WO2017155933A1 - Ceramic additive formulation and method of making - Google Patents
Ceramic additive formulation and method of making Download PDFInfo
- Publication number
- WO2017155933A1 WO2017155933A1 PCT/US2017/021070 US2017021070W WO2017155933A1 WO 2017155933 A1 WO2017155933 A1 WO 2017155933A1 US 2017021070 W US2017021070 W US 2017021070W WO 2017155933 A1 WO2017155933 A1 WO 2017155933A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- formulation
- ceramic glaze
- ceramic
- unfritted
- Prior art date
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2092—Resistance against biological degradation
Definitions
- the present invention relates generally to ceramic glazes, more particularly to a ceramic glaze additive formulation, a method of making the ceramic glaze additive formulation, and a ceramic glazed article.
- Sanitary ware requires a significant increase in the amount of zinc to give it the desired aesthetic color and appearance.
- Bismuth and zinc are two of the most difficult antimicrobial components to put into a glaze. Bismuth particles melt at a lower temperature than zinc, and zinc may not go into solution with the other components of the glaze.
- the bismuth and the zinc can cause problems with increased fluidity and dripping of the glaze. In not blended well, both can cause discolorations.
- Bismuth produces clear spots in a white glaze, and zinc produces whiter areas. There is also dimpling. Zinc can also react with chrome and tin to alter the resulting glaze color.
- the present invention relates to a ceramic glaze additive formulation, a method of making the ceramic glaze additive formulation, and a ceramic glazed article.
- a method of making a ceramic glaze formulation having an antimicrobial property for use with a ceramic article comprises fritting an antimicrobial formulation in a flux frit, wherein the flux frit is present in the ceramic glaze formulation in an amount of 45 weight % to 55 weight %, based on a dry weight basis of the ceramic glaze formulation; providing least one unfritted antimicrobial component; providing a silver carrier in a glass matrix; combining the flux frit, the at least one unfritted component, and the silver carrier in the glass matrix to form the ceramic glaze formulation; wherein the silver carrier is combined at an addition rate of at least 1 weight % based on a dry weight basis of the ceramic glaze formulation.
- the method comprises fritting an antimicrobial formulation in a flux frit, wherein the flux frit is present in the ceramic glaze formulation in an amount of 1 weight % to 10 weight %, based on a dry weight basis of the ceramic glaze formulation; providing at least one unfritted antimicrobial component; providing a silver carrier in a glass matrix; combining the flux frit, the at least one unfritted antimicrobial component, and the silver carrier in the glass matrix to form the ceramic glaze formulation; wherein the silver carrier is added to the ceramic glaze formulation at an addition rate of at least 10 weight % based on a dry weight basis of the ceramic glaze formulation.
- a ceramic glaze additive formulation comprising: 0.1% to 1% by weight of silver carrier; 12% to 21% by weight of Bi 2 0 3 ; 29% to 37% by weight of ZnO; and 45% to 55% by weight of flux frit, wherein a weight percentage is based upon the weight of the ceramic glaze additive formulation.
- Another ceramic glaze additive formulation is provided comprising: 5% to 15% by weight of silver carrier; 80% to 90% by weight of ZnO; and 1% to 10% by weight of flux frit, wherein a weight percentage is based upon the weight of the ceramic glaze additive formulation.
- a ceramic glazed article comprising a ceramic glaze additive formulation applied on a surface of the ceramic article, the ceramic glaze additive formulation comprising: 0.1% to 1% by weight of silver carrier; 12% to 21% by weight of Bi 2 0 3 ; 29% to 37% by weight of ZnO; and 45% to 55% by weight of flux frit, wherein a weight percentage is based upon the weight of the ceramic glaze additive formulation.
- another ceramic glazed article comprising a ceramic glaze additive formulation comprising: 5% to 15%) by weight of silver carrier; 80% to 90% by weight of ZnO; and 1% to 10% by weight of flux frit, wherein a weight percentage is based upon the weight of the ceramic glaze additive formulation.
- microbe or “microbial” should be interpreted to refer to any of the microscopic organisms studied by microbiologists or found in the use environment of a ceramic article or ceramic-glazed article. Such organisms include, but are not limited to, bacteria and fungi as well as other single-celled organisms such as mold, mildew and algae. Viral particles and other infectious agents are also included in the term microbe.
- antimicrobial includes biostatic activity, i.e., where the proliferation of microbiological species is reduced or eliminated, and true biocidal activity where microbiological species are killed.
- biostatic activity i.e., where the proliferation of microbiological species is reduced or eliminated
- true biocidal activity where microbiological species are killed.
- this detailed description may make reference to bacteria and antibacterial agents. This method of presentation should not be interpreted as limiting the scope of the invention in any way.
- antimicrobial and like terms should be interpreted as encompassing both microbe-killing as well as microbiostatic activities. That is, it herein is considered efficacious if an antimicrobial composition reduces the number of microbes on a substrate or it the composition retards the normal rate of microbial growth.
- microbes and antimicrobial used to denote a broad spectrum activity (e.g. against bacteria and fungi).
- the more focused term will be used (e.g. antifungal to denote efficacy against fungal growth in particular).
- microbes and antimicrobial used to denote a broad spectrum activity (e.g. against bacteria and fungi).
- the more focused term will be used (e.g. antifungal to denote efficacy against fungal growth in particular).
- Glazes are generally made from powdered glass combined with colored oxides of such elements as cobalt, chrome, manganese, or nickel.
- the powder mixture is suspended in water and applied to the ceramic surface by spraying, brushing, dipping, or other known application methods.
- the suspension, or slip, in which the glaze is applied to the ceramic surface must have particular properties to ensure that the glaze is easy to apply, does not run during glaze application, and adheres well both when wet and after firing.
- slip properties are often obtained by adding a small amount of clay to the suspension and by controlling both the amount of water in the slip as well as the size of the powder particles.
- Organic surface-active agents e.g. surfactants, detergents
- Colors in glazes are controlled by adding coloring agents to the glassy components of the glaze.
- a ceramic production glaze formulation is a combination of ceramic materials that have been developed for production application to specific ceramic articles.
- a ceramic glaze additive formulation is a combination of antimicrobial components that are combined in a ceramic production glaze formulation to result in an antimicrobial ceramic production glaze formulation.
- the ceramic glaze additive formulation of the present invention comprises a fritted antimicrobial composition, an unfritted antimicrobial component(s), and a silver carrier in a glass matrix.
- fritting means melting an antimicrobial agent(s) or constituent(s) into a glass, quenching the glass to freeze the amorphous condition, and then grinding to a desired particle size.
- the fritted antimicrobial composition is a more homogeneous composition and allows higher amounts of the components than is acceptable in the oxide form. Using a flux frit as the entire source or the partial source of the antimicrobial components permits a much wider range of compositions. Fritting the composition creates an antimicrobial additive that is more easily combined with a base (untreated) glaze.
- the fritted material is also better tolerated in faster firing cycles with a reduction in surface defects due to varying firing cycles with a reduction in surface defects due to varying melting points and viscosities.
- the fritted material has fewer firing limitations because the dissociation of its components has already occurred during fritting.
- the fritted antimicrobial composition comprises an antimicrobial selected from the group consisting of bismuth oxide (Bi 2 0 3 ), zinc oxide (ZnO), and a combination thereof.
- the unfritted components are selected from the group consisting of bismuth oxide (Bi 2 0 3 ), zinc oxide (ZnO), and a combination thereof.
- a first ceramic glaze formulation comprises 0.1% to 1% by weight of silver carrier; 12% to 21% by weight of Bi 2 0 3 ; 29% to 37% by weight of ZnO; and 45% to 55% by weight of flux frit, based upon the weight of the ceramic glaze formulation.
- a second ceramic glaze formulation comprises 5% to 15% by weight of silver carrier; 80% to 90% by weight of ZnO; and 1% to 10% by weight of flux frit, based upon the weight of the ceramic glaze formulation.
- a method of making a ceramic glaze having an antimicrobial property for use with a ceramic article is provided.
- the method generally comprises fritting an antimicrobial formulation in a flux frit, wherein the flux frit is present in the ceramic glaze formulation in an amount of 45 weight % to 55 weight %, based on a dry weight basis of the ceramic glaze formulation; providing at least one unfritted antimicrobial component; providing a silver carrier in a glass matrix; combining the flux frit, the at least one unfritted antimicrobial component, and the silver carrier in the glass matrix to form the ceramic glaze formulation.
- the silver carrier is combined at an addition rate of at least 1 weight % based on a dry weight basis of the glaze formulation.
- the method generally comprises fritting an antimicrobial formulation in a flux frit, wherein the flux frit is present in the ceramic glaze additive formulation in an amount of 1 weight % to 10 weight %, based on a dry weight basis of the ceramic glaze formulation; providing at least one unfritted antimicrobial component; providing a silver carrier in a glass matrix; combining the flux frit, the at least one unfritted antimicrobial component, and the silver carrier in the glass matrix to form the ceramic glaze formulation.
- the silver carrier is combined at an addition rate of at least 10 weight % based on a dry weight basis of the ceramic glaze formulation.
- the silver carrier can be combined with the flux frit.
- the silver carrier can be mixed into the frit. It may require a larger amount of silver ions on the surface of the carrier.
- Another method by which the silver carrier can be combined with the flux frit is by a treatment material such as a chemical bath. It is possible to preferentially put silver into a glass matrix such that it is on the surface of the carrier.
- the antimicrobial formulation comprises an antimicrobial selected from the group consisting of zinc oxide, bismuth oxide, titanium oxide, tin oxide, silver compound, and a combination thereof.
- the antimicrobial formulation comprises an antimicrobial selected from the group consisting of bismuth oxide, zinc oxide, and a combination thereof. It was surprisingly found that there is a synergistic effect with zinc oxide and bismuth oxide in certain combinations when used in the method of this invention.
- the flux frit further comprises a glass former.
- the glass formers are typically glass constituents having no efficacious history.
- B12O3 is present in the flux frit in a range of 50% to 56% by weight, preferably in a range of 52% to 54% by weight, of the flux frit.
- ZnO is present in the flux frit in a range of 1% to 5% by weight, of the flux frit.
- unfritted B12O3 is present in the ceramic glaze formulation in a range of 12% to 20% by weight, preferably in a range of 14% to 18% by weight, of the ceramic glaze formulation.
- unfritted ZnO is present in the ceramic glaze formulation in a range of 29% to 37% by weight, preferably in a range of 31%> to 35% by weight, of the ceramic glaze formulation.
- unfritted B12O3 is present in the ceramic glaze formulation in a range of 0% to 5% by weight, preferably 0% by weight, of the ceramic glaze formulation.
- unfritted ZnO is present in the ceramic glaze formulation in a range of 80% to 90% by weight, preferably in a range of 83% to 87% by weight, of the ceramic glaze formulation.
- a ceramic article in another embodiment, comprises a fritted antimicrobial composition comprising an antimicrobial selected from the group consisting of bismuth oxide, zinc oxide, and a combination thereof; and a silver carrier in a glass matrix.
- the bismuth oxide is present in a range of 59% to 68% by weight of the ceramic glaze formulation
- zinc oxide is present in an amount of 30% to 40% by weight of the ceramic glaze formulation
- the silver carrier is present in a range of 0.1% to 1% by weight of the ceramic glaze formulation.
- the bismuth oxide is present in a range of 0% to 10% by weight of the ceramic glaze formulation
- zinc oxide is present in an amount of 80% to 90% by weight of the ceramic glaze formulation
- the silver carrier is present in a range of 5% to 15% by weight of the ceramic glaze formulation.
- the ceramic article of the present invention is any article having a ceramic glaze including, but not limited to, toilets, bidets, washbasins, towel rails, soap holders, toilet roll holders, water control fixtures (e.g., hot and cold water handles), and tiles.
- the present invention surprisingly solves the need of making faster fired ceramic articles.
- the term "faster fired” refers to a shorter time required for the ceramic article to cycle through the kiln while maintaining the required properties and quality produced using the longer firing time.
- the method reduces the firing time for various components of the glaze formulation.
- a ceramic formulation goes through various combinations of time and temperature (heat treatment) in a kiln to develop a vitreous or crystalline bond necessary to provide the properties associate with a ceramic material.
- This heat treatment (combination of time and temperature) is necessary to remove those materials which are given off at various points within the kiln. Examples of these are water of formation, chemical water, carbonates, phosphates, and all included organic materials.
- a ceramic production glaze formulation that is to be applied to a ceramic production substrate or article, comprises about 2 weight % to about 12 weight % on a dry weight basis of zinc oxide that it is possible to reduce the amount of zinc oxide in the antimicrobial addition.
- the amount of zinc oxide can range from 0 weight % to 10 weight % in the antimicrobial formulation depending upon the amount of zinc oxide already present in the ceramic production glaze formulation. This is as a component of the antimicrobial formulation that is then added to the ceramic production glaze formulation at 4 weight % to 10 weight % on a dry weight basis.
- the fritting method of the present invention can be used to implement the different antimicrobial combinations into an untreated glaze or as an application of these materials in an aqueous solution or organic carrier onto the top surface of an unfired glaze.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17763860.8A EP3426621A4 (en) | 2016-03-09 | 2017-03-07 | Ceramic additive formulation and method of making |
MX2018010783A MX2018010783A (en) | 2016-03-09 | 2017-03-07 | Ceramic additive formulation and method of making. |
CN201780016016.3A CN109071353B (en) | 2016-03-09 | 2017-03-07 | Ceramic additive preparation and preparation method thereof |
BR112018068031-1A BR112018068031B1 (en) | 2016-03-09 | 2017-03-07 | METHOD FOR MANUFACTURING A CERAMIC GLASS FORMULATION |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/064,777 US9974310B2 (en) | 2016-03-09 | 2016-03-09 | Ceramic additive formulation and method of making |
US15/064,777 | 2016-03-09 |
Publications (1)
Publication Number | Publication Date |
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WO2017155933A1 true WO2017155933A1 (en) | 2017-09-14 |
Family
ID=59787617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2017/021070 WO2017155933A1 (en) | 2016-03-09 | 2017-03-07 | Ceramic additive formulation and method of making |
Country Status (5)
Country | Link |
---|---|
US (2) | US9974310B2 (en) |
EP (1) | EP3426621A4 (en) |
CN (1) | CN109071353B (en) |
MX (1) | MX2018010783A (en) |
WO (1) | WO2017155933A1 (en) |
Cited By (2)
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CN111269029A (en) * | 2020-03-09 | 2020-06-12 | 广东四维新材料有限公司 | Pure silver glaze, high-temperature co-fired ceramic silverware and preparation methods of pure silver glaze and high-temperature co-fired ceramic silverware |
US10899657B1 (en) | 2016-03-09 | 2021-01-26 | Microban Products Company | Ceramic additive formulation and method of making |
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BRPI0807590B8 (en) * | 2007-02-20 | 2019-08-13 | Microban Products | antimicrobial ceramic enamel composition, enameled ceramic substrate, and methods for manufacturing an enameled ceramic substrate and antimicrobial ceramic enamel composition |
US9974310B2 (en) | 2016-03-09 | 2018-05-22 | Microban Products Company | Ceramic additive formulation and method of making |
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2016
- 2016-03-09 US US15/064,777 patent/US9974310B2/en active Active
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2017
- 2017-03-07 WO PCT/US2017/021070 patent/WO2017155933A1/en active Application Filing
- 2017-03-07 EP EP17763860.8A patent/EP3426621A4/en active Pending
- 2017-03-07 CN CN201780016016.3A patent/CN109071353B/en active Active
- 2017-03-07 MX MX2018010783A patent/MX2018010783A/en unknown
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- 2018-04-23 US US15/960,063 patent/US10299483B2/en active Active
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10899657B1 (en) | 2016-03-09 | 2021-01-26 | Microban Products Company | Ceramic additive formulation and method of making |
US11767256B1 (en) | 2016-03-09 | 2023-09-26 | Microban Products Company | Ceramic additive formulation and method of making |
CN111269029A (en) * | 2020-03-09 | 2020-06-12 | 广东四维新材料有限公司 | Pure silver glaze, high-temperature co-fired ceramic silverware and preparation methods of pure silver glaze and high-temperature co-fired ceramic silverware |
Also Published As
Publication number | Publication date |
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EP3426621A4 (en) | 2019-11-20 |
US9974310B2 (en) | 2018-05-22 |
CN109071353A (en) | 2018-12-21 |
US20170258092A1 (en) | 2017-09-14 |
BR112018068031A2 (en) | 2019-01-08 |
MX2018010783A (en) | 2018-11-29 |
US10299483B2 (en) | 2019-05-28 |
US20180235233A1 (en) | 2018-08-23 |
EP3426621A1 (en) | 2019-01-16 |
CN109071353B (en) | 2022-03-29 |
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