dispersion .
  • the positive charge of the cerium oxide particles can be determined via the zeta potential.
  • the zeta potential is a measure of the surface charge of the particles, which can be shifted by polymeric, anionic dispersing additives which accumulate on the surface.
  • Zeta potential is to be understood as meaning the potential at the shear plane within the electrochemical double layer cerium oxide particle/electrolyte in the dispersion.
  • An important parameter in relation to the zeta potential is the isoelectric point (IEP) for a particle.
  • the IEP indicates the pH at which the zeta potential is zero.
  • the zeta potential of the cerium oxide particles is determined in the pH range 6-8 by means of the electrokinetic sound amplitude.
  • a dispersion which contains 1% by weight of cerium oxide with water as the liquid phase is prepared.
  • the dispersing is effected using an ultrasound rod (400 W) .
  • the dispersion is stirred with a magnetic stirrer and pumped via a peristaltic pump through the PPL-80 sensor of the ESA-8000 apparatus from Matec.
  • the potentiometric titration with 5M NaOH to pH 8 starts from the initial pH.
  • the back- titration to pH 6 is carried out with 5M HNO3.
  • the evaluation is effected according to
  • ⁇ p Density difference between particle and liquid
  • c Sound velocity in the suspension
  • ⁇ Viscosity of the liquid
  • ⁇ Dielectric constant of the suspension
  • G ( ⁇ ) I Inertial correction.
  • the zeta potential of the cerium oxide particles present in the dispersion according to the invention is preferably +20 to +60 mV, particularly preferably +30 to +40 mV.
  • polishing rates which are achieved with the dispersion according to the invention are as a rule lower than polishing rates achieved with the dispersion disclosed in US6221119.
  • the quality of glass surfaces can be substantially improved with the dispersion according to the invention.
  • a polishing process with the dispersion disclosed in US6221119 is based on the theory that the interaction between polyacrylate and cerium oxide particles during the polishing process is only slight at neutral or basic pH .
  • the interaction between cerium oxide particles and anionic dispersing additive during the polishing process is a strong one, i.e. the cerium oxide particles are surrounded by a layer of the anionic dispersing additive.
  • Such a strong interaction between cerium oxide particles and anionic dispersing additive is explicitly ruled out in US 6221119 since the interaction between cerium oxide particles and glass surface would be adversely affected thereby.
  • cerium oxide particles present in the dispersion according to the invention have a BET surface area of 25 to 150 m 2 /g.
  • cerium oxide particles having a BET surface area of 30 to 100 m 2 /g can be used.
  • the BET surface area can be determined by means of DIN 66131.
  • the cerium oxide particles may be present in the form of isolated individual particles as well as in the form of aggregated primary particles.
  • the mean particle diameter, the mean aggregate diameter in the case of aggregated primary particles, is preferably less than 200 nm. A range from 50 to 150 nm may be particularly preferred. The value can be determined, for example, by means of dynamic light scattering .
  • the dispersion according to the invention may comprise cerium oxide particles with a proportion of sodium of not more than 5 ppm and of chlorine of not more than 20 ppm.
  • a particularly preferred dispersion may be one in which the cerium oxide particles
  • the primary particles • have a mean diameter of 5 to 50 nm and
  • a very particularly preferred dispersion may be one in which the cerium oxide particles
  • the primary particles have a mean diameter of 5 to 50 nm
  • - carbonate groups are present on the surface and in a layer close to the surface, where in a layer close to the surface, i.e. a layer about 5 nm thick, the carbonate concentration decreases inwards, starting from the surface, on which the carbonate concentration is highest, and • the carbon content originating from the carbonate groups is 5 to 50 area percent on the surface and is 0 to 30 area percent in the layer close to the surface, at a depth of about 5 nm.
  • cerium oxide particles are disclosed, for example, in DE-A-102005038136.
  • the dispersion according to the invention also comprises polymeric, anionic dispersing additives.
  • the proportion thereof is preferably 0.1 to 100 parts by weight, particularly preferably 0.5 to 5 parts by weight, based in each case on cerium oxide.
  • the polymeric, anionic dispersing additive can preferably be selected from the group consisting of acrylic acid polymers and salts thereof, methacrylic acid polymers and salts thereof, ammonium lauryl sulphate and polyoxyethylene lauryl ether ammonium sulphate.
  • salts of polyacrylic acids in particular ammonium polyacrylates .
  • the average molecular weight (number-averaged) can preferably be 500 to 50000, a range from 1000 to 30000 being particularly preferred.
  • the liquid phase of the dispersion according to the invention is as a rule one whose main constituent is water.
  • the proportion of water is at least 80% by weight in a preferred embodiment and at least 95% by weight, based in each case on the dispersion, in a particularly preferred embodiment.
  • the preparation of the dispersion according to the invention can be effected, for example, by dispersing a predispersion containing cerium oxide particles with an energy input of at least 200 KJ/m 3 and subsequently adding one or more polymeric, anionic dispersing additives with lower energy input, for example by stirring.
  • Suitable dispersing units having an energy input of at least 200 KJ/m 3 are in particular systems according to the rotor-stator principle, for example Ultra-Turrax machines, or stirred ball mills. Higher energy inputs are possible with a planetary kneader/mixer .
  • the energy input can also be effected by means of ultrasound.
  • the dispersing and milling apparatuses can also be used in combination.
  • the invention furthermore relates to the use of the dispersion according to the invention for polishing glasses, in particular in high-precision optics.
  • Polishing dispersions - Cerium oxide dispersion (according to the invention) : 2% by weight of cerium oxide particles (DE-A-102005038136, Example 2), 3% by weight of ammonium polyacrylate (based on a polyacrylic acid having an average molecular weight M w of 2000, the pH of which is adjusted with ammonia), based on cerium oxide; remainder water;
  • Cerium oxide dispersion CERI 3000 (comparison) : proportion of cerium oxide: 60 - 65% by weight, total proportion of rare earth metals 86 - 91% by weight, average individual particle size: 0.7 ⁇ m (Sedigraph) , maximum particle size (95% less than:) 2.0 ⁇ m, pH: 8 - 10, specific gravity: 1.8 - 2.0.
  • 2-spindle polishing machine with lever control, adjustable weights and additional weights can be added, speed of the spindle and lever arms continuously electronically controllable independently of one another.
  • pitch polishing technology utilises the flow of the pitch in order to achieve "independent" levelling or adaptation to the ideal form to be achieved (auto correction principle) .
  • the pitch applied to the metal dish serves here as a polish carrier. Accuracies of shape down to a few nanometres and roughnesses to 0.2 nm rms are obtained.
  • Figure 1 shows the roughness of the surface (quartz glass Ql) after polishing with CERI 3000.
  • Figure 2 shows the roughness of the surface after polishing with the dispersion according to the invention.
  • the cerium oxide dispersion according to the invention shows uniform material removal with a finely structured surface. The planarities are noticeably improved. Similar results are also achieved with the other glass qualities tested.
  • the dispersion according to the invention Compared with the Syton used in the prior art, an alkaline suspension with colloidal Si ⁇ 2 particles, the dispersion according to the invention has the advantage that a high accuracy of shape is achieved even with a long processing time .

Landscapes

  • 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)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne une dispersion qui contient des particules d'oxyde de cérium et un ou plusieurs additifs de dispersion anioniques, polymères, qui sont solubles dans la phase liquide de la dispersion, et qui présente un pH compris dans la plage allant de 6 à 8, les particules d'oxyde de cérium étant positivement chargées dans ladite plage et étant présentes dans une proportion comprise entre 0,01% et 10% en poids dans la dispersion.
PCT/EP2008/067625 2008-02-08 2008-12-16 Dispersion contenant des particules d'oxyde de cérium et son utilisation pour polir des verres WO2009097938A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200810008183 DE102008008183A1 (de) 2008-02-08 2008-02-08 Ceroxidpartikel enthaltende Dispersion und deren Verwendung zum Polieren von Gläsern
DE102008008183.3 2008-02-08

Publications (1)

Publication Number Publication Date
WO2009097938A1 true WO2009097938A1 (fr) 2009-08-13

Family

ID=40513970

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/067625 WO2009097938A1 (fr) 2008-02-08 2008-12-16 Dispersion contenant des particules d'oxyde de cérium et son utilisation pour polir des verres

Country Status (2)

Country Link
DE (1) DE102008008183A1 (fr)
WO (1) WO2009097938A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221119B1 (en) * 1999-07-14 2001-04-24 Komag, Inc. Slurry composition for polishing a glass ceramic substrate
US20060213126A1 (en) * 2005-03-28 2006-09-28 Cho Yun J Method for preparing a polishing slurry having high dispersion stability
DE102005038136A1 (de) * 2005-08-12 2007-02-15 Degussa Ag Ceroxid-Pulver und Ceroxid-Dispersion
WO2007088868A1 (fr) * 2006-01-31 2007-08-09 Hitachi Chemical Co., Ltd. Abrasif cmp destine a polir un film isolant, procede de polissage et composant electronique semi-conducteur poli a l'aide d'un tel procede de polissage
US20070199477A1 (en) * 2005-08-25 2007-08-30 Degussa Ag Paste containing nanoscale powder and dispersant and dispersion made therefrom

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US621119A (en) 1899-03-14 Mattress-filling machine

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221119B1 (en) * 1999-07-14 2001-04-24 Komag, Inc. Slurry composition for polishing a glass ceramic substrate
US20060213126A1 (en) * 2005-03-28 2006-09-28 Cho Yun J Method for preparing a polishing slurry having high dispersion stability
DE102005038136A1 (de) * 2005-08-12 2007-02-15 Degussa Ag Ceroxid-Pulver und Ceroxid-Dispersion
EP1757560A2 (fr) * 2005-08-12 2007-02-28 Degussa AG Poudre d'oxyde de cérium et dispersion la contenant
US20070199477A1 (en) * 2005-08-25 2007-08-30 Degussa Ag Paste containing nanoscale powder and dispersant and dispersion made therefrom
WO2007088868A1 (fr) * 2006-01-31 2007-08-09 Hitachi Chemical Co., Ltd. Abrasif cmp destine a polir un film isolant, procede de polissage et composant electronique semi-conducteur poli a l'aide d'un tel procede de polissage
US20090047786A1 (en) * 2006-01-31 2009-02-19 Masato Fukasawa CMP Abrasive Slurry for Polishing Insulation Film, Polishing Method, and Semiconductor Electronic Part Polished by the Polishing Method

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Publication number Publication date
DE102008008183A1 (de) 2009-08-13

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