US20210269370A1 - Antimicrobial Glaze and Porcelain Enamel via Double Layer Glaze with High Zinc Content - Google Patents
Antimicrobial Glaze and Porcelain Enamel via Double Layer Glaze with High Zinc Content Download PDFInfo
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- US20210269370A1 US20210269370A1 US17/322,027 US202117322027A US2021269370A1 US 20210269370 A1 US20210269370 A1 US 20210269370A1 US 202117322027 A US202117322027 A US 202117322027A US 2021269370 A1 US2021269370 A1 US 2021269370A1
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- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 35
- 239000011701 zinc Substances 0.000 title description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 11
- 229910052725 zinc Inorganic materials 0.000 title description 11
- 239000000037 vitreous enamel Substances 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 10
- 230000007547 defect Effects 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 76
- 239000011787 zinc oxide Substances 0.000 abstract description 37
- 210000003298 dental enamel Anatomy 0.000 abstract description 7
- 239000004927 clay Substances 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
- 150000003379 silver compounds Chemical class 0.000 description 5
- 239000003570 air Substances 0.000 description 4
- 239000004599 antimicrobial Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 241001212789 Dynamis Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- 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
-
- 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
-
- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- 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 to antimicrobial sanitary ware, in particular, the ceramic glaze layer.
- the invention provides for a cost-effective and practical antimicrobial glaze system and glazing process.
- the oligodynamic effect is the term given to the ability of small amounts of heavy metals to exert a lethal effect on bacteria (from the Greek: oligos, small; dynamis, power).
- the effectiveness of heavy metals as antimicrobials is believed to be due to the high affinity of cellular proteins for metallic ions. Bacteria cells die due to the cumulative effects of ions within the cell, even if the concentration of ions in a solution is miniscule.
- Metals that generally show a strong oligodynamic effect are (in order of decreasing strength) Hg>Ag>Cu>Zn>Fe>Pb>Bi.
- silver and zinc have been used in materials for various applications and industries, such as materials for use in medical devices, food processing products, textiles, and sanitary ware.
- Oligodynamic elements other than silver and zinc either due to human toxicity or some incompatibility with the intended matrix material (e.g. changes in color), are rarely used as antimicrobial agents in material applications.
- silver and its salts exert a much stronger antimicrobial effect against common bacteria such as Staphylococcus Aureus and Escherichia coli .
- Zinc oxide generally shows much better efficacy than silver against various fungi.
- Another practical factor from a manufacturing standpoint is that silver is far more expensive than zinc, with a market price over 100 times greater per unit weight compared to zinc.
- U.S. Pat. Nos. 5,807,641 and 5,882,808 relate to antimicrobial sanitary ware produced by adding silver compounds to the ceramic glaze layer.
- the silver is added to the glaze slurry as a salt or oxide.
- the glaze slurry is applied to the ceramic body and fired at a temperature generally exceeding 1100° C.
- This approach can provide good antibacterial efficacy, but in practice, the level of silver required to obtain this effect results in an unacceptably large increase in the cost of the glaze. For example, a typical toilet and tank combination contains about 6.5 lbs of glaze.
- an antimicrobial silver compound Due to the relatively high vapor pressure of silver and its compounds at temperatures above 1200° C., at least 2 wt % of an antimicrobial silver compound is needed to impart strong antimicrobial efficacy to the fired sanitaryware body.
- the cost of antimicrobial silver compounds is roughly $100/1b, which at 2% loading results in an added cost of $13 per toilet and tank combo. This cost requires a price increase for antimicrobial sanitaryware that is well beyond what many consumers in the Americas and Europe are willing to pay for the feature.
- a large part of the silver in the glaze vaporizes and condenses on the walls of the kiln, which over time can build up to troublesome levels and result in manufacturing downtime, thereby further increasing the cost of manufacturing these pieces.
- Zinc oxide is already used as a flux material in some sanitaryware glaze systems, albeit at levels that are too low to yield any significant antimicrobial effect.
- Japanese Patent Application 10-227686 relates to an antimicrobial glaze formulation that contains 6-20 wt of zinc compounds measured as zinc oxide. The inventors state that at least 6 wt % of zinc compounds is necessary to obtain consistent antimicrobial efficacy.
- porcelain enamel is the general term applied to such glass coatings on metallic substrates.
- porcelain enamels are widely applied to steel and cast iron bodies in the manufacture of sinks, bathtubs, hot water heaters, cookware, and some appliances.
- a cost-effective and practical antimicrobial glaze/enamel system and glazing process can be achieved by the herein described glazing technology, employing at least two glaze layers.
- the antimicrobial glaze/enamel of the present invention is made of at least two layers: a base layer and a top layer.
- the base layer consists of typical glaze materials that are widely used in sanitary ware manufacture.
- the base layer glaze is sprayed directly onto the clay body surface.
- the top layer contains a high level of zinc oxide (ZnO).
- the level of ZnO in the top layer is between about 8.0 wt % to about 35.0 wt %, preferably about 10.0 wt % to about 25.0 wt %.
- the top layer thickness may be in the range between about 25 ⁇ m to about 250 ⁇ m, and preferably about 25 ⁇ m to about 150 ⁇ m in order to achieve good glaze quality.
- FIG. 1 is a chart comparing the antimicrobial efficacy of ceramic tile samples with thin top glaze layers containing 6.0, 10.0, and 15.0 weight percent zinc oxide relative to a ceramic control tile with no top layer.
- the top glaze layers of the samples compared in FIG. 1 are approximately 150 ⁇ m thick.
- FIG. 2 is a chart comparing the antimicrobial efficacy test results of ceramic tile samples that have top layers containing 10.0 weight percent zinc oxide at a thickness of 150 ⁇ m and 300 ⁇ m. The efficacy is reported relative to ceramic control tiles with no top layer glaze.
- the antimicrobial glaze/enamel of the present invention is made of at least two layers: a base layer and a top layer.
- the base layer consists of typical glaze materials that are widely used in sanitary ware manufacture.
- the base layer glaze is sprayed directly onto the clay body surface.
- the top layer contains a high level of zinc oxide (ZnO).
- the level of ZnO in the top layer is between about 8.0 wt % to about 35.0 wt %, preferably about 10.0 wt % to about 25.0 wt %.
- the top layer thickness may be in the range between about 25 ⁇ m to about 250 ⁇ m, and preferably about 25 to about 150 ⁇ m in order to achieve good glaze quality.
- a typical glaze formula is used as the first layer (base layer), and may be sprayed on the clay body surface directly.
- the thickness of the base glaze layer is preferably in the range of about 300 ⁇ m to about 600 ⁇ m. With about 0 wt % to about 8.0 wt % ZnO in the base layer, the glaze can be made free of pits and other surface irregularity defects.
- the base layer is then dried or fired. After firing a typical base glaze layer composition may be that shown in Table 2.
- a second, top glaze layer with a higher ZnO level than the base layer is sprayed on the top of the base layer.
- the thickness of the top glaze layer is maintained at 25 ⁇ m to 250 ⁇ m.
- the ZnO level in the top glaze layer glaze is between about 8.0 wt % and about 35.0 wt %.
- top glaze layer formula after firing is listed in Table 3.
- Table 3 An example of a top glaze layer formula after firing is listed in Table 3.
- the surface of the top glaze layer is smooth, uniform, and has a high gloss.
- the top layer thickness needs to be in the range of about 25 ⁇ m to about 250 vim, preferably about 100 pin to about 200 ⁇ m.
- the total ZnO content in the overall glaze is less than about 5.0 wt %.
- a glaze system that requires about 5.0% ZnO can be manufactured at about 1/50 th of the cost of a glaze with about 2.0 wt % of antimicrobial silver compound.
- the zinc-based glaze will give equal or better antimicrobial performance because the surface of the glaze in contact with bacteria can have a zinc content that is orders of magnitude higher than the silver content in commercially available antimicrobial chinaware.
- the antimicrobial glaze/enamel is made of at least two layers: a base layer and a top layer.
- the base glaze layer consists of typical or normal glaze which is widely used in sanitary ware, and preferably has low levels of ZnO; about 0-8.0 wt %.
- An example of a base glaze layer composition after firing is shown in Table 3.
- the base glaze layer is preferably between 300 ⁇ m and 1000 ⁇ m thick after firing.
- the base glaze layer is sprayed directly on the clay body surface.
- the top glaze layer material contains high ZnO levels in the range of between about 6.0 wt % and about 35.0 wt %, preferably about 10.0 wt % to about 25.0 wt %.
- ingredients in the top layer may include, but are not limited to, Al 2 O 3 , SiO 2 , and other oxides, such as, but not limited to, K 2 O, Na 2 O, Li 2 O, MgO, CaO, B 2 O 3 , BaO, MoO, SnO, and SrO
- the top layer's thickness needs to be controlled in the range of between about 25 ⁇ m to about 250 ⁇ m, and preferably from about 25 ⁇ m to about 150 ⁇ m in order to achieve good glaze quality.
- a top glaze layer is sprayed and fired to a thickness of between about 25 ⁇ m and 250 ⁇ m in which the top 10 ⁇ l of the top glaze layer have between 8.0 wt % and 15.0 wt % ZnO, but due to diffusion between the top glaze layer and the bottom glaze layer the overall wt % ZnO in the top layer is less than 8.0 wt %.
- oligodynamic elements or compounds other than zinc are added to increase the antimicrobial efficacy of the glaze or enamel, including but not limited to Hg, Ag, Cu, Fe, Pb, Bi, and/or a rare earth element or elements.
- Example 1 A series of ceramic tiles were prepared with base layer compositions according to Table 1 and top layer compositions containing 6.0 wt %, 10.0 wt %, 15.0 wt %, and 25.0 wt ZnO.
- the base layer was sprayed to give a post-fire thickness of approximately 450 ⁇ m.
- the top layer was sprayed on to the base layer to a post-fire thickness of approximately 150 ⁇ m.
- the tiles were then fired in air at a temperature of 1215° C. for a soak time of 45 minutes. Upon cooling and removal from the furnace, the samples were subjected to antimicrobial efficacy testing in accordance with the procedures outlined in the Japanese Standard JIS Z2801.
- a ceramic tile with the identical base layer and no top layer was prepared at the same time and used as the control tile.
- the results of these tests are shown in Table 4 and FIG. 1 .
- the results indicate that the sample with 6 wt ZnO in the top layer has little of no efficacy against Staph aureus relative to the control tile with no top layer glaze.
- the sample with top layer glaze containing 10 wt % ZnO exhibited significantly improved antimicrobial efficacy compared to the 6.0 wt ZnO glaze, with a roughly Log 2.0 reduction relative to the control tile.
- the sample with top layer glaze containing 15.0 wt ZnO exhibited a Log 3.8 reduction relative to the control tile.
- Example 2 Additional sample tiles were prepared according to the procedure given in Example 1, with the exception that the post-fire thickness of the top layer was varied from 150 ⁇ m to 300 ⁇ m. These samples were then subjected to antimicrobial efficacy testing in accordance with the procedures outlined in the Japanese Standard JIS Z2801.
- FIG. 2 shows the difference in antimicrobial efficacy against Staph aureus of samples with a 10 wt ZnO top glaze layer at different thickness. The efficacy is improved when the thickness is increased from 150 ⁇ m to 300 ⁇ m.
Abstract
Description
- All documents cited or referenced herein (“herein cited documents”), and all documents cited or referenced in herein cited documents, together with any manufacturer's instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be employed in the practice of the invention.
- The present invention relates to antimicrobial sanitary ware, in particular, the ceramic glaze layer. The invention provides for a cost-effective and practical antimicrobial glaze system and glazing process.
- The oligodynamic effect is the term given to the ability of small amounts of heavy metals to exert a lethal effect on bacteria (from the Greek: oligos, small; dynamis, power). The effectiveness of heavy metals as antimicrobials is believed to be due to the high affinity of cellular proteins for metallic ions. Bacteria cells die due to the cumulative effects of ions within the cell, even if the concentration of ions in a solution is miniscule. Metals that generally show a strong oligodynamic effect are (in order of decreasing strength) Hg>Ag>Cu>Zn>Fe>Pb>Bi. Among these metals, silver and zinc have been used in materials for various applications and industries, such as materials for use in medical devices, food processing products, textiles, and sanitary ware. Oligodynamic elements other than silver and zinc, either due to human toxicity or some incompatibility with the intended matrix material (e.g. changes in color), are rarely used as antimicrobial agents in material applications, Compared to zinc, silver and its salts exert a much stronger antimicrobial effect against common bacteria such as Staphylococcus Aureus and Escherichia coli. Zinc oxide, however, generally shows much better efficacy than silver against various fungi. Another practical factor from a manufacturing standpoint is that silver is far more expensive than zinc, with a market price over 100 times greater per unit weight compared to zinc.
- U.S. Pat. Nos. 5,807,641 and 5,882,808 relate to antimicrobial sanitary ware produced by adding silver compounds to the ceramic glaze layer. The silver is added to the glaze slurry as a salt or oxide. The glaze slurry is applied to the ceramic body and fired at a temperature generally exceeding 1100° C. This approach can provide good antibacterial efficacy, but in practice, the level of silver required to obtain this effect results in an unacceptably large increase in the cost of the glaze. For example, a typical toilet and tank combination contains about 6.5 lbs of glaze. Due to the relatively high vapor pressure of silver and its compounds at temperatures above 1200° C., at least 2 wt % of an antimicrobial silver compound is needed to impart strong antimicrobial efficacy to the fired sanitaryware body. The cost of antimicrobial silver compounds is roughly $100/1b, which at 2% loading results in an added cost of $13 per toilet and tank combo. This cost requires a price increase for antimicrobial sanitaryware that is well beyond what many consumers in the Americas and Europe are willing to pay for the feature. Additionally, a large part of the silver in the glaze vaporizes and condenses on the walls of the kiln, which over time can build up to troublesome levels and result in manufacturing downtime, thereby further increasing the cost of manufacturing these pieces. Thus, there is a need for a more cost effective means than using silver for producing antimicrobial sanitaryware for these markets.
- Of the other metals that have strong oligodynamic effects, zinc is most suited for use in sanitaryware applications. Mercury, lead, and bismuth present toxicity and/or environmental issues, whereas iron and copper compounds would eliminate the possibility of producing white pieces. Zinc oxide is already used as a flux material in some sanitaryware glaze systems, albeit at levels that are too low to yield any significant antimicrobial effect. For example, Japanese Patent Application 10-227686 relates to an antimicrobial glaze formulation that contains 6-20 wt of zinc compounds measured as zinc oxide. The inventors state that at least 6 wt % of zinc compounds is necessary to obtain consistent antimicrobial efficacy. Using such a large amount of zinc in a sanitaryware glaze system, although it might provide antimicrobial properties at a cost much lower than that obtainable through the use of silver compounds, presents manufacturing issues that severely limit the practicality of this approach. Such a sanitary ware glaze system having more than 6 wt % zinc oxide, will begin to suffer severe pitting and surface irregularity defects. These defects become even more severe if the circulation of air in the kiln is not sufficient.
- Similar needs and issues exist for antimicrobial porcelain enamel systems. Whereas glazes are glass coatings applied to ceramic substrates (bodies), porcelain enamel is the general term applied to such glass coatings on metallic substrates. For example, porcelain enamels are widely applied to steel and cast iron bodies in the manufacture of sinks, bathtubs, hot water heaters, cookware, and some appliances.
- Therefore, there remains a need for a cost-effective and practical (from a manufacturing viewpoint) approach to providing sanitary ware with antimicrobial properties. The invention described herein provides a solution to this problem. A cost-effective and practical antimicrobial glaze/enamel system and glazing process can be achieved by the herein described glazing technology, employing at least two glaze layers.
- The antimicrobial glaze/enamel of the present invention is made of at least two layers: a base layer and a top layer. The base layer consists of typical glaze materials that are widely used in sanitary ware manufacture. The base layer glaze is sprayed directly onto the clay body surface. The top layer contains a high level of zinc oxide (ZnO). The level of ZnO in the top layer is between about 8.0 wt % to about 35.0 wt %, preferably about 10.0 wt % to about 25.0 wt %. The top layer thickness may be in the range between about 25 μm to about 250 μm, and preferably about 25 μm to about 150 μm in order to achieve good glaze quality.
- These and other embodiments are disclosed or are obvious from and encompassed by, the following Detailed Description.
- These and other objects and features are illustrated and described in the following specification to be read in conjunction with the sheets of drawings in which:
-
FIG. 1 is a chart comparing the antimicrobial efficacy of ceramic tile samples with thin top glaze layers containing 6.0, 10.0, and 15.0 weight percent zinc oxide relative to a ceramic control tile with no top layer. The top glaze layers of the samples compared inFIG. 1 are approximately 150 μm thick. -
FIG. 2 is a chart comparing the antimicrobial efficacy test results of ceramic tile samples that have top layers containing 10.0 weight percent zinc oxide at a thickness of 150 μm and 300 μm. The efficacy is reported relative to ceramic control tiles with no top layer glaze. - The antimicrobial glaze/enamel of the present invention is made of at least two layers: a base layer and a top layer. The base layer consists of typical glaze materials that are widely used in sanitary ware manufacture. The base layer glaze is sprayed directly onto the clay body surface. The top layer contains a high level of zinc oxide (ZnO). The level of ZnO in the top layer is between about 8.0 wt % to about 35.0 wt %, preferably about 10.0 wt % to about 25.0 wt %. The top layer thickness may be in the range between about 25 μm to about 250 μm, and preferably about 25 to about 150 μm in order to achieve good glaze quality.
- A typical glaze formula, an example of which is listed in Table 1, is used as the first layer (base layer), and may be sprayed on the clay body surface directly. The thickness of the base glaze layer is preferably in the range of about 300 μm to about 600 μm. With about 0 wt % to about 8.0 wt % ZnO in the base layer, the glaze can be made free of pits and other surface irregularity defects. The base layer is then dried or fired. After firing a typical base glaze layer composition may be that shown in Table 2.
-
TABLE 1 Typical glaze formula used in base layer. Raw Materials Formula (wt %) Feldspar 32.0-42.0 Whiting 8.0-18.0 ZnO 0-8.0 Talc 0-3.0 Frit 0-10.0 Silica 13.0-23.0 Opacifier 7.0-15.0 Clay 0-12.0 Other <10.0 -
TABLE 2 Typical composition of base glaze after firing. Chemical Ingredients Formula (wt %) SiO2 40-70 Al2O3 0-15 ZrO2 0-15 ZnO 0-8 CaO 0-20 TiO2 0-20 B2O3 0-20 Others (e.g., K2O, Na2O, MgO, Li2O) 0-20 - After the base layer is dried or fired, preferably dried in air at a temperature below about 200° C., a second, top glaze layer with a higher ZnO level than the base layer is sprayed on the top of the base layer. To avoid the formation of surface defects, the thickness of the top glaze layer is maintained at 25 μm to 250 μm. To achieve sufficient antimicrobial efficacy, the ZnO level in the top glaze layer glaze is between about 8.0 wt % and about 35.0 wt %.
- An example of a top glaze layer formula after firing is listed in Table 3. In order to reduce the possibility of the top glaze layer forming pits and other surface defects, that layer is kept thin and more exposed to air circulation. The surface of the top glaze layer is smooth, uniform, and has a high gloss. For optimal efficacy, surface appearance, and gloss, the top layer thickness needs to be in the range of about 25 μm to about 250 vim, preferably about 100 pin to about 200 μm. After finishing spraying of the top glaze layer, the parts can be sent to kiln for firing at normal firing temperature, typically around 1200° C.
-
TABLE 3 Top layer glaze composition (after firing) Raw Materials Formula (wt %) Al2O3 8 SiO2 61 ZnO 25 Other Flux 6 - Because only a thin layer contains high levels of ZnO, the total ZnO content in the overall glaze is less than about 5.0 wt %. As the cost of ZnO is about $1/lb, a glaze system that requires about 5.0% ZnO can be manufactured at about 1/50th of the cost of a glaze with about 2.0 wt % of antimicrobial silver compound. The zinc-based glaze will give equal or better antimicrobial performance because the surface of the glaze in contact with bacteria can have a zinc content that is orders of magnitude higher than the silver content in commercially available antimicrobial chinaware.
- To summarize the present invention, the antimicrobial glaze/enamel is made of at least two layers: a base layer and a top layer. The base glaze layer consists of typical or normal glaze which is widely used in sanitary ware, and preferably has low levels of ZnO; about 0-8.0 wt %. An example of a base glaze layer composition after firing is shown in Table 3. The base glaze layer is preferably between 300 μm and 1000 μm thick after firing.
- The base glaze layer is sprayed directly on the clay body surface. The top glaze layer material contains high ZnO levels in the range of between about 6.0 wt % and about 35.0 wt %, preferably about 10.0 wt % to about 25.0 wt %. Other ingredients in the top layer may include, but are not limited to, Al2O3, SiO2, and other oxides, such as, but not limited to, K2O, Na2O, Li2O, MgO, CaO, B2O3, BaO, MoO, SnO, and SrO The top layer's thickness needs to be controlled in the range of between about 25 μm to about 250 μm, and preferably from about 25 μm to about 150 μm in order to achieve good glaze quality.
- In another embodiment, a top glaze layer is sprayed and fired to a thickness of between about 25 μm and 250 μm in which the top 10 μl of the top glaze layer have between 8.0 wt % and 15.0 wt % ZnO, but due to diffusion between the top glaze layer and the bottom glaze layer the overall wt % ZnO in the top layer is less than 8.0 wt %.
- In another embodiment, oligodynamic elements or compounds other than zinc are added to increase the antimicrobial efficacy of the glaze or enamel, including but not limited to Hg, Ag, Cu, Fe, Pb, Bi, and/or a rare earth element or elements.
- The invention will now be further described by way of the following non-limiting examples.
- Example 1. A series of ceramic tiles were prepared with base layer compositions according to Table 1 and top layer compositions containing 6.0 wt %, 10.0 wt %, 15.0 wt %, and 25.0 wt ZnO. The base layer was sprayed to give a post-fire thickness of approximately 450 μm. After allowing approximately 5 minutes for the base layer to dry in ambient air, the top layer was sprayed on to the base layer to a post-fire thickness of approximately 150 μm. The tiles were then fired in air at a temperature of 1215° C. for a soak time of 45 minutes. Upon cooling and removal from the furnace, the samples were subjected to antimicrobial efficacy testing in accordance with the procedures outlined in the Japanese Standard JIS Z2801. A ceramic tile with the identical base layer and no top layer was prepared at the same time and used as the control tile. The results of these tests are shown in Table 4 and
FIG. 1 . The results indicate that the sample with 6 wt ZnO in the top layer has little of no efficacy against Staph aureus relative to the control tile with no top layer glaze. The sample with top layer glaze containing 10 wt % ZnO exhibited significantly improved antimicrobial efficacy compared to the 6.0 wt ZnO glaze, with a roughly Log 2.0 reduction relative to the control tile. The sample with top layer glaze containing 15.0 wt ZnO exhibited a Log 3.8 reduction relative to the control tile. This corresponds to a reduction in Staph aureus count of 99.98% over the 24 hour test period. Additionally, the antimicrobial efficacy of the sample having 25.0 wt ZnO in the top layer (not shown) exhibited a >Log 3.0 reduction against Staph aureus. However, the cosmetic quality of the glaze began to suffer from surface defects due to the high ZnO content. - Example 2. Additional sample tiles were prepared according to the procedure given in Example 1, with the exception that the post-fire thickness of the top layer was varied from 150 μm to 300 μm. These samples were then subjected to antimicrobial efficacy testing in accordance with the procedures outlined in the Japanese Standard JIS Z2801.
FIG. 2 shows the difference in antimicrobial efficacy against Staph aureus of samples with a 10 wt ZnO top glaze layer at different thickness. The efficacy is improved when the thickness is increased from 150 μm to 300 μm. -
TABLE 4 Bacteria counts (in colony forming units/cm2) during JIS Z2801 testing of samples described in Example 1. Contact time against Staph Aureus ZnO level in top glaze layer 0 hours 24 hours Control Tile (0% ZnO) 6.5 × 103 8.3 × 103 6.0 wt % ZnO, 150 μm 6.5 × 103 4.0 × 103 10.0 wt % ZnO, 150 μm 6.5 × 103 8.3 × 101 15.0 wt % ZnO, 150 μm 6.5 × 103 1.1 × 100 - Having thus described in detail the preferred embodiments of the present invention, it is to be understood that the invention defined by the above paragraphs is not to be limited to the particular details set forth in the above description. Many apparent variations thereof are possible without departing from the spirit or scope of the present invention.
- In this application, terms such as “comprises”, “comprised”, “comprising” and the like, can have the meaning attributed to it in U.S. patent law; e.g., they can mean “includes”, “included”, “including”, and the like; and terms such as “consisting essentially of” and “consists essentially of,” have the meaning ascribed to them in U.S. patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention.
- Citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention.
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US17/322,027 US20210269370A1 (en) | 2005-05-09 | 2021-05-17 | Antimicrobial Glaze and Porcelain Enamel via Double Layer Glaze with High Zinc Content |
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US16/588,677 US11066338B2 (en) | 2005-05-09 | 2019-09-30 | Antimicrobial glaze and porcelain enamel via double layer glaze with high zinc content |
US17/322,027 US20210269370A1 (en) | 2005-05-09 | 2021-05-17 | Antimicrobial Glaze and Porcelain Enamel via Double Layer Glaze with High Zinc Content |
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EP2118038B1 (en) | 2007-02-20 | 2017-06-14 | Microban Products Company | Ceramic glaze having antimicrobial property |
US10159255B2 (en) * | 2008-02-16 | 2018-12-25 | Microban Products Company | Biocidal glazing composition, method, and article |
ES2406354B1 (en) * | 2011-09-20 | 2014-04-09 | Consejo Superior De Investigaciones Científicas (Csic) - | COMBINATION AND PROCEDURE FOR OBTAINING BACTERICIDE CERAMIC Enamels FOR CERAMIC PRODUCTS |
ITRM20120362A1 (en) * | 2012-07-25 | 2014-01-26 | Maioliche S N C Di Ermellini Gr Azia U E Magn U | COMPOSITION OF ENAMEL FOR DECORATED PORCELAIN AND METHOD FOR THE CONSTRUCTION OF A DECORATED PORCELAIN MANUFACTURE |
CN103274764B (en) * | 2013-05-08 | 2014-06-04 | 祥丰(浙江)金属制品有限公司 | High and low-temperature resistant porcelain glaze for enamel |
CN103880476B (en) * | 2014-04-08 | 2015-05-20 | 武汉工程大学 | Cold ceramic glaze with sterilization and antibacterial functions and preparation method thereof |
DE102015101609B3 (en) * | 2015-02-04 | 2016-06-30 | Duravit Aktiengesellschaft | Ceramic article and method of making such |
US10064273B2 (en) | 2015-10-20 | 2018-08-28 | MR Label Company | Antimicrobial copper sheet overlays and related methods for making and using |
CN105565670B (en) * | 2016-01-12 | 2018-08-14 | 曹文 | A kind of ceramics or enamel sterilization glazing type material and preparation method thereof and its application |
US10899657B1 (en) | 2016-03-09 | 2021-01-26 | Microban Products Company | Ceramic additive formulation and method of making |
US9974310B2 (en) | 2016-03-09 | 2018-05-22 | Microban Products Company | Ceramic additive formulation and method of making |
US11844351B2 (en) | 2016-10-31 | 2023-12-19 | Microban Products Company | Method of treating a glazed ceramic article |
CN107824130A (en) * | 2017-11-08 | 2018-03-23 | 常熟市永达化工设备厂 | Glass-lined reactor |
CN108840720B (en) * | 2018-08-01 | 2022-05-10 | 广东金意陶陶瓷集团有限公司 | Self-cleaning ceramic tile and preparation method thereof |
CN111847877B (en) * | 2020-08-05 | 2022-07-01 | 佛山市华力达材料科技有限公司 | Metal dry particle glaze, metal luster ceramic tile and preparation method thereof |
JP2022184067A (en) * | 2021-05-31 | 2022-12-13 | Toto株式会社 | sanitary ware |
CN113248146B (en) * | 2021-06-03 | 2021-09-24 | 佛山欧神诺陶瓷有限公司 | Composite process antibacterial ceramic tile and preparation method thereof |
CN113429221B (en) * | 2021-07-28 | 2022-08-19 | 广东中印陶瓷科技有限公司 | Antibacterial wear-resistant glaze and preparation method thereof |
CN113860854A (en) * | 2021-09-27 | 2021-12-31 | 蒙娜丽莎集团股份有限公司 | Ceramic plate with stable and durable antibacterial performance and preparation method thereof |
CN114315136B (en) * | 2021-12-02 | 2024-01-09 | 江苏高淳陶瓷股份有限公司 | Low-cost antibacterial ceramic glaze and preparation method thereof |
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JP2000044368A (en) * | 1998-07-27 | 2000-02-15 | Toto Ltd | Pottery having antimicrobial property |
JP3702703B2 (en) * | 1999-04-20 | 2005-10-05 | 東陶機器株式会社 | Manufacturing method of sanitary ware |
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