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WO1992010286A2 - Procede et composition servant a preparer des oxydes de cermet - Google Patents

Procede et composition servant a preparer des oxydes de cermet Download PDF

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Publication number
WO1992010286A2
WO1992010286A2 PCT/US1991/008976 US9108976W WO9210286A2 WO 1992010286 A2 WO1992010286 A2 WO 1992010286A2 US 9108976 W US9108976 W US 9108976W WO 9210286 A2 WO9210286 A2 WO 9210286A2
Authority
WO
WIPO (PCT)
Prior art keywords
metal oxide
resin
silicon
oxide
composition
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1991/008976
Other languages
English (en)
Other versions
WO1992010286A3 (fr
Inventor
Sivananda S. Jada
R. Michael Fay
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johns Manville Corp
Original Assignee
Manville Corp
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 Manville Corp filed Critical Manville Corp
Publication of WO1992010286A2 publication Critical patent/WO1992010286A2/fr
Publication of WO1992010286A3 publication Critical patent/WO1992010286A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • 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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/002—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of fibres, filaments, yarns, felts or woven material
    • 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
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
    • 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
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/02—Fibres; Filaments; Yarns; Felts; Woven material
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/20—Glass-ceramics matrix
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/30—Methods of making the composites

Definitions

  • the present invention is concerned with encapsulated materials and the manufacture of ceramic metal oxides utilizing sol gel technology as it pertains to delivery systems of the ceramic metal oxide to end uses such as in the fiber glass field.
  • tetraethylorthosilicate (TEOS), Si(OEt) 4 has flash point of 103°F, 1-4 mm Hg vapor pressure at 20°C, 28.5% SiO 2 and is insoluble in water.
  • these alkoxides have special applications when applied as coating or films on glassy or plastic substrate which has a chemically reactive surface.
  • coatings/films are refractory, corrosive and thermal resistant, electrically insulating and superconducting.
  • the coating process is typically done in controlled environment such as closed chamber, non-oxidizing atmosphere and at ambient temperature and pressure.
  • these metal or non-metal oxide based coatings are made by the so-called sol-gel pro- cess.
  • alkoxides of network forming cations e.g., Si, Zr, Al, Ti, B, Ba, etc., are used as glass or ceramic precursors.
  • the typical hydrolysis (partial of full) and the subsequent oligomerization can be represented by the following equations using silicon alkoxide (e.g., ethoxide) as an example.
  • 4,874,667 describes a microencapsulated platinum group metal wherein the encapsulating wall is one or two layers of thermoplastic organic polymers.
  • the microcapsules can be incorporated into storage stable one part polyorganosiloxane compositions that cure by platinum catalyzed hydrosilation reaction.
  • the objective of this invention is to develop a process for the preparation and production of an application of microencapsulated monomeric or oligomeric alkoxide comprising from cations of Si, Al, Zr, Ti, and the like, suitable for use as polymer matrix for fiber reinforce composite and preferably for use as inorganic binder/coating for fiber glass material to enhance thermal resistance of insulated product.
  • the object of the invention is, furthermore, to use high temperature resistant resins, preferably formaldehyde based resin, to encapsulate monomeric or oligomeric metal or non-metal alkoxides. It is important that such microencapsulated alkoxide based materials could be sprayed in current industrial environment and using the existing machinery without any fire hazard.
  • microcapsulated ceramic oxides wherein the encapsulated wall is comprised of heat resistant resins as thermosetting or thermoplastic compositions. It is also an object of the present invention to bind fiberglass compositions utilizing the microencapsulated ceramic metal oxide composition whereby the ceramic metal oxide escapes from the encapsulated wall to thereby coat the individual fibers of the fiber glass composition so that where the coated fibers intersect, the coating forms a bond, thereby binding the fibrous matrix together.
  • Described is a method of preparing an encapsulated ceramic metal oxide and/or silicon oxide precursor comprising the steps:
  • the present invention is concerned with microencapsulated ceramic metal oxide precursor compositions wherein the encapsulating wall is of a heat resistant resin, e.g., thermoset or thermoplastic composition.
  • the starting point for the encapsulated ceramic metal oxide is to prepare ceramic metal oxide compositions, e.g., precursor solutions, that can be inserted within the microencapsulated wall utilizing sol gel technology and encapsulation technology.
  • the metal oxide can be a dispersion, e.g., colloidal, solution or emulsion of one or more ceramic metal oxides which include zirconium oxide, TiO 2 , Cr 2 O 3 , WO 3 , ThO 2 , Fe 2 O 3 , MgO, Y 2 O 3 , ZrO 2 , HfO 2 , V 2 O 5 , Nb 2 O 5 , UO 2 , BeO, CoO, NiO, CuO, ZnO, ln 2 O 3 , Sb 2 O 3 , Al 2 O 3 , SnO 2 , and mixtures thereof such as ZnO- -TiO 2 , TiO 2 - -Fe 2 O 3 , SnO 2 - -TiO 2 , Nd 2 O 3 - -TiO 2 , Al 2 O 3 - -Cr 2 O 3 , MgO- -Al 2 O 3 , MgO- -TiO 2 ,
  • dispersion or sols of said ceramic metal oxides in combination or admixture with dispersions or sols of one or more metal oxides which are unstable in normal air environment (such as Li 2 O, Na 2 O, K 2 O, CaO, SrO, and BaO) and/or ceramic nonmetal oxides having an atomic number of 14 or greater (such as SiO 2 , As 2 O 3 , and P 2 O 5 ) , representative combinations including Al 2 O 3 - -Li 2 O, TiO 2 - -K 2 O, ZrO 2 - -CaO, ZrO 2 - -Al 2 O 3 - -CaO, ZrO 2 - -SrO, TiO 2 - -BaO, TiO 2 - -ZrO 2 - -BaO, Al 2 O 3 - -Na 2 O, MgO- -SiO 2 , Fe 2 O 3 - -Ba
  • a number of the above-described oxides useful in this invention are commercially available in the form of aqueous sols or dry powders which can be readily dispersed in water to form sols, such as Al 2 O 3 , Cr 2 O 3 and Fe 2 O 3 sols sold under the trademark "Nalco”, silica sols sold under the trademarks “Nalco,” “Ludox,” “Syton” and “Nyacol,” and Al 2 O 3 colloidal powder sold under the trademark “Dispal,” aluminum oxychloride powder sold under the trademark "Chlorhydrol Micro-Dry,” and the like.
  • the precursor material in the form of dispersion or sols of said oxides, it is within the scope of this invention to use the precursor material in the form of water soluble or dispersible inorganic or organic compounds which are calcinable to the corresponding oxide.
  • These compounds representatively include many carboxylates and alcoholates, e.g.
  • acetates formates, oxalates, lactates, propylates, citrates, and acetylacetonates
  • salts of mineral acids e.g., bromides, chlorides, chlorates, nitrates, sulfates, phosphates, and oxysalts of mineral and organic acids, e.g., oxybromides, oxychlorides, oxychlorates, oxynitrates and oxyacetates, selection of the particular precursor compound being dictated by availability and ease of handling.
  • Representative precursor compounds useful in this invention include ferric chloride or nitrate, chromium chloride, cobalt nitrate, nickel chloride, copper nitrate, zinc chloride or carbonate, lithium propylate, sodium carbonate or oxalate, potassium chloride, beryllium chloride, magnesium acetate, calcium lactate, strontium nitrate, barius acetate, yttrium bromide, zirconium acetate, hafnium oxychloride, vanadium chloride, ammonium tungstate, aluminum chloride, indium iodide, titanium acetylacetonate, stannic sulfate, lead formate, antimony chloride, bismuth nitrate, neodymium chloride, phosphoric acid, cerium nitrate, uranium nitrate, and thorium nitrate.
  • the Al 2 O 3 precursor can be aluminum alkoxide.
  • the aluminum alkoxides can be those of the aluminum containing materials further comprising hydrocarbyl containing lower alkyl radicals from 1 to 15 carbon atoms, preferably isopropyl.
  • Illustrative materials are aluminum tri-sec-butoxide, aluminum tri-tert-butoxide, aluminum triethoxide, aluminum n-butoxide, aluminum secbutoxide stearate, aluminum t-butoxide, aluminum di(sec-butoxide) acetoacetic esterchelate, aluminum di(iso-propoxide, aluminum phenoxide, and the like.
  • the most preferred material is aluminum oxychloride which on sintering gives the aluminum oxide.
  • Controlled amounts of additives and/or mineralizers are added as sintering aids to reduce the higher temperatures required for grain-growth inhibitors and toughening agents.
  • the additives added most frequently include Fe 2 O 3 , Cr 2 O 3 , TiO 2 , ZrO 2 , Ga 2 O 3 , MgO, Na 2 O, K 2 O, B 2 O 3 and V 2 O 3 .
  • ZrO 2 increases the toughness by a grain-boundarystrengthening mechanism by adding up to 0.05 wt% ZrO 2 .
  • the Na 2 O, Fe 2 O 3 and B 2 O 3 reduce the temperature, e.g., of mullite formation and crystallization.
  • B 2 O 3 is a preferred mineralizer (concentrations ⁇ 2%) added to the precursor solution in the form of boric acid.
  • ceramic metal oxide materials are prepared from a silica containing aqueous material which is modified to adjust the ph to acidic ph and then that composition is homogeneously blended with ceramic metal oxide solution or dispersion as described above.
  • the silicon that may be employed either alone or with metal oxides as identified above can generally be characterized as silicon oxides or alkoxides.
  • the silicon oxides can be silicon dioxide or oligomers or polymers thereof.
  • the silicon alkoxides can be those comprised of the silicon containing materials further comprising hydrocarbyl containing lower alkyl radicals from 1 to 6 carbon atoms, preferably ethyl.
  • Illustrative materials are tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane and amyltriethoxysilane, and the like.
  • the silicon material be colloidal silica which has an acidic ph, preferably a ph of 3-5 when it is reacted with the above identified metal oxides.
  • the colloidal silica is preferably in an aqueous state with a particle size less than 50 nanometers, preferably 0.5-25 nanometers.
  • the ph is adjusted from the normal ph of colloidal silica which is basic, usually about 8 to 10 by the use of acidic materials. Any acidic material that does not interfere with subsequent processing steps may be employed whether it be organic or inorganic, although preferably organic acids of less than 6 carbon atoms and even more preferably acetic acid is employed.
  • the colloidal silica be a very fine particle size.
  • the silica concentration should be less than 50% and preferably approximately 10- 30%, and even more preferably, about 20% by weight.
  • the purpose in adding the acidic material is to produce a negative electrostatic charge on the silica particles.
  • Colloidal silica particles exhibit a significant negative electrostatic charge in the ph range of from 3 to 5 and a value within this range is selected for matching with the ph of the aqueous metal oxide solution.
  • the ph adjusted colloidal silica solution are added to the slurry containing the metal oxide and the mixture is stirred, preferably in the presence of ultrasonic treatment to facilitate the reaction.
  • the colloidal silica particles with a negative electrostatic charge are attracted to the positively charged metal ion (for example the zeta potential for zirconia at a ph of 3-5 is approximately 58-64 millivolts and for alumina at a ph of 3-5 is about 45-50 millivolts).
  • the ratio of silicon material to metal oxide is from 0.5 to 1.1 (silica calculated as silica dioxide) to 1 (metal oxide calculated as metal dioxide) mole ratio. Most preferably, the mole ratio is 1:1.
  • the metal oxide to silicon dioxide corresponds to the moles of Al 2 O 3 to the moles of SiO 2 .
  • Ultrasonic treatment may be utilized for desirable blending.
  • the processing parameters are at ambient temperature and pressure and that the frequency ranges from 0.01 to 1 kilohertz, preferably less than 0.1 kilohertz, e.g., 0.05 to 0.07 kilohertz.
  • the concentration ranges from 10 to 80° wt %.
  • the viscosity of the solution or dispersion ranges from 1 to 40 Centipoise (CPS).
  • CPS Centipoise
  • the solution or mixture of materials which approaches the gel state may be dried prior to blending with the polymeric composition.
  • the metal oxide sol is blended in the liquid state with the liquid polymer composition.
  • heat resistant is meant a resin capable of withstanding temperatures of at least 350° F or higher. Lower temperature resins may not permit proper processing in the fiber glass field. Too low a temperature resistance may have the ceramic oxide and/or silicon oxide materials erupt from the ruptured resin wall because the resin could not withstand the heat.
  • Suitable materials may be crystalline polypropylene, urea formaldehyde polymers, phenolformaldehyde polymers such as phenolic resins, melamine resins, e.g., melamine formaldehyde resins, melamine urea-formaldehyde resins, polyimides, polybenzimidazole, polyphenylquinoxaline, polyamide-imides, polyarylsulfone, poly(arylethersulfone), polyphenylene, aromatic polyester, polyamides as aromatic polyamide, polyphenylene sulfide, acrylic and methacrylic acid and esters and copolymers thereof with vinyl materials as styrene, vinylchloride, and the like. The most preferred however are the least expensive such as the formaldehyde resins and the phenolic resins.
  • the thermoplastic or thermosetting compositions may be available as solutions, dispersions or emulsions of the various resinous compositions.
  • Encapsulation techniques are well known in the art. See, for example, U.S. Patent No. 3,516,941, describing encapsulation by acid catalyzing a urea-formaldehyde precondensate and forming the microcapsule cell wall.
  • the ceramic metal oxide and/or silicon oxide precursor solutions and the polymer composition it is preferred that this be conducted at ambient temperature and pressure. It is to be appreciated, however, that in order to obtain suitable processing conditions, the temperatures may need to be increased to less than boiling temperature of the various materials, and correspondingly, the pressure may need to be increased or decreased to above or below atmospheric pressure to improve the solubilizing/mixing processing conditions.
  • the two liquids, the one being the aqueous metal oxide and/or silicon oxide precursor solution and the second being the resinous composition are blended together. Due to the relative immiscibility or insolubility of the metal oxide liquid, the wall of the polymeric material forms about the metal oxide precursor solutions.
  • the encapsulant is cured and solidified.
  • Curing by heating or by other mechanisms such as adjustment of ph of the solution or addition of cross-linking agents may be utilized providing the agents have no detrimental effect on the ceramic metal oxide precursor solutions. Cooling of the thermoplastic material will solidify the wall about the ceramic oxide and/or silicon oxide.
  • the product is obtained by evaporating to dryness the composition or by separating out by filtration or other separation techniques the encapsulated metal oxide composition.
  • increasing the temperature will cause the thermosetting composition to cure further about the ceramic metal oxide materials.
  • curing may be done by the application of heat. These materials have a curing temperature of at least 350°F.
  • R' represents a reactive functional group, such as - OH, -COOH, halide, aldehyde, hydrolyzable ester and/or ether, hydrocarbyl, alkene, alkyne, or an alkoxy radical
  • X represents entity on which R' radicals are substituted
  • n is an integer of l or greater.
  • the use of the capsulated ceramic metal oxide and/or silicon oxide is for refractory purposes, e.g., utilizing the ceramic metal oxide in usual refractory purposes but delivered to a site under the protective envelope of the microencapsulated wall.
  • the microencapsulated spheres are applied to glass fibers to bind the fibers together.
  • the temperature, that the encapsulated ceramic metal oxide is subjected to is such that it will exceed the temperature of stabilization of the polymeric material preferably in excess of 350°F.
  • the temperature of degradation will vary with the type of polymer used to encapsulate. For many fiber glass applications, an activation temperature would be as low as 350°F - 400°F. At this point, the polymeric material will degrade and release the ceramic metal oxide and/or silicon oxide contained therein which will coat the fiber glass. Where the coated fibers intersect, the coating forms a bond thereby binding the fibrous matrix together.
  • the ceramic metal oxide and/or silicon oxide is applied to the fiber glass in any desired technique such as by spraying from an aqueous containing composition such as a dispersion or emulsion of same.
  • the amount of encapsulated metal oxide in the aqueous composition ranges from 1 to 75% by weight.
  • the fiberglass substrates to which the encapsulated ceramic metal oxide is applied are well known fiber glass compositions such as those that contain silica, aluminum and/or iron oxide, calcium oxide, magnesia, and optionally, other materials such as alkali oxide such as potassium or sodium oxide, boron oxides and the like.
  • the fiberglass materials can be made from pure or natural ingredients or from mineral or slag wool or the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Procédé de préparation d'un précurseur d'oxyde de cermet capsulé et/ou d'un précurseur d'oxyde de silicium capsulé; ledit procédé de préparation comprenant les étapes suivantes: (1) l'utilisation d'une composition de précurseur d'oxyde de cermet et/ou d'oxyde de silicium; (2) l'utilisation d'une composition de résine résistant à la chaleur; (3) le mélange des compositions; (4) l'encapsulage du précurseur d'oxyde de cermet et/ou d'oxyde de silicium avec la résine; et (5) la récupération de l'oxyde de cermet capsulé et/ou de l'oxyde de silicium capsulé. Cette invention concerne également des produits résultant de ce procédé et un procédé permettant de fixer des substrats de fibres de verre à l'aide du précurseur d'oxyde de cermet capsulé.
PCT/US1991/008976 1990-12-10 1991-12-02 Procede et composition servant a preparer des oxydes de cermet Ceased WO1992010286A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62459190A 1990-12-10 1990-12-10
US624,591 1990-12-10

Publications (2)

Publication Number Publication Date
WO1992010286A2 true WO1992010286A2 (fr) 1992-06-25
WO1992010286A3 WO1992010286A3 (fr) 1992-08-06

Family

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PCT/US1991/008976 Ceased WO1992010286A2 (fr) 1990-12-10 1991-12-02 Procede et composition servant a preparer des oxydes de cermet

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111151124A (zh) * 2020-01-08 2020-05-15 山东鲁阳浩特高技术纤维有限公司 一种具有催化导电功能的纳米板及其制备方法和应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891572A (en) * 1965-06-10 1975-06-24 Ici Ltd Production of stable dispersion of solid particles encapsulated in synthetic polymer
GB1172513A (en) * 1965-11-11 1969-12-03 Ici Ltd Polymer Coated Particles
DE1771558B1 (de) * 1968-06-08 1970-12-03 Quarzwerke Gmbh Verfahren zum Beschichten von feinkoernigem Schuettgut,insbesondere Quarzsand und Quarzmehl
DE2404880C3 (de) * 1973-02-03 1984-11-08 Yamaguchi, Tadashi, Dr., Sendai, Miyagi Verfahren zur Beschichtung anorganischer Pulver
US4349456A (en) * 1976-04-22 1982-09-14 Minnesota Mining And Manufacturing Company Non-vitreous ceramic metal oxide microcapsules and process for making same
US4421660A (en) * 1980-12-15 1983-12-20 The Dow Chemical Company Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111151124A (zh) * 2020-01-08 2020-05-15 山东鲁阳浩特高技术纤维有限公司 一种具有催化导电功能的纳米板及其制备方法和应用

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