WO1999000336A1 - Revetement a base d'alliage chrome-cobalt resistant a la corrosion - Google Patents

Revetement a base d'alliage chrome-cobalt resistant a la corrosion Download PDF

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Publication number
WO1999000336A1
WO1999000336A1 PCT/US1998/012845 US9812845W WO9900336A1 WO 1999000336 A1 WO1999000336 A1 WO 1999000336A1 US 9812845 W US9812845 W US 9812845W WO 9900336 A1 WO9900336 A1 WO 9900336A1
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WO
WIPO (PCT)
Prior art keywords
cobalt
chromium
coating
spinner
recited
Prior art date
Application number
PCT/US1998/012845
Other languages
English (en)
Inventor
Dennis L. Mcgarry
Original Assignee
Owens Corning
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 Owens Corning filed Critical Owens Corning
Publication of WO1999000336A1 publication Critical patent/WO1999000336A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
    • C03B37/047—Selection of materials for the spinner cups
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/06—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases
    • C23C10/14—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases more than one element being diffused in one step

Definitions

  • This invention relates generally to alloy coatings that inhibit the corrosion of surfaces subjected to highly corrosive environments. More particularly, the present invention relates to corrosion resistant alloy coatings applied to the surface of spinners used to produce filaments from molten glass and other molten mineral materials. Even more particularly, the present invention relates to corrosion resistant chromium and cobalt containing alloy coatings for application to at least the inner peripheral surfaces of glass fiber spinner orifices in order to reduce the rate of orifice enlargement during the fabrication of glass fiber from molten glass. The present invention also relates to spinners having the alloy coatings of the invention applied thereto, and further is directed to methods by which the alloy coatings of the invention may be uniformly applied to the surfaces of glass fiber spinners.
  • the spinner's chamber includes a peripheral wall having a large number (generally, from about a few hundred to about several thousand) of radially disposed, substantially cylindrical orifices.
  • the orifices typically are less than one millimeter in diameter. Molten glass or other molten mineral material introduced into the chamber is extruded through the orifices by centrifugal force and forms filaments as the spinner rotates.
  • the orifices typically are produced by laser or electron beam drilling through the spinner's peripheral wall, but also may be formed by other conventional techniques such as, for example, mechanical drilling.
  • Spinners typically are constructed of high-rupture strength alloys, also known as "superalloys", which commonly are cobalt-base alloys that may also include, for example, carbon, chromium, nickel, silicon, tantalum, tungsten, zirconium, hafnium, and boron. Spinners also may be constructed of nickel-base superalloys that typically also contain one or more of carbon, chromium, silicon, tantalum, tungsten, titanium, molybdenum, and zirconium. Typical spinner designs and their constituent alloys are more fully described in United States Patent Nos. 3,933,484, 4,820,324, and 4,877,435, each of which is hereby incorporated herein by reference.
  • a glass filament spinner having corrosion-resistant precious metal tubular inserts that are press-fit into the spinner orifices.
  • the inserts protect the spinner orifices from contact with the extruded molten material and thereby inhibit enlargement of the orifices' diameter.
  • the additional materials and manufacturing steps necessary to provide the inserts and press fit them in place into the numerous orifices can significantly increase the cost of producing glass fiber.
  • 5,417,735 discloses a glass fiber spinner having a corrosion-resistant coating comprising layers of at least partially interdiffused chromium and nickel adhered to the surface of the fiber-forming orifices.
  • nickel is difficult to deposit in pure form.
  • electroless nickel coatings contain boron or phosphorous. Both of these elements reduce the melting temperature of the electroless coatings and, therefore, the coatings generally are not useful for high-temperature applications.
  • the techniques disclosed in the '735 patent for producing the interdiffused chromium-nickel coatings require several steps, and each step can increase the cost of the coating.
  • the present invention relates to durable and corrosion-resistant metallic alloy coatings.
  • the coatings may be applied to the surfaces of the fiber-forming orifices of glass fiber or other mineral fiber spinners to inhibit the corrosion of the orifices during fiber production.
  • the present invention's coatings include 20 to 80 weight percent cobalt, with the balance being chromium plus incidental impurities, the weight percentages based on the entire weight of the coating.
  • the coatings include at least 40 weight percent cobalt, and the coatings most preferably include equal parts by weight of cobalt and chromium.
  • the coatings of the invention may be applied using any of the conventional coating methods known to those of skill in the art.
  • the coatings of the - present invention may be applied by a "pack cementation" chemical vapor deposition process in which the object to be coated, for example, a glass fiber spinner, is heated along with particles of chromium and cobalt metals and an activator compound that will form a metal carrier gas when heated.
  • the weights and proportion of the chromium and cobalt metal particles are selected to provide a coating having the desired alloy composition.
  • the metal particles and activator are then heated and the metal is transferred in vapor form to the surface of the object.
  • the inner peripheral surfaces of the spinner's fiber-forming orifices may be coated.
  • the metallic alloy coatings of the present invention will enhance the corrosion resistance of glass or other mineral fiber spinners constructed of practically any of the alloys conventionally used to produce spinners.
  • the coatings of the invention can significantly reduce corrosion of the spinner orifices, and thereby reduce uncontrolled enlargement of orifice diameter and substantially increase spinner life.
  • the coatings do not incorporate expensive precious metals, and the pack cementation process described herein does not require numerous steps, thereby significantly limiting the cost of producing the coatings.
  • FIG. 1 is a semi-schematic, front elevational view of a rotary fiber-forming system for producing glass fiber wool
  • FIG. 2 is an enlarged cross-sectional view of the spinner shown in FIG. 1.
  • rotary or centrifugal fiber forming system 40 is comprised of a flow means or channel 42 having a body of molten inorganic material 44, such as glass, therein.
  • a stream of molten glass 46 is supplied to spinner 50 from channel 42, as is known in the art.
  • spinner 50 which is adapted to be rotated at high speeds, is comprised of a quill 52 and a circumferential or peripheral stream-defining working wall 54 defining an interior of the spinner 50 and having a plurality of orifices 55 therethrough to supply a plurality of pre-filament or primary streams of the molten inorganic material to be fiberized.
  • the hundreds or thousands of orifices 55 are formed in the circumferential wall 54 by, for example, electron beam drilling.
  • a shroud 56 and circumferential blower or fluid attenuation means 57 are adapted to assist in the attenuation of the streams of molten material into fibers or filaments 60.
  • a binder material or coating may be applied to the fibers 60 by means of binder applicators 58 as is known in the art.
  • the fibers 60 may then be collected as a pack or mat to produce "wool" type glass fiber insulation.
  • glass fiber refers to vitreous fibers of glass, slag, or other mineral material.
  • spinner 50 receives a post-fabrication treatment (i.e., a treatment at some time subsequent to the formation of orifices 55 in circumferential wall 54) wherein a corrosion-resistant metallic alloy coating is applied to at least the inner peripheral surfaces of the fiber-forming orifices 55.
  • a corrosion-resistant metallic alloy coating is applied to at least the inner peripheral surfaces of the fiber-forming orifices 55.
  • metallic chromium-cobalt alloy coatings comprising 20 to 80 weight percent cobalt and the balance chromium enhance the corrosion resistance of the spinner orifices and inhibit orifice enlargement, thereby prolonging the useful service life of the spinner.
  • the coatings of the present invention preferably are binary alloys of cobalt and chromium including at least 40 weight percent cobalt, and most preferably are binary alloys of equal parts by weight of cobalt and chromium.
  • the present inventor has discovered that the chromium content of the coatings of the invention strongly influences the coatings' corrosion rates.
  • the corrosion resistance of the present invention's coatings containing 20 weight percent chromium are significantly improved relative to pure cobalt or chromium coatings, and corrosion resistance continues to improve as the chromium content is increased, up to 50 weight percent chromium. As chromium content exceeds 50 weight percent, corrosion resistance decreases slightly.
  • a 1:1 ratio of cobalt to chromium is the most preferred coating composition because such a composition provides superior corrosion resistance compared to substantially greater or lesser cobalt-to- chromium ratios.
  • coatings of the invention including about 45-55 weight percent cobalt (based on the entire weight of the coating) have one-half to one-third the corrosion rate of a binary cobalt-chromium alloy coating including 70-80 weight percent cobalt.
  • the coatings of the invention may also include incidental impurities.
  • the impurities may be, for example, picked up from the walls of any containment vessels used in the production of the coatings or may be impurities inherent within the starting materials utilized to produce the coatings. Such impurities should in general be limited to 1% of the total weight of the coating.
  • any metallic surface will increase the resistance of such surface to the corrosive effects of molten glass or other molten mineral material.
  • the coatings when applied to the metallic surface of glass fiber spinners, for example spinner 50, provide increased durability and corrosion resistance to contact with molten glass or other molten mineral material.
  • the coatings of the present invention stay in good mechanical contact with the spinner body, and do not spall, crack, or otherwise mechanically fail in use.
  • the coatings are resistant to the corrosive effects of molten glass or other molten mineral material when applied to the surfaces of the fiber-forming orifices of rotary glass fiber spinners constructed of practically any of the cobalt, nickel, iron, or refractory metal -base superalloys conventionally employed in constructing such spinners.
  • superalloys that may be used to produce glass fiber spinners, the durability and corrosion properties of which it is believed would be augmented by application of the coating of the present invention, are found in United States Patent Nos. 4,668,265, 4,820,324, 4,767,432, 3,933,484, and 4,761,169.
  • the coatings of the invention may be applied using any method known to those of skill in the art for forming a uniform metallic alloy coating or layer on a metallic surface and wherein the coating either is adhered to the surface or is at least partially interdiffused into the surface.
  • Such methods include various known chemical vapor deposition
  • CVD chemical vapor deposition
  • pack cementation gas phase CVD
  • Gas phase CVD typically is carried out in a chamber into which gaseous species are transported to react with the surface of the part to be coated.
  • United States Patent Nos. 3,804,665, 3,767,456, 4,992,305, and 4,938,999 describe a few of the uses of CVD coating techniques, and-the entire disclosure of those references is incorporated herein by reference.
  • Methods useful for forming the coatings of the present invention on metal surfaces also include the method described in United States Patent No. 5,417,735, the entire disclosure of which is hereby incorporated herein by reference, wherein the metals comprising the metallic coating are applied in pure layers and then are interdiffused in situ.
  • the pack cementation process is carried out in a containment vessel, or "pack", containing particles, powders, or a similar form of the one or more metals to be coated onto the target surface along with an activator compound that will form a metal carrier gas when heated.
  • the metals and activator are then heated and the metals are transferred in vapor form to the surface of the target part, which is also in or just above the pack.
  • pack cementation will be less expensive than a gas phase CVD process employing a cell into which gaseous reactants are introduced.
  • a uniform coating of the chromium-cobalt alloy of the present invention may be readily provided using a conventional gas phase CVD process carried out in a chamber. It is believed that deposition of metallic coatings using gas phase CVD will permit the growth of thicker coatings than can be achieved using pack cementation.
  • the pack cementation CVD process is known to those of skill in the art and, therefore, one of ordinary skill may readily determine, without significant experimentation, the appropriate starting materials, equipment, and procedures necessary to form the coatings of the present invention on metallic objects of a given size, shape, and construction. Nevertheless, for the reader's convenience, the inventor provides the following more detailed description of the procedure by which the coatings of the present invention may be applied by the pack cementation process.
  • the metal powders included in the pack are selected so that heating the powders with the activator produces gases that will decompose to form an alloy of cobalt and chromium when the gases contact the exposed surfaces of the part to be coated.
  • the mixture of metal powders and activator must decompose when heated to form gaseous halides of the metals to be deposited on the object surface.
  • the metal powders and activator are selected to form gaseous chromium chloride and cobalt chloride.
  • the activator is preferably a halide salt, for example ammonium chloride or a metal chloride such as zirconium chloride, and provides the source of carrier gas, usually chloride.
  • the activator in powder form and the metal compounds are mixed along with an inert filler powder, preferably alumina powder. With respect to the incidental impurity elements mentioned above, some impurities may be picked up in the coating from the inert filler.
  • the containment vessel used to carry out the pack cementation process must be able to withstand the temperatures necessary to produce the coating on the target surface.
  • the containment vessel must also maintain a seal to keep ambient air from entering the vessel during the coating reaction.
  • Containment vessels constructed of a nickel-base superalloy are preferred over those of an iron-base superalloy to avoid introducing iron impurities into the coating.
  • the mesh size of the inert filler is generally not critical; however, the mesh size must not be so large as to become lodged in any orifices in the object to be coated, such as, for example, the fiber-forming orifices of rotary glass fiber spinners. For that reason, it is preferred that when coating glass fiber spinners, the activator particles should be at least as small as 200 mesh.
  • the mesh size of the activator compound is not believed to be critical.
  • the mesh sizes of the cobalt and chromium metals placed into the pack should be chosen so that the particles' ratio of surface area to volume is large. Metal particles that are at least as small as -200 mesh are preferred. Metal briquettes may also be used.
  • the temperature of the pack cementation process and the time at temperature control the coating rate. It is preferred that the pack cementation reaction used to produce the coatings of the present invention on spinners be carried out at from 900°C to 1200°C. Reaction temperatures significantly higher than 1200°C may melt the activator, which may adversely affect the coating of surface roughness. Temperatures below 900°C may require long time periods for satisfactory coating.
  • the most preferred time and temperature to form the coatings of the present invention on glass fiber spinners by the pack cementation process is 12 hours at 1150°C. Before raising the temperature of the pack to 1150°C, it should be flushed with an inert gas, preferably argon, for a short time at low temperature, preferably for about 2 hours at about 300°C.
  • an inert gas preferably argon
  • the pack When the pack has reached the 1150°C reaction temperature, it should be stagnant with little or no argon flow.
  • the ratio of cobalt metal to the entire weight of the cobalt and chromium metal in the pack preferably should be greater than 0.3 to avoid carbide formation.
  • the preferred chromium metal to cobalt metal ratio in the pack is 1 : 1.
  • Such a ratio not only should result in the least amount of detrimental chromium carbide in the coating, but also has been found to provide optimal corrosion resistance and is the most preferred composition of the coating.
  • powdered ammonium chloride activator as an example, the activator forms ammonia and chlorine gases when heated. The chlorine gas reacts with cobalt powder within the pack to form gaseous cobalt chloride.
  • the gaseous cobalt chloride travels to the surface of the part and reacts at any surface that is not pure cobalt, depositing cobalt and freeing chloride gas.
  • the free chloride gas then reacts with additional cobalt metal particles to form additional gaseous cobalt chloride, and the cycle repeats.
  • chromium powder By also adding chromium powder to the pack, some of the chloride gas reacts to form chromium chloride gas that is free to move to the part, where it will decompose and deposit chromium.
  • the stepwise deposition of metal at the part surface provides an alloy coating of the deposited metals.
  • Coatings of the present invention formed on glass fiber spinners by the pack cementation method are generally uniformly thick along the length of the interior of the fiber-forming orifices.
  • coatings may contain voids, it is believed that about 10-20% void volume can be tolerated without adversely affecting the corrosion performance, durability, or strength of the coatings.
  • the coatings of the present invention exhibit excellent bonding to spinner surfaces and have been shown to withstand thermal cycles and some slight creep by matching the dimensional changes of the spinner in operation.
  • a corresponding weight proportion of metal powders is placed within the pack. For example, if a coating containing equal weight percentages of chromium and cobalt is desired, equal weights of chromium and cobalt metal powders will be included in the pack along with an amount of activator sufficient to transfer the necessary amount of coating constituent elements to the target surface.
  • the appropriate amounts of starting materials may be readily ascertained by those of skill in the art.
  • the pack is prepared so as to contain excess metal powder and a slight excess of activator.
  • the pack preferably should contain 10-100 times the weight of metal to be deposited.
  • the amount of activator added to the pack should be about 1/10 the total weight of the coating metal within the pack.
  • Prepared in this way, a single pack can be used multiple times. The number of times that a single pack of starting materials may be used depends on a number of factors and to ascertain when a new pack should be provided for further coating, test samples may be coated in the pack periodically so that the quality and thickness of the resultant coating can be determined by sectioning and inspection.
  • Coatings of the invention as thin as 10 microns produced by pack cementation can significantly augment spinner life in some applications.
  • certain fiber forming processes will run satisfactorily until up to 100 microns of coating metal have been removed from the surfaces of the fiber-forming orifices.
  • coatings having a relatively significant thickness are required.
  • a gas phase CVD operation can deposit 50 to 100 microns of a coating in a reasonable time. Therefore, if the fiber- forming orifices of a spinner are drilled with a diameter that is 50 microns larger than the target fiber diameter, then coated back to the target diameter, the spinner ' s service life can be doubled.
  • three containers are provided.
  • One such container includes therein chromium briquettes or powder, another container includes therein cobalt briquettes or powder, and the third container includes therein the part to be coated.
  • the three containers are connected in series by gas-conducting pathways, with the container having the object therein connected last in the series.
  • the chromium metal, cobalt metal, and object are heated and chlorine gas is passed through the containers having the chromium and cobalt therein and into the container including the object.
  • the chlorine gas reacts with the metals to produce cobalt and chromium chloride gases, which in turn react with the surface of the part to be coated to form a chromium-cobalt alloy coating thereon.
  • the metallic alloy coatings of the present invention has been applied to spinner superalloys, it is believed that the inventive coatings may be applied to any metallic surface and will reduce the corrosive effects of molten glass or other material and reduce oxidation on that surface. Accordingly, while the present invention has been described in connection with the foregoing preferred embodiment, it is to be understood that the present invention's coatings may be advantageously applied to different starting materials and that the present invention may be modified without departing from the scope of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un revêtement à base d'alliage métallique contenant du cobalt et du chrome, permettant d'améliorer la durabilité et la résistance à la corrosion des objets. Ce revêtement comprend de préférence de 20 à 80 % en poids de cobalt, le reste étant composé de chrome et d'impuretés accidentelles. Dans un mode d'application le revêtement est appliqué sur des paniers centrifugeurs (50) servant à produire des fibres (60) à partir de verre en fusion (44) ou d'autres matières minérales en fusion (44). Le revêtement augmente la durabilité et la résistance à la corrosion des orifices (55) du panier centrifugeur servant à former les fibres, et qui entrent ainsi en contact avec la matière en fusion (44). On peut appliquer par exemple le revêtement à base d'alliage par des techniques de dépôt chimique en phase vapeur comprenant un procédé de cémentation en milieu pulvérulent dans lequel un gaz vecteur transporte à température élevée les métaux de revêtement sous forme de particules métalliques vers le panier centrifugeur.
PCT/US1998/012845 1997-06-30 1998-06-19 Revetement a base d'alliage chrome-cobalt resistant a la corrosion WO1999000336A1 (fr)

Applications Claiming Priority (2)

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US88597197A 1997-06-30 1997-06-30
US08/885,971 1997-06-30

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1266747A1 (fr) * 2001-06-11 2002-12-18 Takeda Chemical Industries, Ltd. Poinçon et matrice en alliage de cobalt pour préparer des comprimés
WO2013050696A1 (fr) 2011-10-06 2013-04-11 Saint-Gobain Adfors Dispositif delivrant des fibres de verre a teneur reduite en metaux precieux
CN107555967A (zh) * 2017-08-02 2018-01-09 山东玻纤集团股份有限公司 一种玻璃纤维拉丝漏板陶瓷喷涂工艺

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US3286684A (en) * 1962-12-24 1966-11-22 Ling Temco Vought Inc Cementation coating pack
US4024294A (en) * 1973-08-29 1977-05-17 General Electric Company Protective coatings for superalloys
US4034142A (en) * 1975-12-31 1977-07-05 United Technologies Corporation Superalloy base having a coating containing silicon for corrosion/oxidation protection
US4518406A (en) * 1983-12-06 1985-05-21 Owens-Corning Fiberglas Corporation Drain bushing
US4536202A (en) * 1983-12-06 1985-08-20 Owens-Corning Fiberglas Corporation Drain bushing
US4634460A (en) * 1986-01-17 1987-01-06 Manville Service Corporation Drain bushing
US4717411A (en) * 1986-05-06 1988-01-05 Manville Corporation Drain bushing
US4963395A (en) * 1988-06-24 1990-10-16 Combustion Engineering, Inc. Method of chromizing large size articles
US4992305A (en) * 1988-06-22 1991-02-12 Georgia Tech Research Corporation Chemical vapor deposition of transistion metals
US5417735A (en) * 1993-12-23 1995-05-23 Mcgarry; Dennis L. Interdiffused chromium/nickel corrosion-resistant coating for fiberglass spinner bores
US5582707A (en) * 1993-11-09 1996-12-10 Golan Galvanics, Ltd. Electrolyte for electroplating of chromium based coating, having improved wear resistance, corrosion resistance and plasticity

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3286684A (en) * 1962-12-24 1966-11-22 Ling Temco Vought Inc Cementation coating pack
US4024294A (en) * 1973-08-29 1977-05-17 General Electric Company Protective coatings for superalloys
US4034142A (en) * 1975-12-31 1977-07-05 United Technologies Corporation Superalloy base having a coating containing silicon for corrosion/oxidation protection
US4518406A (en) * 1983-12-06 1985-05-21 Owens-Corning Fiberglas Corporation Drain bushing
US4536202A (en) * 1983-12-06 1985-08-20 Owens-Corning Fiberglas Corporation Drain bushing
US4634460A (en) * 1986-01-17 1987-01-06 Manville Service Corporation Drain bushing
US4717411A (en) * 1986-05-06 1988-01-05 Manville Corporation Drain bushing
US4992305A (en) * 1988-06-22 1991-02-12 Georgia Tech Research Corporation Chemical vapor deposition of transistion metals
US4963395A (en) * 1988-06-24 1990-10-16 Combustion Engineering, Inc. Method of chromizing large size articles
US5582707A (en) * 1993-11-09 1996-12-10 Golan Galvanics, Ltd. Electrolyte for electroplating of chromium based coating, having improved wear resistance, corrosion resistance and plasticity
US5417735A (en) * 1993-12-23 1995-05-23 Mcgarry; Dennis L. Interdiffused chromium/nickel corrosion-resistant coating for fiberglass spinner bores

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1266747A1 (fr) * 2001-06-11 2002-12-18 Takeda Chemical Industries, Ltd. Poinçon et matrice en alliage de cobalt pour préparer des comprimés
WO2013050696A1 (fr) 2011-10-06 2013-04-11 Saint-Gobain Adfors Dispositif delivrant des fibres de verre a teneur reduite en metaux precieux
CN107555967A (zh) * 2017-08-02 2018-01-09 山东玻纤集团股份有限公司 一种玻璃纤维拉丝漏板陶瓷喷涂工艺
CN107555967B (zh) * 2017-08-02 2023-04-14 山东玻纤集团股份有限公司 一种玻璃纤维拉丝漏板陶瓷喷涂工艺

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