CN106702355B - thermotropic in-situ reaction conversion type nanometer heat-absorbing coating material and preparation method thereof - Google Patents

thermotropic in-situ reaction conversion type nanometer heat-absorbing coating material and preparation method thereof Download PDF

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CN106702355B
CN106702355B CN201611141575.0A CN201611141575A CN106702355B CN 106702355 B CN106702355 B CN 106702355B CN 201611141575 A CN201611141575 A CN 201611141575A CN 106702355 B CN106702355 B CN 106702355B
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陆雯婕
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

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Abstract

The application discloses thermotropic in-situ reaction conversion type nanometer heat-absorbing coating materials, which are characterized in that the thermotropic in-situ reaction conversion type heat-absorbing coating materials are prepared by calcining tin-copper alloy and silicon-containing compounds in a mass ratio of 1-1: 20 in hot air at 300-600 ℃, wherein the tin-copper alloy is converted into CuO and SnO in situ2Functional substance, in-situ conversion of said silicon-containing compound to amorphous SiO2CuO-SnO formed by matrix2‑SiO2And (3) coating materials. The coating material obtains the heat-absorbing coating material jointly consisting of nano copper oxide, nano tin oxide and amorphous silicon dioxide through the composite and thermally induced in-situ reaction transformation process of the low-melting-point nano tin-copper alloy and the silicon-containing compound, and realizes the selective heat-absorbing and energy-saving strengthening functions of a stainless steel pot or an aluminum alloy pot.

Description

thermotropic in-situ reaction conversion type nanometer heat-absorbing coating material and preparation method thereof
Technical Field
The application relates to nanometer heat-absorbing energy-saving coating materials for household metal cookware, in particular to thermotropic in-situ reaction conversion type nanometer heat-absorbing coating materials and a preparation method thereof.
Background
The cookware made of stainless steel and aluminum alloy has excellent shape, abundant expressive force and corrosion resistance, and can be widely applied to in modern kitchens, however, due to the high light reflection characteristic of the stainless steel and the aluminum alloy, the cookware can absorb and utilize the energy of gas flame, and is not beneficial to energy conservation and emission reduction in the field of civil gas.
The strong heat radiation effect on the surface of the high-temperature material can reduce the heat energy utilization efficiency of the material, the corresponding heat energy radiation loss can be inhibited by reducing the infrared emissivity in the high-temperature heat radiation wavelength region of the material, and the heat absorbing material with the heat radiation inhibition function characteristic is generally called as a selective absorbing material. The selective absorption material is mainly used in the field of solar water heaters at present, and is mostly a film material prepared by adopting methods such as magnetron sputtering or vacuum coating, and the like, and the film material has a complex preparation process and is easy to lose effectiveness by high-temperature oxidation.
In 2015, selective absorption type photothermal conversion ceramic composite materials capable of meeting the requirements of atmospheric environment and medium-high temperature use and a preparation method thereof were disclosed in a patent No. 201310520658.0 entitled " selective absorption type photothermal conversion ceramic composite materials and a preparation method thereof".
The basic principle of the method is that different elements or chemicals are subjected to chemical reaction under conditions to generate or more ceramic phase particles in a metal matrix so as to achieve the purpose of improving the performance of a single metal alloy.
So far, selective heat-absorbing coating materials with simple preparation process, good low-temperature film-forming property and good high-temperature oxidation resistance, in particular selective heat-absorbing energy-saving coating materials which can be used for household stainless steel pots and aluminum alloy pots, have not been reported.
Therefore, in order to overcome the above-mentioned drawbacks of the prior art, the present application is specifically proposed.
Disclosure of Invention
aims to provide thermotropic in-situ reaction conversion type nanometer heat-absorbing coating materials aiming at the defects in the prior art, the coating materials obtain the heat-absorbing coating materials consisting of nanometer copper oxide, nanometer tin oxide and amorphous silicon dioxide through the compounding of low-melting-point nanometer tin-copper alloy and silicon-containing compounds and the thermotropic in-situ reaction conversion process, and the selective heat-absorbing strengthening energy-saving function of a stainless steel pot or an aluminum alloy pot is realized.
In order to achieve the purpose, the following technical scheme is adopted in the application:
thermotropic in-situ reaction conversion type nanometer heat-absorbing coating materials, which are characterized in that the thermotropic in-situ reaction conversion type heat-absorbing coating materials are prepared by calcining tin-copper alloy and silicon-containing compounds in a mass ratio of 1-1: 20 in hot air at 300-600 ℃, wherein the tin-copper alloy is converted into CuO and SnO in situ2A functional substance,The silicon-containing compound is converted in situ to amorphous SiO2CuO-SnO formed by matrix2-SiO2And (3) coating materials.
Preferably, the particle size of the tin-copper alloy is 20-200 nanometers, and preferably, the particle size is 50-150 nanometers.
Preferably, the melting point of the tin-copper alloy is 300-500 ℃; and the copper content in the tin-copper alloy is 10-50 wt%; preferably, the copper content in the tin-copper alloy is 40-50 wt%.
Preferably, the silicon-containing compound is a mixture of sodium silicate, siloxane, tin oxide and alcohol, and the sodium silicate content is 0.01-10 wt%, the siloxane content is 0.5-25 wt%, and the tin oxide content is 0.01-5 wt%.
Preferably, the siloxane is one or two of tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and .
Preferably, the alcohol is methanol or ethanol, or a mixed solution of methanol and ethanol.
Another objective of the present application is to provide a preparation method of thermal in-situ reaction conversion type nano endothermic coating materials.
In order to achieve the purpose, the following technical scheme is adopted in the application:
method for preparing thermotropic in-situ reaction conversion type nanometer heat-absorbing coating material, which is characterized by comprising the following steps:
(1) weighing sodium silicate, siloxane, tin oxide and an alcohol solution according to the mass ratio;
(2) mixing weighed sodium silicate, siloxane, tin oxide and an alcohol solution, and uniformly stirring to obtain a silicon-containing compound solution;
(3) weighing the nano tin-copper alloy and the silicon-containing compound solution obtained in the step (2) according to the mass ratio;
(4) and adding the weighed nano tin-copper alloy into the weighed silicon-containing compound solution, and uniformly stirring to obtain the thermotropic in-situ reaction conversion type nano heat-absorbing coating material.
Preferably, in the step (2), the stirring time is 10-60 minutes; in the step (4), the stirring time is 1-2 hours.
Preferably, in the step (4), after the uniform stirring, the process of calcining in hot air at 300-600 ℃ is further included.
Preferably, the calcination time is 1-2 h.
thermotropic in-situ reaction conversion type nanometer heat-absorbing coating materials, wherein the heat-absorbing coating materials take low-melting-point nanometer tin-copper alloy as a functional object precursor and a silicon-containing compound as a matrix precursor, the mass ratio of the nanometer tin-copper alloy to the silicon-containing compound is 1-1: 20, and the nanometer tin-copper alloy is calcined in a hot air environment at 300-600 ℃ to be converted into nanometer CuO and nanometer SnO2The functional substance, the silicon-containing compound, is converted into an inorganic silicate compound.
The size of the low-melting-point nano tin-copper alloy particles is 20-200 nanometers, and the preferable particle size is 50-150 nanometers; the copper content in the tin-copper alloy is 10-50 wt%, preferably 40-50 wt%; the melting point is between 300 and 500 ℃.
The silicon-containing compound is a mixture of sodium silicate, siloxane, tin oxide and alcohol, wherein the content of the sodium silicate is 0.01-10 wt%, the content of the siloxane is 0.5-25 wt%, the content of the tin oxide is 0.01-5 wt%, and the balance is an alcohol solution.
The silicon-containing compound contains siloxane which is one or two of tetramethoxysilane, tetraethoxysilane, dimethyl dimethoxysilane, dimethyl diethoxysilane and .
The alcohol contained in the silicon-containing compound is a mixed solution of methanol and ethanol in any proportion.
The preparation method of thermotropic in-situ reaction conversion type nanometer heat-absorbing coating materials is characterized by comprising the following steps:
(1) weighing sodium silicate, siloxane, tin oxide and alcohol solution according to the stoichiometric ratio of sodium silicate, siloxane, tin oxide and alcohol in the silicon-containing compound, wherein the siloxane is one or two of tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and , and the alcohol is a mixed solution of methanol and ethanol in any proportion.
(2) Mixing weighed sodium silicate, siloxane, tin oxide and alcohol solution at , stirring for 10-60 minutes to form uniform silicon-containing compound solution;
(3) weighing quantitative nano tin-copper alloy and the silicon-containing compound solution prepared in the step (2) according to the stoichiometric ratio of 1-1: 20;
(4) and adding the weighed nano tin-copper alloy into a silicon-containing compound solution, and stirring for 1-2 hours to obtain the required thermotropic in-situ reaction conversion type nano heat-absorbing coating material.
The beneficial effect of this application lies in:
1) the nano tin-copper alloy used in the application has the characteristic of low melting point, and is easy to form a film at a low temperature after being compounded with a silicon-containing compound, and becomes a novel heat-absorbing coating material with excellent selective absorption characteristic through a corresponding thermal in-situ reaction transformation process.
2) The nano tin-copper alloy and the silicon-containing compound used in the method can be converted into nano copper oxide and nano tin oxide through high-temperature action conversion, and the silicon-containing compound is converted into inorganic amorphous silicon dioxide, so that the heat-absorbing coating has excellent high-temperature oxidation resistance.
3) The thermotropic in-situ reaction conversion type nanometer heat absorption coating material can enhance the selective heat absorption capacity of stainless steel pot products and aluminum alloy pot products, can improve the energy utilization rate of gas flame by more than 25 percent, and has obvious gas energy-saving effect.
Drawings
FIG. 1 is a graph showing diffuse reflectance spectra for stainless steel and aluminum metal.
FIG. 2 is a graph showing a diffuse reflection spectrum of a coating according to example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of this application were all purchased commercially and are shown in the following table:
name (R) Manufacturer of the product
Sodium silicate Shanghai Tech chemical Co Ltd
Tetramethoxysilane Shanghai Aladdin Biotechnology Ltd
Tetraethoxysilane Shanghai Aladdin Biotechnology Ltd
Dimethyldimethoxysilane Sigma Aldrich trade company
Dimethyldiethoxysilane Sigma Aldrich trade company
Methanol Shanghai Lingfeng Chemicals Co., Ltd
Ethanol Subson chemical Co Ltd of Wuxi City
Tin oxide powder Shanghai super Wei nano science and technology limitedCompany(s)
Nano tin-copper alloy Shanghai ultramicro nanotechnology Co., Ltd
Example 1
method for preparing thermal in-situ reaction conversion type nanometer heat-absorbing coating material, comprising the following steps:
(1) according to the mass ratio of 0.04 wt% of sodium silicate, 1 wt% of siloxane (the mass ratio of tetramethoxysilane to dimethyldiethoxysilane is 1:1), 0.02 wt% of tin oxide and 98.94 wt% of methanol, 0.04 g of nano sodium silicate powder, 1 g of mixed solution of tetramethoxysilane and dimethyldiethoxysilane, 0.02 g of tin oxide powder and 98.94 g of methanol solution are weighed.
(2) Mixing weighed sodium silicate, siloxane, tin oxide and methanol solution at , stirring for 30 minutes to form uniform silicon-containing compound solution;
(3) weighing 15 g of nano tin-copper alloy (with the particle size of 150 nm and the copper content of 30%) and 15 g of the silicon-containing compound solution prepared in the step (2) according to the mass ratio of 1: 1;
(4) and adding the weighed nano tin-copper alloy into the silicon-containing compound solution, and stirring for 1.5 hours to obtain the required thermotropic phase transition type nano heat-absorbing coating material.
According to the calculation of figure 1, the light absorptivity of the stainless steel in the ultraviolet-visible-near infrared band is 0.64, and the light absorptivity of the aluminum sheet in the band is 0.55; according to the results of the emissivity tester, the emissivity of the infrared region is 0.14 and 0.06 respectively. And the coating has the light absorptivity of 0.88 in the ultraviolet-visible-near infrared band calculated according to the figure 2; according to the results of the emissivity test, the emissivity of the coating in the infrared region is 0.89. The results show that the coating material has better heat absorption performance and can obviously improve the utilization rate of fuel gas.
Example 2
method for preparing thermal in-situ reaction conversion type nanometer heat-absorbing coating material, comprising the following steps:
(1) according to the mass ratio of 10 wt% of sodium silicate, 15 wt% of siloxane (the mass ratio of tetramethoxysilane to dimethyldiethoxysilane is 1:1), 1 wt% of tin oxide and 74 wt% of methanol, 10 g of nano sodium silicate powder, 15 g of mixed solution of tetramethoxysilane and dimethyldiethoxysilane, 1 g of tin oxide powder and 74 g of methanol solution are weighed.
(2) Mixing weighed sodium silicate, siloxane, tin oxide and methanol solution at , stirring for 40 minutes to form uniform silicon-containing compound solution;
(3) weighing 15 g of nano tin-copper alloy (with the particle size of 150 nm and the copper content of 30%) and 100 g of the silicon-containing compound solution prepared in the step (2) according to the mass ratio of 3: 20;
(4) and adding the weighed nano tin-copper alloy into the silicon-containing compound solution, and stirring for 1.5 hours to obtain the required thermotropic phase transition type nano heat-absorbing coating material.
Example 3
method for preparing thermal in-situ reaction conversion type nanometer heat-absorbing coating material, comprising the following steps:
(1) according to the mass ratio of 5 wt% of sodium silicate, 25 wt% of dimethyl dimethoxy silane, 2 wt% of tin oxide and 68 wt% of alcohol (the mass ratio of methanol to ethanol is 3:1), 5 g of sodium silicate powder, 25 g of dimethyl dimethoxy silane siloxane, 2 g of tin oxide powder and 68 g of methanol-ethanol mixed alcohol solution are weighed.
(2) Mixing with weighed mixed alcohol solution of sodium silicate, siloxane, tin oxide and methanol-ethanol, and stirring for 10 minutes to form uniform silicon-containing compound solution;
(3) weighing 10 g of nano tin-copper alloy (with the particle size of 100 nanometers and the copper content of 50%) and 100 g of the silicon-containing compound solution prepared in the step (2) according to the mass ratio of 1: 10;
(4) and adding the weighed nano tin-copper alloy into the silicon-containing compound solution, and stirring for 1 hour to obtain the required thermotropic phase transition type nano heat-absorbing coating material.
Example 4
method for preparing thermal in-situ reaction conversion type nanometer heat-absorbing coating material, comprising the following steps:
(1) according to the mass ratio of 10 wt% of sodium silicate, 0.5 wt% of tetraethoxysilane, 5 wt% of tin oxide and 74.5 wt% of alcohol (the mass ratio of methanol to ethanol is 5:1), 10 g of sodium silicate powder, 0.5 g of tetraethoxysilane, 5 g of tin oxide powder and 74.5 g of methanol-ethanol mixed alcohol solution are weighed.
(2) Mixing with weighed mixed alcohol solution of sodium silicate, siloxane, tin oxide and methanol-ethanol, and stirring for 60 minutes to form uniform silicon-containing compound solution;
(3) weighing 10 g of nano tin-copper alloy (with the particle size of 100 nanometers and the copper content of 50%) and 200 g of the silicon-containing compound solution prepared in the step (2) according to the mass ratio of 1: 20;
(4) and adding the weighed nano tin-copper alloy into the silicon-containing compound solution, and stirring for 2 hours to obtain the required thermotropic phase transition type nano heat-absorbing coating material.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1, thermotropic in-situ reaction conversion type nanometer heat-absorbing coating materials, characterized in that, the thermotropic in-situ reaction conversion type heat-absorbing coating materials are prepared by calcining tin-copper alloy and silicon-containing compound with the mass ratio of 1-1: 20 in hot air at 300-600 ℃, wherein the tin-copper alloy is converted into CuO and SnO in situ2Functional substance, in-situ conversion of said silicon-containing compound to amorphous SiO2CuO-SnO formed by matrix2-SiO2And (3) coating materials.
2. The nano heat absorption coating material of claim 1, wherein the tin-copper alloy particle size is 50-150 nm.
3. The thermally induced in-situ reaction converted nano heat absorption coating material as claimed in claim 1, wherein the tin-copper alloy melting point is 300-500 ℃; and the copper content in the tin-copper alloy is 40-50 wt%.
4. The thermally-induced in-situ reaction conversion type nano heat absorption coating material according to any of claims 1-3, wherein the silicon-containing compound is a mixture of sodium silicate, siloxane, tin oxide and alcohol, and the sodium silicate content is 0.01-10 wt%, the siloxane content is 0.5-25 wt%, and the tin oxide content is 0.01-5 wt%.
5. The thermally induced in-situ reaction converted nano endothermic coating material according to claim 4, wherein the siloxane is one or two of tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and .
6. The thermally-induced in-situ reaction converted nano endothermic coating material according to claim 4, wherein the alcohol is methanol or ethanol, or a mixture of methanol and ethanol.
7, method for preparing the nano endothermic coating material with the thermal in-situ reaction conversion type according to any of claims 1 to 6, wherein the method comprises the following steps:
(1) weighing sodium silicate, siloxane, tin oxide and an alcohol solution according to the mass ratio;
(2) mixing weighed sodium silicate, siloxane, tin oxide and an alcohol solution, and uniformly stirring to obtain a silicon-containing compound solution;
(3) weighing the nano tin-copper alloy and the silicon-containing compound solution obtained in the step (2) according to the mass ratio;
(4) and adding the weighed nano tin-copper alloy into the weighed silicon-containing compound solution, and uniformly stirring to obtain the thermotropic in-situ reaction conversion type nano heat-absorbing coating material.
8. The method according to claim 7, wherein in the step (2), the stirring time is 10 to 60 minutes; in the step (4), the stirring time is 1-2 hours.
9. The method according to claim 7, wherein the step (4) further comprises a step of calcining the mixture in hot air at 300-600 ℃ after the mixture is uniformly stirred.
10. The method according to claim 9, characterized in that the calcination time is 1-2 h.
CN201611141575.0A 2016-12-12 2016-12-12 thermotropic in-situ reaction conversion type nanometer heat-absorbing coating material and preparation method thereof Active CN106702355B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553634A (en) * 2013-10-29 2014-02-05 南京工业大学 Selective absorption type photothermal conversion ceramic composite material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553634A (en) * 2013-10-29 2014-02-05 南京工业大学 Selective absorption type photothermal conversion ceramic composite material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
THE SELECTIVE SOLAR ABSORPHON OF OXIDE FILMS GROWN IN SITU ON ICe-, Ni-, AND Cu-BASE ALLOYS;M.Z.WU et al.;《Solar Energy Materials》;19881231(第17期);119-136 *
太阳能光谱选择性吸收涂层研究进展;马鹏军等;《材料导报Ａ：综述篇》;20150131;第29卷(第1期);48-54 *

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