RU2207992C2 - Composite of glassy silicate enamel - Google Patents

Composite of glassy silicate enamel Download PDF

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RU2207992C2
RU2207992C2 RU2001124710A RU2001124710A RU2207992C2 RU 2207992 C2 RU2207992 C2 RU 2207992C2 RU 2001124710 A RU2001124710 A RU 2001124710A RU 2001124710 A RU2001124710 A RU 2001124710A RU 2207992 C2 RU2207992 C2 RU 2207992C2
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oxide
composite
enamel
silver
titanium
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RU2001124710A
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RU2001124710A (en
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В.М. Соболев
М.Ю. Смирнов
С.В. Цыганков
Н.А. Козина
В.В. Малахова
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Открытое акционерное общество "Кировский завод"
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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
    • C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16—Halogen containing crystalline phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
    • 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
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • 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
    • C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
    • C03C2207/04—Compositions specially applicable for the manufacture of vitreous enamels for steel
    • 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
    • C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
    • C03C2207/06—Compositions specially applicable for the manufacture of vitreous enamels for cast iron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/04—Particles; Flakes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

FIELD: glass industry. SUBSTANCE: invention relates to composites of glassy silicate enamels used for coating cast iron and steel sanitary-technical articles, such as bathes, shower trays, washing machines, low-ground bowls and so on. The composition comprises the following components, wt. -%: silicon oxide, 15.0-35.0; potassium oxide, 1.5-7.0; sodium oxide, 11.0-18.0; boron oxide, 19.0-35.0; magnesium oxide, 0.5-1.3; titanium oxide, 4.0-18.0; aluminium oxide, 7.5-21.0; phosphorus oxide, 1.0-10.0; silver oxide, 0.01-0.1; fluorine, 1.2-6.5. The composite comprises titanium dioxide as anatase. The presence of silver ions inhibits microorganisms growth being in the most degree for Bacillus subtilis and Staphylococcus and in the less degree for Escherichia coli. The composite provides the disinfection effect. Enamel coating exhibits uniform bright white-snow color. EFFECT: improved quality and properties of composite. 2 cl, 1 tbl

Description

Изобретение относится к составам стекловидных силикатных эмалей для покрытия чугунных и стальных санитарно-технических изделий, таких как ванны купальные, душевые поддоны, мойки, напольные чаши и т.д. The invention relates to compositions of vitreous silicate enamels for coating cast iron and steel sanitary products, such as bathtubs, shower trays, sinks, floor bowls, etc.

Известен состав стекловидной силикатной эмали для покрытия санитарно-технических изделий, содержащий следующие компоненты, мас.%: оксид кремния 18,8-26,5, оксид бора 5,4-7,5, оксид натрия 14,2-17,0, оксид титана 7,3-10, оксид алюминия 3,5-4,8, оксид фосфора 0,1-5,0, оксид циркония 19,7-22,8, оксид бария 7,3-10,0, оксид кальция 3,0-3,6, фтор 0,3-4,0, оксид меди 0,4-4,0 (см. авторское свидетельство СССР 607800, 25.04.1978). A known composition of vitreous silicate enamel for coating sanitary products, containing the following components, wt.%: Silicon oxide 18.8-26.5, boron oxide 5.4-7.5, sodium oxide 14.2-17.0, titanium oxide 7.3-10, aluminum oxide 3.5-4.8, phosphorus oxide 0.1-5.0, zirconium oxide 19.7-22.8, barium oxide 7.3-10.0, calcium oxide 3.0-3.6, fluorine 0.3-4.0, copper oxide 0.4-4.0 (see USSR copyright certificate 607800, 04.25.1978).

Наиболее близким составом стекловидной силикатной эмали для покрытия санитарно-технических изделий является состав, содержащий следующие компоненты, мас. %: оксид кремния 19-23, оксид калия 1,3-4,5, оксид бора 28-35, оксид натрия 13,8-17,2, оксид магния 0,1-0,4, оксид титана 4,6-5,0, оксид алюминия 19-24, оксид молибдена 0,08-0,12 (см. авторское свидетельство СССР 554225, 06.07.1977). The closest composition of glassy silicate enamel for coating sanitary products is a composition containing the following components, wt. %: silicon oxide 19-23, potassium oxide 1.3-4.5, boron oxide 28-35, sodium oxide 13.8-17.2, magnesium oxide 0.1-0.4, titanium oxide 4.6- 5.0, aluminum oxide 19-24, molybdenum oxide 0.08-0.12 (see USSR copyright certificate 554225, 07/06/1977).

К недостаткам наиболее близкого состава можно отнести низкие антибактериологические свойства эмалевого покрытия, а также низкий коэффициент диффузного отражения, что придает белому цвету покрытия грязный оттенок. The disadvantages of the closest composition include the low antibacterial properties of the enamel coating, as well as the low coefficient of diffuse reflection, which gives the white color of the coating a dirty shade.

Задачей изобретения является устранение вышеперечисленных недостатков. The objective of the invention is to remedy the above disadvantages.

Поставленная задача решается тем, что состав стекловидной силикатной эмали для покрытия санитарно-технических изделий, содержащий оксид кремния, оксид калия, оксид натрия, оксид бора, оксид магния, оксид титана и оксид алюминия, дополнительно содержит оксид фосфора, оксид серебра и фтор при следующем соотношении компонентов, мас.%:
Оксид кремния - 15,0-35,0
Оксид калия - 1,5-7,0
Оксид натрия - 11,0-18,0
Оксид бора - 19,0-35,0
Оксид магния - 0,5-1,3
Оксид титана - 4,0-18,0
Оксид алюминия - 7,5-21,0
Оксид фосфора - 1,0-10,0
Оксид серебра - 0,01-0,1
Фтор - 1,2-6,5
Поставленная задача также решается тем, что состав содержит двуокись титана в виде анатаза.The problem is solved in that the composition of the vitreous silicate enamel for coating sanitary products, containing silicon oxide, potassium oxide, sodium oxide, boron oxide, magnesium oxide, titanium oxide and aluminum oxide, additionally contains phosphorus oxide, silver oxide and fluorine in the following the ratio of components, wt.%:
Silica - 15.0-35.0
Potassium oxide - 1.5-7.0
Sodium oxide - 11.0-18.0
Boron oxide - 19.0-35.0
Magnesium Oxide - 0.5-1.3
Titanium Oxide - 4.0-18.0
Alumina - 7.5-21.0
Phosphorus Oxide - 1.0-10.0
Silver oxide - 0.01-0.1
Fluoride - 1.2-6.5
The problem is also solved in that the composition contains titanium dioxide in the form of anatase.

Сущность изобретения состоит в следующем. The invention consists in the following.

Компоненты в эмали и их количественные соотношения подобраны таким образом, чтобы получилась бездефектная, долговечная эмаль, обладающая длительным бактериостатическим эффектом, ярким белым цветом и блеском. Для этого также из состава эмали исключается оксид молибдена, который присутствует в прототипе изобретения. The components in enamel and their quantitative ratios are selected in such a way as to obtain a defect-free, durable enamel with a long bacteriostatic effect, bright white color and gloss. For this, molybdenum oxide, which is present in the prototype of the invention, is also excluded from the enamel.

Дополнительное введение в эмаль оксида серебра в заявленных количествах придает эмали антибактерицидные свойства. Количество оксида серебра выбрано из условия равномерного его распределения как внутри эмали, так и на ее поверхности. An additional introduction to the enamel of silver oxide in the declared amounts gives the enamel antibacterial properties. The amount of silver oxide is selected from the condition of its uniform distribution both inside the enamel and on its surface.

Дополнительное введение оксида фосфора в заявленных количествах предотвращает переход анатаза в рутил, что обеспечивает получение эмали с высоким коэффициентом диффузного отражения (т.е. белизны). The additional introduction of phosphorus oxide in the declared amounts prevents the transfer of anatase to rutile, which provides enamel with a high diffuse reflection coefficient (i.e. whiteness).

Введение фтора позволяет наносить более тонкий слой эмали. The introduction of fluorine allows you to apply a thinner layer of enamel.

Изобретение может быть проиллюстрировано следующим примером. The invention can be illustrated by the following example.

Для получения шихты в качестве сырьевых материалов использовали кварцевый песок, полевой шпат, буру, соду кальцинированную, плавиковый шпат. Селитру калиевую и натриевую, анатаз, криолит, триполифосфат и азотнокислое серебро. To obtain the mixture, quartz sand, feldspar, borax, soda ash, and fluorspar were used as raw materials. Potassium and sodium nitrate, anatase, cryolite, tripolyphosphate and silver nitrate.

Компоненты шихты тщательно смешивали, засыпали во вращающуюся газовую плавильную печь или электрическую печь, расплавляли при температуре около 1300oС в течение 2 часов с последующей грануляцией в воде. Полученную фритту далее размалывали в барабанах.The components of the mixture were thoroughly mixed, poured into a rotary gas melting furnace or an electric furnace, melted at a temperature of about 1300 o C for 2 hours, followed by granulation in water. The resulting frit was further milled in drums.

Эмаль наносилась на санитарно-технические изделия и закреплялась обжигом. Enamel was applied to sanitary products and fixed by firing.

В таблице приведен состав полученной эмали. The table shows the composition of the obtained enamel.

Нанесенную эмаль исследовали под микроскопом. Дефекты в виде пузырей не обнаружены. The applied enamel was examined under a microscope. Defects in the form of bubbles were not detected.

Изделия, покрытые данными составами, имеют равномерную блестящую белоснежную окраску. Коэффициент диффузного отражения для составов 1 и 2 составляет 83%, а для состава 3 - 87%. Products coated with these compositions have a uniform brilliant snow-white color. The diffuse reflection coefficient for compositions 1 and 2 is 83%, and for composition 3 - 87%.

Присутствие ионов серебра подавляет рост микроорганизмов, в наибольшей степени Bacillus Subtilius и Staphylococcus, в меньшей степени - Escherichia coli. Создается эффект дезинфекции. The presence of silver ions inhibits the growth of microorganisms, to the greatest extent Bacillus Subtilius and Staphylococcus, to a lesser extent Escherichia coli. The effect of disinfection is created.

Вытяжка из эмали с добавкой ионов серебра не обладает выраженной токсичностью, кожно-раздражающим действием и способностью проникать через неповрежденную кожу, а также кумулятивным и сенсибилизирующим эффектами. An extract from enamel with the addition of silver ions does not have a pronounced toxicity, skin irritating effect and the ability to penetrate intact skin, as well as cumulative and sensitizing effects.

Claims (1)

1. Состав стекловидной силикатной эмали для покрытия санитарно-технических изделий, содержащий оксид кремния, оксид калия, оксид натрия, оксид бора, оксид магния, оксид титана и оксид алюминия, отличающийся тем, что он дополнительно содержит оксид фосфора, оксид серебра и фтор при следующем соотношении компонентов, мас.%:
Оксид кремния - 15,0-35,0
Оксид калия - 1,5-7,0
Оксид натрия - 11,0-18,0
Оксид бора - 19,0-35,0
Оксид магния - 0,5-1,3
Оксид титана - 4,0-18,0
Оксид алюминия - 7,5-21,0
Оксид фосфора - 1,0-10,0
Оксид серебра - 0,01-0,1
Фтор - 1,2-6,5
2. Состав по п.1, отличающийся тем, что содержит двуокись титана в виде анатаза.1. The composition of vitreous silicate enamel for coating sanitary products containing silicon oxide, potassium oxide, sodium oxide, boron oxide, magnesium oxide, titanium oxide and aluminum oxide, characterized in that it further comprises phosphorus oxide, silver oxide and fluorine when the following ratio of components, wt.%:
Silica - 15.0-35.0
Potassium oxide - 1.5-7.0
Sodium oxide - 11.0-18.0
Boron oxide - 19.0-35.0
Magnesium Oxide - 0.5-1.3
Titanium Oxide - 4.0-18.0
Alumina - 7.5-21.0
Phosphorus Oxide - 1.0-10.0
Silver oxide - 0.01-0.1
Fluoride - 1.2-6.5
2. The composition according to claim 1, characterized in that it contains titanium dioxide in the form of anatase.
RU2001124710A 2001-09-07 2001-09-07 Composite of glassy silicate enamel RU2207992C2 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2662339A1 (en) * 2012-05-10 2013-11-13 LG Electronics, Inc. Enamel composition, preparation method thereof, and cooking appliance including the same
CN103435263A (en) * 2013-08-30 2013-12-11 湖南立发釉彩科技有限公司 Primary enameling glaze and preparation method thereof
WO2017016952A1 (en) * 2015-07-24 2017-02-02 Onderzoekscentrum Voor Aanwending Van Staal N.V. Method for providing a co- and ni-free vitreous enamelled metal coated steel substrate and a primer composition therefor

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2662339A1 (en) * 2012-05-10 2013-11-13 LG Electronics, Inc. Enamel composition, preparation method thereof, and cooking appliance including the same
US9296642B2 (en) 2012-05-10 2016-03-29 Lg Electronics Inc. Enamel composition, preparation method thereof, and cooking appliance including the same
CN103435263A (en) * 2013-08-30 2013-12-11 湖南立发釉彩科技有限公司 Primary enameling glaze and preparation method thereof
WO2017016952A1 (en) * 2015-07-24 2017-02-02 Onderzoekscentrum Voor Aanwending Van Staal N.V. Method for providing a co- and ni-free vitreous enamelled metal coated steel substrate and a primer composition therefor
EA035826B1 (en) * 2015-07-24 2020-08-17 Ондерзуксентрум Вор Анвендинг Ван Стал Н.В. METHOD FOR PROVIDING A Co- AND Ni-FREE VITREOUS ENAMELLED METAL COATED STEEL SUBSTRATE AND PRIMER COMPOSITION THEREFOR

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