WO2005000756A3 - Microspheres comprising titania and bismuth oxide - Google Patents

Microspheres comprising titania and bismuth oxide Download PDF

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Publication number
WO2005000756A3
WO2005000756A3 PCT/US2004/012173 US2004012173W WO2005000756A3 WO 2005000756 A3 WO2005000756 A3 WO 2005000756A3 US 2004012173 W US2004012173 W US 2004012173W WO 2005000756 A3 WO2005000756 A3 WO 2005000756A3
Authority
WO
WIPO (PCT)
Prior art keywords
microspheres
titania
bismuth oxide
relates
beads
Prior art date
Application number
PCT/US2004/012173
Other languages
French (fr)
Other versions
WO2005000756A2 (en
Inventor
Matthew H Frey
Original Assignee
3M Innovative Properties Co
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 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Priority to US10/556,978 priority Critical patent/US20060293161A1/en
Priority to JP2006532440A priority patent/JP2007501183A/en
Priority to EP04785734A priority patent/EP1631530A2/en
Publication of WO2005000756A2 publication Critical patent/WO2005000756A2/en
Publication of WO2005000756A3 publication Critical patent/WO2005000756A3/en

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    • 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
    • C03C12/00—Powdered glass; Bead compositions
    • C03C12/02—Reflective beads
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C03B19/102—Forming solid beads by blowing a gas onto a stream of molten glass or onto particulate materials, e.g. pulverising
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C03B19/1045—Forming solid beads by bringing hot glass in contact with a liquid, e.g. shattering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C03B19/1055—Forming solid beads by extruding, e.g. dripping molten glass in a gaseous atmosphere
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/127—Silica-free oxide glass compositions containing TiO2 as glass former
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/12—Reflex reflectors
    • G02B5/126—Reflex reflectors including curved refracting surface
    • G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
    • C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/60—Silica-free oxide glasses
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/528—Spheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9653—Translucent or transparent ceramics other than alumina
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Abstract

The present invention relates to microspheres (i.e., beads) that comprise at least 50 wt-% titania and at least 5 wt-% bismuth oxide. The glass microspheres further comprise zirconia. The invention also relates to retroreflective articles, and in particular pavement markings, comprising such microspheres.
PCT/US2004/012173 2003-06-11 2004-04-20 Microspheres comprising titania and bismuth oxide WO2005000756A2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/556,978 US20060293161A1 (en) 2003-06-11 2004-04-20 Microspheres comprising titania and bismuth oxide
JP2006532440A JP2007501183A (en) 2003-06-11 2004-04-20 Microspheres comprising titania and bismuth oxide
EP04785734A EP1631530A2 (en) 2003-06-11 2004-04-20 Microspheres comprising titania and bismuth oxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/458,955 2003-06-11
US10/458,955 US20040259713A1 (en) 2003-06-11 2003-06-11 Microspheres comprising titania and bismuth oxide

Publications (2)

Publication Number Publication Date
WO2005000756A2 WO2005000756A2 (en) 2005-01-06
WO2005000756A3 true WO2005000756A3 (en) 2005-04-28

Family

ID=33516933

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/012173 WO2005000756A2 (en) 2003-06-11 2004-04-20 Microspheres comprising titania and bismuth oxide

Country Status (6)

Country Link
US (4) US20040259713A1 (en)
EP (1) EP1631530A2 (en)
JP (1) JP2007501183A (en)
KR (1) KR20060023556A (en)
CN (1) CN1802326A (en)
WO (1) WO2005000756A2 (en)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040259713A1 (en) * 2003-06-11 2004-12-23 3M Innovative Properties Company Microspheres comprising titania and bismuth oxide
CN1878914A (en) 2003-11-06 2006-12-13 3M创新有限公司 Retroreflective elements comprising a bonded resin core and pavement markings
JP2007022832A (en) * 2005-07-14 2007-02-01 Nippon Electric Glass Co Ltd Manufacturing method of glass powder
US7513941B2 (en) 2005-11-14 2009-04-07 3M Innovative Properties Company Pavement marking, reflective elements, and methods of making micospheres
RU2008147149A (en) * 2006-05-01 2010-06-10 Асахи Гласс Компани, Лимитед (Jp) METHOD FOR PRODUCING GLASS
US8701441B2 (en) * 2006-08-21 2014-04-22 3M Innovative Properties Company Method of making inorganic, metal oxide spheres using microstructured molds
US20080280034A1 (en) * 2007-05-11 2008-11-13 3M Innovative Properties Company Pavement marking and reflective elements having microspheres comprising lanthanum oxide and aluminum oxide with zirconia, titania, or mixtures thereof
US8840956B2 (en) * 2008-10-31 2014-09-23 Potters Industries, Llc Retroreflective coating and method for applying a retroreflective coating on a structure
US7884055B2 (en) * 2008-12-04 2011-02-08 Intevep, S.A. Ceramic microspheres for cementing applications
US20100272962A1 (en) * 2009-04-22 2010-10-28 Potters Industries Inc. Reflective substrate surface system, reflective assembly, and methods of improving the visibility of a substrate surface
CN102574730A (en) 2009-08-21 2012-07-11 3M创新有限公司 Pavement markings, reflective elements, and methods of making microspheres
CN102574729A (en) * 2009-08-21 2012-07-11 3M创新有限公司 Pavement markings, reflective elements, and methods of making microspheres
US8647013B2 (en) * 2010-02-09 2014-02-11 Potters Industries, Llc Reflective substrate surface system, reflective assembly, and methods of improving the visibility of a substrate surface
US9340934B2 (en) 2011-09-01 2016-05-17 3M Innovative Properties Company Pavement marking materials and methods
US20130105735A1 (en) * 2011-10-27 2013-05-02 Willard Scott Rader Thermally induced flash synthesis of photoluminescent compositions
FR2981952B1 (en) * 2011-11-02 2015-01-02 Fabien Gaben PROCESS FOR MAKING THIN FILMS DENSED BY ELECTROPHORESIS
KR102126363B1 (en) 2012-10-29 2020-06-24 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Pavement marking compositions
US10259947B2 (en) 2014-04-04 2019-04-16 3M Innovative Properties Company Wet or damp surface preparation compositions
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US10605967B2 (en) 2014-08-08 2020-03-31 3M Innovative Properties Company Retroreflective elements including particles
GB201415005D0 (en) * 2014-08-22 2014-10-08 Univ Nottingham Porous and non-pourous bodies
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CN104944778A (en) * 2015-06-17 2015-09-30 安徽环泰新材料科技有限公司 High-temperature resistant glass bead for reflective film, and preparation method of glass bead
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WO2024003637A1 (en) 2022-06-29 2024-01-04 3M Innovative Properties Company Curable adhesive and articles for bonding pavement and concrete

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293051A (en) * 1963-08-22 1966-12-20 Cataphote Corp High titanate glass beads
US4192576A (en) * 1978-11-20 1980-03-11 Minnesota Mining And Manufacturing Company Ultra-high-index glass microspheres and products made therefrom

Family Cites Families (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE209431C (en)
DE242038C (en)
US2354018A (en) * 1940-08-03 1944-07-18 Minnesota Mining & Mfg Light reflector sheet
US2713286A (en) * 1949-10-22 1955-07-19 Minnesota Mining & Mfg Reflex light reflectors and glass bead elements thereof
US2853393A (en) * 1951-07-05 1958-09-23 Minnesota Mining & Mfg High-index glass elements
DE1065580B (en) * 1953-08-12 1959-09-17 Minnesota Mining and Manufacturing Company, Saint Paul, Minn. (V. St. A.) Transparent glass element with a thickness of no more than 2 mm
US2726161A (en) * 1953-09-21 1955-12-06 Minnesota Mining & Mfg High-index glass elements
US2842446A (en) * 1954-12-27 1958-07-08 Minnesota Mining & Mfg High-index glass elements
US2873197A (en) * 1955-01-21 1959-02-10 Carborundum Co Refractory fibrous material
US2963378A (en) * 1955-04-25 1960-12-06 Minnesota Mining & Mfg Ass beads hemispherically reflectorled with metallic coating and compositions thereof
US2870030A (en) * 1955-07-18 1959-01-20 Minnesota Mining & Mfg High-index glass elements
US2924533A (en) * 1956-05-28 1960-02-09 Carborundum Co Spheroidal refractory material and method of making
US2960594A (en) * 1958-06-30 1960-11-15 Plasma Flame Corp Plasma flame generator
US3145114A (en) * 1960-10-24 1964-08-18 Prismo Safety Corp Process for increasing the index of refraction of glass and an article made thereby
US3228897A (en) * 1961-10-26 1966-01-11 Minnesota Mining & Mfg Reflective coating compositions containing glass beads, metal flake pigment and binder
US3149016A (en) * 1962-04-02 1964-09-15 Minnesota Mining & Mfg Nucleated glass particle and process for making it
CA919195A (en) * 1963-02-14 1973-01-16 Fang Tung Chi High index glass elements
US3419403A (en) * 1963-03-18 1968-12-31 Cataphote Corp High index of refraction glass compositions
DE1250977B (en) * 1963-04-22 1967-09-28
US3294558A (en) * 1963-04-22 1966-12-27 Cataphote Corp Colorless high index glass compositions
US3323888A (en) * 1964-03-17 1967-06-06 Cataphote Corp Method for manufacturing glass beads
FR1404190A (en) 1964-08-10 1965-06-25 Minnesota Mining & Mfg Transparent beads
US3416936A (en) * 1965-03-01 1968-12-17 Gen Steel Ind Inc Abrasion resistant glass bead with sharp softening range and process for making the same
US3432314A (en) * 1966-08-02 1969-03-11 Us Air Force Transparent zirconia composition and process for making same
US3410185A (en) * 1966-08-08 1968-11-12 Minnesota Mining & Mfg Marking
US3499857A (en) * 1967-04-17 1970-03-10 Cataphote Corp Thermoplastic resinous compositions,particularly using unsaturated triglycerides
US3523029A (en) * 1967-08-21 1970-08-04 Cataphote Corp Hot melt highway marking composition
US3560074A (en) * 1968-10-21 1971-02-02 Cataphote Corp 95% titanium dioxide glass spheroids
US3709706A (en) * 1969-05-16 1973-01-09 Minnesota Mining & Mfg Refractory fibers and other articles of zirconia and silica mixtures
US3645933A (en) * 1969-11-12 1972-02-29 Sherwin Williams Co Coating composition including isocyanate-modified polyester and chlorinated rubber
US3684536A (en) * 1970-11-04 1972-08-15 Du Pont Bismuthate glass-ceramic precursor compositions
US3795524A (en) * 1971-03-01 1974-03-05 Minnesota Mining & Mfg Aluminum borate and aluminum borosilicate articles
US3749763A (en) * 1971-08-03 1973-07-31 Humphreys Corp Processing of silicate ores and product thereof
IT1045437B (en) * 1972-12-28 1980-05-10 Eigenmann Ludwig REFINEMENT OF REFLECTIVE DOUBLE-FOCUSED CATA MATERIALS, IN PARTICULAR FOR ROAD SIGNAGE
US3864113A (en) * 1973-10-19 1975-02-04 Corning Glass Works Method of Producing Glass by Flame Hydrolysis
US3915771A (en) * 1974-03-04 1975-10-28 Minnesota Mining & Mfg Pavement-marking tape
US3923051A (en) * 1974-03-18 1975-12-02 Samuel Soichet Inflatable intrauterine contraceptive device for postpartum use
US4082427A (en) * 1974-07-02 1978-04-04 Fukuoka Tokushu Garasu Kabushiki Kaisha High refractive index glass compositions
JPS5828210B2 (en) 1974-11-07 1983-06-14 オノダセメント カブシキガイシヤ Kobutsu Sen Imataha Beads Seibutsu
US4137086A (en) * 1975-05-13 1979-01-30 Pilkington Brothers Limited Glass compositions for use in curable compositions
FR2320276A1 (en) * 1975-08-06 1977-03-04 Prod Refractaires Europ BALLS IMPROVED IN CERAMIC MATERIAL
US4056602A (en) * 1975-08-20 1977-11-01 Thagard Technology Company High temperature chemical reaction processes utilizing fluid-wall reactors
US4095974A (en) * 1975-09-24 1978-06-20 Thagard Technology Company High temperature chemical reaction processes utilizing fluid-wall reactors
JPS5939378B2 (en) 1976-08-13 1984-09-22 旭硝子株式会社 Glass composition for fibers
JPS5388815A (en) 1977-01-18 1978-08-04 Tokyo Shibaura Electric Co High reeractiveeindex glass for glass beads
JPS53102325A (en) 1977-02-18 1978-09-06 Obara Optical Glass Abrasionn and chemicallproof glass
JPS5415919A (en) * 1977-06-07 1979-02-06 Fukuoka Tokushiyu Garasu Kk Glass having high refractive index
JPS546241A (en) 1977-06-13 1979-01-18 Nissan Diesel Motor Co Ltd Automotive parking brake device
US4367919A (en) * 1977-08-01 1983-01-11 Minnesota Mining And Manufacturing Company Durable glass elements
JPS5520254A (en) 1978-07-28 1980-02-13 Matsushita Electric Works Ltd Production of low melting point crystallized glass
JPS608983B2 (en) 1978-07-28 1985-03-07 松下電工株式会社 Manufacturing method of low melting point glass with crystallization ability
JPS55126548A (en) 1979-03-20 1980-09-30 Ohara Inc Glass for bead
JPS55126547A (en) 1979-03-20 1980-09-30 Ohara Inc Glass for bead
US4248932A (en) * 1979-06-14 1981-02-03 Minnesota Mining And Manufacturing Company Extended-life pavement-marking sheet material
JPS5641852A (en) 1979-09-17 1981-04-18 Ohara Inc Glass for bead
JPS6022656B2 (en) 1980-08-21 1985-06-03 ホ−ヤ株式会社 optical glass
FR2493910A1 (en) * 1980-11-13 1982-05-14 Produits Refractaires ZIRCONIA AND SILICA BASE AGENT FOR DEEP GEOLOGICAL FRACTURES
JPS5815067A (en) 1981-07-13 1983-01-28 セントラル硝子株式会社 Bi2o3 composition of mainly delta phase at ordinary temperature, specific use, manufacture and manufacturing apparatus
DE3216451C2 (en) * 1982-05-03 1984-04-19 Schott Glaswerke, 6500 Mainz Lightweight optical glass with a refractive index? 1.70, an Abbe number? 22 and a density ≦ 3.5 g / cm? 3?
JPS6022656A (en) 1983-07-18 1985-02-05 Murata Mfg Co Ltd Frost detector
US4621936A (en) * 1983-10-14 1986-11-11 Corning Glass Works Zirconia pen balls
JPS60215549A (en) 1984-04-11 1985-10-28 Toshiba Glass Co Ltd Abrasive-resistant glass beads
DE3430906A1 (en) 1984-08-22 1986-02-27 Boehringer Mannheim Gmbh, 6800 Mannheim METHOD FOR DETERMINING FIBRINE MONOMER IN PLASMA
JPS6168349A (en) 1984-09-07 1986-04-08 Toshiba Glass Co Ltd Wear resistant glass bead
US4564556A (en) * 1984-09-24 1986-01-14 Minnesota Mining And Manufacturing Company Transparent non-vitreous ceramic particulate
DE3504625C1 (en) * 1985-02-11 1986-07-03 Schott Glaswerke, 6500 Mainz High-index optical glass in the SiO2-TiO2-Nb2O5-BaO alkali oxide system with refractive indices? 1.83 and pay off? 25, and with very good chemical resistance
US4721743A (en) * 1985-03-25 1988-01-26 The Dow Chemical Company Non-thermoset thermally stable capped epoxy resin compositions
JPS61270235A (en) 1985-05-24 1986-11-29 Ohara Inc Glass for bead
US4772511A (en) * 1985-11-22 1988-09-20 Minnesota Mining And Manufacturing Company Transparent non-vitreous zirconia microspheres
AU586300B2 (en) * 1986-01-13 1989-07-06 Minnesota Mining And Manufacturing Company Pavement markings containing transparent non-vitreous ceramic microspheres
JPS62242038A (en) 1986-04-14 1987-10-22 苅部　正夫 Anchor device for pc steel material
US4837069A (en) * 1987-01-07 1989-06-06 Minnesota Mining And Manufacturing Company Transparent alumina microspheres
JP2610004B2 (en) 1988-04-28 1997-05-14 東芝硝子株式会社 Glass beads
US5227221A (en) * 1988-06-09 1993-07-13 Minnesota Mining And Manufacturing Company Patterned skid preventative sheet
US4988555A (en) * 1988-06-09 1991-01-29 Minnesota Mining And Manufacturing Company Patterned pavement marking
AU658871B2 (en) * 1991-02-28 1995-05-04 Minnesota Mining And Manufacturing Company Pavement markers with silicone adhesive
JPH0585771A (en) 1991-03-29 1993-04-06 Nippon Electric Glass Co Ltd Composition for hollow glass sphere
US5268789A (en) * 1992-02-18 1993-12-07 Minnesota Mining And Manufacturing Company Retroreflective assembly and process for making same
JPH0646905B2 (en) 1992-02-19 1994-06-22 株式会社ナーサリーテクノロジー Plant regeneration method from rice callus
US5286682A (en) * 1992-02-19 1994-02-15 Minnesota Mining And Manufacturing Company Yellow retroreflective pavement markings
DE4210011C1 (en) 1992-03-27 1993-07-15 Schott Glaswerke, 6500 Mainz, De
FR2714905B1 (en) * 1994-01-11 1996-03-01 Produits Refractaires Melted ceramic balls.
DE4423794C1 (en) * 1994-07-01 1996-02-08 Ivoclar Ag Glass ceramic containing Zr0¶2¶, process for its production and its use
IT1268814B1 (en) * 1994-12-13 1997-03-06 Calp Spa GLAZING MIXTURE FOR QUALITY GLASS
EP0804514B1 (en) * 1995-01-18 1999-02-24 The Dow Chemical Company Fast hardening aqueous coating composition and paint
US5674616A (en) * 1995-02-06 1997-10-07 Conversion Technologies International, Inc. Glass beads having improved fracture toughness
CA2216116C (en) * 1995-04-18 2006-09-19 Geoffrey P. Morris Acid-resistant glass
US5576097A (en) * 1995-04-24 1996-11-19 Brite-Line Industries, Inc. High brightness durable retro-reflecting microspheres and method of making the same
ATE241153T1 (en) * 1996-02-05 2003-06-15 Minnesota Mining & Mfg DURABLE RETROREFLECTIVE ELEMENTS
US5777791A (en) * 1996-11-26 1998-07-07 Minnesota Mining And Manufacturing Company Wet retroreflective pavement marking articles
US6153127A (en) * 1996-12-25 2000-11-28 Nippon Sheet Glass Co., Ltd. Optical thin film, forming composition thereof, and ultraviolet ray absorbing and thermic ray reflecting glass using the same
US6132132A (en) * 1997-02-26 2000-10-17 Rohm And Haas Company Water-based road marking paint
JP3993269B2 (en) * 1997-04-18 2007-10-17 スリーエム カンパニー Transparent beads and method for producing the same
CN1128170C (en) * 1997-06-13 2003-11-19 美国3M公司 Liquid pavement marking composation
US5998482A (en) * 1997-11-10 1999-12-07 David; Sunil A. Use of synthetic polycationic amphiphilic substances with fatty acid or hydrocarbon substituents as anti-sepsis agents
US6365262B1 (en) * 1998-10-20 2002-04-02 3M Innovative Properties Company Pavement marking articles having enhanced retroreflectivity under dry or wet conditions and method for making same
US6245700B1 (en) * 1999-07-27 2001-06-12 3M Innovative Properties Company Transparent microspheres
US20040259713A1 (en) * 2003-06-11 2004-12-23 3M Innovative Properties Company Microspheres comprising titania and bismuth oxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293051A (en) * 1963-08-22 1966-12-20 Cataphote Corp High titanate glass beads
US4192576A (en) * 1978-11-20 1980-03-11 Minnesota Mining And Manufacturing Company Ultra-high-index glass microspheres and products made therefrom

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US7524779B2 (en) 2009-04-28
US20050143248A1 (en) 2005-06-30
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