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WO2013032368A2 - High-temperature heat-shielding coating - Google Patents

High-temperature heat-shielding coating Download PDF

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Publication number
WO2013032368A2
WO2013032368A2 PCT/RU2012/000714 RU2012000714W WO2013032368A2 WO 2013032368 A2 WO2013032368 A2 WO 2013032368A2 RU 2012000714 W RU2012000714 W RU 2012000714W WO 2013032368 A2 WO2013032368 A2 WO 2013032368A2
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WO
WIPO (PCT)
Prior art keywords
microspheres
diameter
wall thickness
binder
heat
Prior art date
Application number
PCT/RU2012/000714
Other languages
French (fr)
Russian (ru)
Other versions
WO2013032368A3 (en
Inventor
Юрий Александрович ГРИГОРЬЕВ
Original Assignee
Общество С Ограниченной Ответственностью "Овк-Руссия"
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Publication of WO2013032368A2 publication Critical patent/WO2013032368A2/en
Publication of WO2013032368A3 publication Critical patent/WO2013032368A3/en

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    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Definitions

  • the invention relates to the production of heat-insulating coatings intended for structures and equipment operated in conditions of high temperatures and aggressive environments, and can be used in construction, engineering, chemical industry, transport, aviation, space and other industries.
  • Heat-resistant coatings are known containing hollow ceramic or glass microspheres, binders in the form of dispersions, emulsions of organosoluble organosilicon resins, acrylic copolymers, polyurethanes, which are used as heat-insulating material for the outer and inner surfaces of building envelopes and structures, pipelines and various technological equipment, for example, paint-coating according to patent RU N ° 2310670 C9, 20.11.2007.
  • this known coating is not applicable for structures and equipment operated under conditions of high temperatures and vibration loads and aggressive environments, due to the low resistance to their effects (operating temperature of the coating does not exceed 200 ° C).
  • the closest in technical essence and the achieved result is a heat-shielding coating containing vacuum (hollow) ceramic or corundum microspheres with a particle diameter of 3 to 100 microns and a bulk density of 300-400 kg / m 3 as a filler, organosilicon, polyether epoxy binder or acrylic dispersions and, as additives, the reflector is aluminum powder and pigment, in the following ratio of components, in wt.%: microspheres 55-70, binder 30-35, reflector - aluminum powder 2.0-5.0, pigment 0.1-0.6 according to patent RU -Nb 2245350 C1, 01/27/2005.
  • the heat-protective coating obtained by applying the known composition is uniform in composition and has a sufficiently high adhesion to the surface to be protected, however, it is not applicable to structures and equipment operated at high temperatures, vibration loads and aggressive environments, due to their low resistance to their effects (working the coating temperature does not exceed 250 ° C) and has insufficiently high thermophysical properties (thermal conductivity, thermal perception and heat transfer).
  • the technical result of the invention is to increase the heat-shielding and thermophysical properties of the coating, its resistance to high temperatures, vibration loads and aggressive media, expanding the range of operating temperatures of the coating while providing low thermal conductivity and high uniformity and adhesion of the coating to the substrate.
  • the heat-protective coating including hollow ceramic or corundum microspheres, a binder and water, as a binder contains one of the group comprising aluminoborophosphate, alumochromophosphate, potassium polytitanate, or a mixture of alumochromophosphate and potassium polytitanate, in the following ratio of components in mass %:
  • hollow ceramic or corundum microspheres 67 - 85 aluminoborphosphate or aluminochromophosphate or polytitanate
  • the thermal barrier coating contains aluminosilicate microspheres of fly ash with a diameter of 3-150 microns and a wall thickness of 1-6 microns.
  • heat-resistant coating contains glass-ceramic microspheres with a diameter of 3-100 microns and a wall thickness of 0.3 - 1.0 microns.
  • the thermal barrier coating contains microspheres with a diameter of 3-90 ⁇ m and a wall thickness of 0.5 - 3.0 ⁇ m.
  • compositions with the minimum allowable binder content are selected to cover the surfaces of structures and equipment operated at high operating temperatures.
  • Compositions with the maximum allowable binder content are selected to cover the surfaces of structures and equipment operated at high vibrations and mechanical loads.
  • hollow aluminosilicate microspheres of fly ash of thermal power plants or glass-ceramic or corundum microspheres in the claimed range of diameters and wall thicknesses obtained by evacuation (foaming) of ground glass-ceramic or corundum materials are used as a filler.
  • the materials of the microspheres are selected taking into account the high operating temperatures of the coating. Glass-ceramic microspheres are used for the operating temperature range up to 600 ° ⁇ , aluminosilicate microspheres are used up to 1400 ° ⁇ , corundum microspheres are up to 2000 ° ⁇ .
  • the diameter of the microspheres is selected in the range of 3 - 150 microns, commensurate with the long wavelength of thermal infrared radiation to ensure conditions for its maximum absorption by the microspheres.
  • the wall thickness of the microspheres in the range of 0.3-6 ⁇ m is selected taking into account the provision of the required strength of the material.
  • microspheres shape of the microspheres, their size and the selected distribution of microspheres by dispersion allow you to change the viscosity of the composition depending on its purpose with obtaining a heat-protective coating with high performance characteristics.
  • Preparation of the composition of the heat-shielding coating is carried out by mixing the initial composition in the dispersant.
  • the proposed coating can be applied to the surface of building structures made of metal, concrete, brick, as well as equipment of the chemical, aviation and railway industries, pipelines and ducts operated at temperatures from minus 60 ° C to plus 2000 ° C. Due to the high thermal properties of the proposed coating, it can be applied to surfaces with temperatures up to 300 ° C without stopping the operation of the equipment in operation.
  • the coating can be applied to the surface to be protected by any method used in the coating technology in the form of a single layer or several layers. Moreover, the thickness of the coating layer and depends on the nature of the surface, the conditions of the temperature regime of operation.
  • a high-temperature heat-shielding coating is firmly bonded to the base and has high performance characteristics.
  • the resulting coating retains high performance at high operating temperatures in the range from 300 to 2000 ° C.
  • Table 1 shows the recommended combinations of a binder and microspheres in the preparation heat-protective coating in accordance with the invention.
  • Tables 2, 3, 4, 5 show the qualitative and quantitative compositions of examples of the preparation of the proposed thermal barrier coating.
  • Table 6 shows the indicators of the properties of the thermal barrier coating for the compositions shown in tables 2-5.
  • the present invention allows to obtain coatings with high uniformity and adhesion strength, with high heat and thermal properties (low thermal conductivity, temperature resistance, chemical resistance, vibration resistance, abrasion resistance and electrical insulation resistance at high temperatures), which makes it possible to widely use it in construction, mechanical engineering, chemical, aviation and railway industries to ensure the protection of structures; Rui in conditions of high temperatures and corrosive environments.

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Abstract

The invention relates to the manufacture of heat-shielding coatings designed for structures and equipment used in high-temperature conditions and corrosive environments, and may be used in construction, mechanical engineering, the chemical industry, transport, aviation, space and other industrial sectors. In the proposed high-temperature heat-shielding coating, comprising hollow ceramic or corundum microspheres, a binder and water, the binder is in the form of one of the group consisting of aluminium borophosphate, aluminium chromophosphate, potassium polytitanate or a mixture of aluminium chromophosphate and potassium polytitanate, in the following ratio of constituents: 67-85 wt% microspheres, 10-30 wt% binder, and the rest water. As hollow ceramic microspheres, the heat-shielding coating contains aluminium silicate microspheres of fly ash with a diameter of 3-150 μm and a wall thickness of 1-6 μm or glass ceramic microspheres with a diameter of 3-100 μm and a wall thickness of 0.3-1.0 μm, and as hollow corundum microspheres, the coating contains microspheres with a diameter of 3-90 μm and a wall thickness of 0.5-3.0 μm.

Description

Высокотемпературное теплозащитное покрытие  High temperature thermal protection coating

Изобретение относится к производству теплозащитных покрытий, предназначенных для конструкций и оборудования, эксплуатируемых в условиях высоких температур и агрессивных сред, и может быть использовано в строительстве, машиностроении, химической промышленности, транспорте, авиационной, космической и других отраслях промышленности. The invention relates to the production of heat-insulating coatings intended for structures and equipment operated in conditions of high temperatures and aggressive environments, and can be used in construction, engineering, chemical industry, transport, aviation, space and other industries.

Известны теплозащитные покрытия содержащие полые керамические или стеклянные микросферы, связующие в виде дисперсий, эмульсий органорастворимых кремнийорганической смолы, акриловых сополимеров, полиуретанов, которые используются в качестве теплоизоляционного материала для наружных и внутренних поверхностей ограждающих строительных конструкций и сооружений, трубопроводов и различного технологического оборудования, например, краска-покрытие по патенту RU N° 2310670 С9, 20.11.2007. Однако указанное известное покрытие не применимо для конструкций и оборудования, эксплуатируемых в условиях высоких температур и вибронагрузок и агрессивных сред, вследствие низкой устойчивости к их воздействию (рабочая температура покрытия не превышает 200°С).  Heat-resistant coatings are known containing hollow ceramic or glass microspheres, binders in the form of dispersions, emulsions of organosoluble organosilicon resins, acrylic copolymers, polyurethanes, which are used as heat-insulating material for the outer and inner surfaces of building envelopes and structures, pipelines and various technological equipment, for example, paint-coating according to patent RU N ° 2310670 C9, 20.11.2007. However, this known coating is not applicable for structures and equipment operated under conditions of high temperatures and vibration loads and aggressive environments, due to the low resistance to their effects (operating temperature of the coating does not exceed 200 ° C).

Наиболее близким по технической сущности и достигаемому результату является теплозащитное покрытие, содержащее в качестве наполнителя вакуумированные (полые) керамические или корундовые микросферы с диаметром частиц от 3 до 100 мкм и насыпной плотностью 300-400 кг/м3 , в качестве связующего смолы кремнийорганические, полиэфирэпоксидные или акриловые дисперсии и в качестве добавок отражатель - алюминиевую пудру и пигмент, при следующем соотношении компонентов, в мас.%: микросферы 55-70, связующее 30-35, отражатель - алюминиевая пудра 2,0-5,0, пигмент 0,1-0,6 по патенту RU -Nb 2245350 С1, 27.01.2005. The closest in technical essence and the achieved result is a heat-shielding coating containing vacuum (hollow) ceramic or corundum microspheres with a particle diameter of 3 to 100 microns and a bulk density of 300-400 kg / m 3 as a filler, organosilicon, polyether epoxy binder or acrylic dispersions and, as additives, the reflector is aluminum powder and pigment, in the following ratio of components, in wt.%: microspheres 55-70, binder 30-35, reflector - aluminum powder 2.0-5.0, pigment 0.1-0.6 according to patent RU -Nb 2245350 C1, 01/27/2005.

Теплозащитное покрытие, полученное при нанесении известного состава, однородно по составу и имеет достаточно высокую прочность сцепления с защищаемой поверхностью, однако оно не применимо для конструкций и оборудования, эксплуатируемых в условиях высоких температур, вибронагрузок и агрессивных сред, вследствие низкой устойчивости к их воздействию (рабочая температура покрытия не превышает 250°С) и обладает недостаточно высокими теплофизическими свойствами (теплопроводностью, тейловосприятием и теплоотдачей).  The heat-protective coating obtained by applying the known composition is uniform in composition and has a sufficiently high adhesion to the surface to be protected, however, it is not applicable to structures and equipment operated at high temperatures, vibration loads and aggressive environments, due to their low resistance to their effects (working the coating temperature does not exceed 250 ° C) and has insufficiently high thermophysical properties (thermal conductivity, thermal perception and heat transfer).

Техническим результатом предлагаемого изобретения является повышение теплозащитных и теплофизических свойств покрытия, устойчивости его к воздействию высоких температур, вибронагрузок и агрессивных сред, расширение области рабочих температур покрытия при обеспечении низкой теплопроводности и высокой однородности и прочности сцепления покрытия с основой.  The technical result of the invention is to increase the heat-shielding and thermophysical properties of the coating, its resistance to high temperatures, vibration loads and aggressive media, expanding the range of operating temperatures of the coating while providing low thermal conductivity and high uniformity and adhesion of the coating to the substrate.

Указанный технический результат достигается тем, что теплозащитное покрытие, включающее полые керамические или корундовые микросферы, связующее и воду, в качестве связующего содержит одно из группы, включающей алюмоборфосфат, алюмохромфосфат, полититанат калия, или смесь алюмохромфосфата и полититаната калия, при следующем соотношении компонентов в масс %:  The specified technical result is achieved in that the heat-protective coating, including hollow ceramic or corundum microspheres, a binder and water, as a binder contains one of the group comprising aluminoborophosphate, alumochromophosphate, potassium polytitanate, or a mixture of alumochromophosphate and potassium polytitanate, in the following ratio of components in mass %:

полые керамические или корундовые микросферы 67 - 85 алюмоборфосфат или алюмохромфосфат или полититанат  hollow ceramic or corundum microspheres 67 - 85 aluminoborphosphate or aluminochromophosphate or polytitanate

калия или алюмохромфосфата и полититаната калия 10-30 вода остальное. В качестве полых керамических микросфер теплозащитное покрытие содержит алюмосиликатные микросферы золы уноса с диаметром 3-150 мкм и толщиной стенок 1-6 мкм.  potassium or alumochromophosphate and potassium polytitanate 10-30 water the rest. As hollow ceramic microspheres, the thermal barrier coating contains aluminosilicate microspheres of fly ash with a diameter of 3-150 microns and a wall thickness of 1-6 microns.

В качестве полых керамических микросфер теплозащитное покрытие содержит стеклокерамические микросферы с диаметром 3-100 мкм и толщиной стенок 0,3 - 1,0 мкм. As hollow ceramic microspheres, heat-resistant coating contains glass-ceramic microspheres with a diameter of 3-100 microns and a wall thickness of 0.3 - 1.0 microns.

В качестве полых корундовых микросфер теплозащитное покрытие содержит микросферы с диаметром 3-90 мкм и толщиной стенок 0,5 - 3,0 мкм.  As hollow corundum microspheres, the thermal barrier coating contains microspheres with a diameter of 3-90 μm and a wall thickness of 0.5 - 3.0 μm.

Составы с минимально допустимым содержанием связующего выбираются для покрытия поверхностей конструкций и оборудования, эксплуатируемых при высоких рабочих температурах.  Compositions with the minimum allowable binder content are selected to cover the surfaces of structures and equipment operated at high operating temperatures.

Составы с максимально допустимым содержанием связующего выбираются для покрытия поверхностей конструкций и оборудования, эксплуатируемых при повышенных вибрациях и механических нагрузках.  Compositions with the maximum allowable binder content are selected to cover the surfaces of structures and equipment operated at high vibrations and mechanical loads.

В предлагаемом составе для теплозащитного покрытия в качестве наполнителя используются полые алюмосиликатные микросферы золы уноса ТЭС или стеклокерамические или корундовые микросферы в заявляемых пределах диаметров и толщин стенок, полученные вакуумированием (вспениванием) измельченных стеклокерамических или корундовых материалов.  In the proposed composition for heat-shielding coatings, hollow aluminosilicate microspheres of fly ash of thermal power plants or glass-ceramic or corundum microspheres in the claimed range of diameters and wall thicknesses obtained by evacuation (foaming) of ground glass-ceramic or corundum materials are used as a filler.

Материалы микросфер выбраны с учетом обеспечения высоких рабочих температур эксплуатации покрытия. Для диапазона рабочих температур до 600°С используются стеклокерамические микросферы, до 1400°С - алюмосиликатные микросферы, до 2000 °С - корундовые микросферы.  The materials of the microspheres are selected taking into account the high operating temperatures of the coating. Glass-ceramic microspheres are used for the operating temperature range up to 600 ° С, aluminosilicate microspheres are used up to 1400 ° С, corundum microspheres are up to 2000 ° С.

Диаметр микросфер выбран в диапазоне 3 - 150 мкм, соразмерным с длинной волны теплового инфракрасного излучения для обеспечения условий его максимального поглощения микросферами. Толщина стенок микросфер в диапазоне 0.3-6 мкм выбрана с учетом обеспечения требуемой прочности материала.  The diameter of the microspheres is selected in the range of 3 - 150 microns, commensurate with the long wavelength of thermal infrared radiation to ensure conditions for its maximum absorption by the microspheres. The wall thickness of the microspheres in the range of 0.3-6 μm is selected taking into account the provision of the required strength of the material.

Выбор материалов и размеров микросфер произведен на основе экспериментальных данных, определяющих их оптимальные соотношения, достаточные для обеспечения требуемых вязкости состава, плотности, температурной стойкости и прочности готового покрытия. The choice of materials and sizes of microspheres was made on the basis of experimental data that determine their optimal ratio, sufficient to provide the required viscosity of the composition, density, temperature resistance and strength of the finished coating.

Форма микросфер, их размеры и подобранное распределение микросфер по дисперсности позволяют изменять вязкость композиции в зависимости от ее назначения с получением теплозащитного покрытия, обладающего высокими эксплуатационными характеристиками.  The shape of the microspheres, their size and the selected distribution of microspheres by dispersion allow you to change the viscosity of the composition depending on its purpose with obtaining a heat-protective coating with high performance characteristics.

Приготовления состава теплозащитного покрытия осуществляется перемешиванием исходного состава в диспергаторе.  Preparation of the composition of the heat-shielding coating is carried out by mixing the initial composition in the dispersant.

Предлагаемое покрытие можно наносить на поверхность строительных конструкций из металла, бетона, кирпича, а также на оборудование химической, авиационной и железнодорожной отраслей, трубопроводы и воздуховоды, эксплуатируемые при температурах от минус 60°С до плюс 2000°С. Благодаря высоким теплотехническим свойствам предлагаемого покрытия его можно наносить покрытия на поверхности с температурами до 300°С, не останавливая работу эксплуатируемого оборудования.  The proposed coating can be applied to the surface of building structures made of metal, concrete, brick, as well as equipment of the chemical, aviation and railway industries, pipelines and ducts operated at temperatures from minus 60 ° C to plus 2000 ° C. Due to the high thermal properties of the proposed coating, it can be applied to surfaces with temperatures up to 300 ° C without stopping the operation of the equipment in operation.

Покрытие может наноситься на защищаемую поверхность любым используемым в технологии нанесения покрытий способом в виде одного слоя или нескольких слоев. Причем толщина слоя покрытия и зависит от природы поверхности, условий температурного режима эксплуатации.  The coating can be applied to the surface to be protected by any method used in the coating technology in the form of a single layer or several layers. Moreover, the thickness of the coating layer and depends on the nature of the surface, the conditions of the temperature regime of operation.

После нанесения на поверхность материала или изделия слоя или нескольких слоев покрытия и последующей сушки образуется высокотемпературное теплозащитное покрытие прочно связанное с основой и обладающего высокими эксплуатационными характеристиками.  After applying a layer or several coating layers to the surface of the material or product and subsequent drying, a high-temperature heat-shielding coating is firmly bonded to the base and has high performance characteristics.

Получаемое покрытие сохраняет высокие эксплуатационные свойства при высоких рабочих температурах в диапазоне от 300 до 2000°С.  The resulting coating retains high performance at high operating temperatures in the range from 300 to 2000 ° C.

Сущность предлагаемого изобретения поясняется примерами выполнения, приведенными в таблицах 1 - 6. В таблице 1 приведены рекомендуемые комбинации связующего и микросфер при приготовлении теплозащитного покрытия в соответствии предлагаемым изобретением. В таблицах 2, 3, 4, 5 приведены качественные и количественные составы примеров приготовления предлагаемого теплозащитного покрытия. The essence of the invention is illustrated by examples shown in tables 1 to 6. Table 1 shows the recommended combinations of a binder and microspheres in the preparation heat-protective coating in accordance with the invention. Tables 2, 3, 4, 5 show the qualitative and quantitative compositions of examples of the preparation of the proposed thermal barrier coating.

В таблице 6 приведены показатели свойств теплозащитного покрытия для составов, приведенных в таблицах 2 -5.  Table 6 shows the indicators of the properties of the thermal barrier coating for the compositions shown in tables 2-5.

Таблица 1 Table 1

Figure imgf000007_0002
Figure imgf000007_0002

Таблица 3 Table 3

Figure imgf000007_0001
Таблица 4
Figure imgf000007_0001
Table 4

Figure imgf000008_0001
Figure imgf000008_0001

Таблица 6  Table 6

Figure imgf000008_0002
Figure imgf000008_0002

Предлагаемое изобретение позволяет получать покрытия с высокой однородностью и прочностью сцепления, обладающие высокими теплозащитными и теплофйзическими свойствами (низкой теплопроводностью, температурной стойкостью, химической стойкостью, вибростойкостью, абразивной стойкостью и электроизоляционной стойкостью в условиях высоких температур), что обуславливает возможность его широкого использования в строительстве, машиностроении, химической, авиационной и железнодорожной отраслях для обеспечения защиты конструкций, эксплуатируемых в условия высоких температур и агрессивных сред. The present invention allows to obtain coatings with high uniformity and adhesion strength, with high heat and thermal properties (low thermal conductivity, temperature resistance, chemical resistance, vibration resistance, abrasion resistance and electrical insulation resistance at high temperatures), which makes it possible to widely use it in construction, mechanical engineering, chemical, aviation and railway industries to ensure the protection of structures; Rui in conditions of high temperatures and corrosive environments.

Claims

Формула изобретения Claim 1. Теплозащитное покрытие, выполненное из композиции, содержащей полые керамические или корундовые микросферы, связующее и воду, отличающееся тем, что в качестве связующего содержит одно из группы, включающей алюмоборфосфат, алюмохромфосфат, полититанат калия, или смесь алюмохромфосфата и полититаната калия, при следующем соотношении компонентов в масс %: 1. Thermal protective coating made of a composition containing hollow ceramic or corundum microspheres, a binder and water, characterized in that the binder contains one of the group comprising aluminoborophosphate, alumochromophosphate, potassium polytitanate, or a mixture of potassium aluminochromophosphate and potassium polytitanate, in the following ratio components in mass%: полые керамические или корундовые микросферы 67-85 алюмоборфосфат или алюмохромфосфат или полититанат  hollow ceramic or corundum microspheres 67-85 aluminoborophosphate or aluminochromophosphate or polytitanate калия или смесь алюмохромфосфата и полититаната калия 10-30 вода остальное.  potassium or a mixture of aluminochromophosphate and potassium polytitanate 10-30 water the rest. 2. Теплозащитное покрытие по п. 1, отличающееся тем, что в качестве полых керамических микросфер содержит алюмосиликатные микросферы золы уноса с диаметром 3- 150 мкм и толщиной стенок 1-6 мкм.  2. Thermal insulation coating according to claim 1, characterized in that as hollow ceramic microspheres contains aluminosilicate microspheres of fly ash with a diameter of 3-150 microns and a wall thickness of 1-6 microns. 3. Теплозащитное покрытие по п. 1, отличающееся тем, что в качестве полых керамических микросфер содержит стеклокерамические микросферы с диаметром 3-100 мкм и толщиной стенок 0,3 - 1,0 мкм.  3. Thermal insulation coating according to claim 1, characterized in that as hollow ceramic microspheres contains glass-ceramic microspheres with a diameter of 3-100 μm and a wall thickness of 0.3 - 1.0 μm. 4. Теплозащитное покрытие по п. 1, отличающееся тем, что в качестве полых корундовых микросфер содержит микросферы с диаметром 3-90 мкм и толщиной стенок 0,5 - 3,0 мкм.  4. Thermal insulation coating according to claim 1, characterized in that as hollow corundum microspheres contains microspheres with a diameter of 3-90 μm and a wall thickness of 0.5 - 3.0 μm.
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