CN113446592B - Coating with multilayer structure for boiler heating surface - Google Patents

Coating with multilayer structure for boiler heating surface Download PDF

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CN113446592B
CN113446592B CN202110538336.3A CN202110538336A CN113446592B CN 113446592 B CN113446592 B CN 113446592B CN 202110538336 A CN202110538336 A CN 202110538336A CN 113446592 B CN113446592 B CN 113446592B
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coating
surface layer
layer
middle coating
horizontal plane
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CN113446592A (en
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戴雷
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Shenzhen Youyi Material Technology Co ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B37/00—Component parts or details of steam boilers
    • F22B37/02—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler
    • F22B37/10—Water tubes; Accessories therefor
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
    • F24H9/00—Details
    • F24H9/0005—Details for water heaters

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention relates to a coating with a multilayer structure for a boiler heating surface, which comprises an inner surface layer, a middle coating A, a middle coating B, a middle coating C and an outer surface layer, wherein the inner surface layer is positioned on the boiler heating surface, the outer surface layer is positioned on the outermost layer of the coating, the middle coating A, the middle coating B and the middle coating C are positioned between the inner surface layer and the outer surface layer, the middle coating A is coated on the inner surface layer, the middle coating B is coated on the middle coating A, and the middle coating C is coated between the middle coating B and the outer surface layer. The cross sections of the inner surface coating, the middle coating A, the middle coating C and the outer surface layer are of trapezoidal structures, the service life of the coating can be further prolonged due to the design of the structure, the influence on the coating after cracks appear in long-time use is reduced, and the effects of corrosion resistance and the like are enhanced.

Description

Coating with multilayer structure for boiler heating surface
Technical Field
The invention belongs to the field of coatings, and particularly relates to a coating with a multilayer structure for a boiler surface.
Background
The coating is widely applied to high-temperature environments such as boilers, pipelines and the like, can effectively comprise metal materials, and is very important for preventing the boiler pipelines from being damaged and protecting the environment. For places such as waste incineration plants and power plants, the coating needs to have high temperature resistance and corrosion resistance due to the dual difficulties of temperature corrosion and gas corrosion.
The research on multilayer coatings has been carried out for a lot, and in the last century, the united states space agency has co-deposited a ceramic layer with heat insulation and a metal bonding layer with adhesive property on a metal surface by means of spraying, so that a high-temperature resistant substrate and a medium can be separated, and the medium can bear a more severe use environment, including a ceramic top layer, a thermally grown oxide layer, a bonding layer and a high-temperature alloy substrate. Chinese patent CN10920875A studies the corrosion-resistant structure of the heated surface of the boiler, which includes a surface coating and an inner coating, and the coatings mainly composed of metal oxides and metal elements are alternately arranged. CN108070836A discloses a micro-laminated coating resistant to ultrahigh temperature oxidation, and the lamination is beneficial to improving the thermal shock resistance of the coating and effectively avoiding the phenomenon that a certain phase in a single-layer coating is exhausted.
Disclosure of Invention
The invention relates to a coating with a multilayer structure, which can more effectively play the effects of corrosion resistance and high-temperature thermal shock resistance. The technical scheme of the invention is as follows.
The invention relates to a coating with a multilayer structure for a boiler heating surface, which comprises five layers, namely an inner surface layer, a middle coating A, a middle coating B, a middle coating C and an outer surface layer, wherein the inner surface layer is positioned on the boiler heating surface, the outer surface layer is positioned on the outermost layer of the coating, the middle coating A, the middle coating B and the middle coating C are positioned between the inner surface layer and the outer surface layer, the middle coating A is coated on the inner surface layer, the middle coating B is coated on the middle coating A, and the middle coating C is coated between the middle coating B and the outer surface layer, namely the coating structure has five layers.
Further, the inner surface layer is Si3N4the/BN composite ceramic coating.
Further, the outer surface layer comprises alumina, zirconium silicate, zirconia, TiO2. The dosage (wt%) of the components can be as follows: 50% of alumina, 2% of zirconium silicate and 3% of zirconium oxide; 1% TiO2，The balance is the conventional auxiliary materials in the field, such as high-temperature adhesive, filler, solvent, auxiliary agent and the like, so as to improve the comprehensive performance of the formed coating; the high-temperature binder comprises one or more of water glass, aluminum dihydrogen phosphate, silica sol, aluminum sol and zirconium sol.
Further, the intermediate coating a and the outer surface layer have the same coating structure.
Further, the intermediate coating layer B and the inner surface layer have the same coating structure.
Further, the intermediate coating C is TiC/Si3N4And (4) coating.
Furthermore, the connecting layer surface of the inner surface layer and the middle coating layer A is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 10-20 degrees; the middle coating B is a horizontal coating; the connection layer of the outer surface layer and the middle coating layer C is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 10-20 degrees and is opposite to the inclination direction of the inner surface layer and the middle coating layer A. I.e. right trapezoid for the inner surface layer, the intermediate coating a, the intermediate coating C and the outer surface layer, respectively, as seen in cross-section, and the intermediate coating B is a horizontal coating.
Further, the components of the coating layer can also comprise a binder, a curing agent, a photoinitiator, a film forming agent and a bonding agent, and can also comprise a dispersing agent, a wetting agent and other components which are conventional in the field. The multilayer structure is in the form of a viscous mass for easy spraying, enabling the coating to achieve the structure described herein. When the material fluidity is large, the material can be obtained by matching a grinding tool with a scraper blade for coating, for example, when a rectangular grinding tool is used, the sprayed coating is to have a certain shape, a trapezoidal structure with a certain inclination angle is realized through the scraper blade, and the multilayer coating is obtained by analogy. When the coating structure is used in scenes such as boilers, pipelines and the like, the coating structure can be prepared preferably in a coating deposition mode; it can also be made by the corresponding grinding tool structure of the coating structure.
The current research on multi-layer coatings is mainly horizontal coating of each layer, for example, patent CN109280875A outlines metal oxide coating 1, metal oxide coating 2, … …, metal substrate. What is important to the innovation of the present invention is the multi-layer structure of the present invention. In the research, the coating structure with a certain inclined angle design has more outstanding corrosion resistance effect than a horizontal coating due to the complex corrosion cause in the boiler and different corrosion degrees. The inner surface coating, the middle coating A, the middle coating C and the outer surface layer are in a trapezoidal structure in cross section, the service life of the coating can be further prolonged due to the design of the structure, the influence on the coating after cracks appear after long-time use is reduced, and the effects of thermal shock resistance, corrosion resistance and the like are enhanced. The inclination angle of the coating is 10-20 degrees, and the inclination directions of the middle coating C and the outer surface coating and the inclination directions of the inner surface coating and the middle coating A are opposite to each other, so that the corrosion resistance effect is further improved. The five-layer structure design of the coating of the invention also ensures that the invention has more stable performance in the aspect of thermal shock resistance.
Drawings
FIG. 1 is a schematic cross-sectional view of a multilayer coating structure of the present invention;
where 1 is the inner surface layer, 2 is the intermediate coating a, 3 is the intermediate coating B, 4 is the intermediate coating C, and 5 is the outer surface layer.
Detailed Description
The coating according to the invention is further illustrated by the following embodiments.
Example 1
The coating with the five-layer structure comprises an inner surface layer, an intermediate coating A, an intermediate coating B, an intermediate coating C and an outer surface layer, wherein the inner surface layer is positioned on a heated surface of a boiler, the outer surface layer is positioned on the outermost layer of the coating, the intermediate coating A, the intermediate coating B and the intermediate coating C are positioned between the inner surface layer and the outer surface layer, the intermediate coating A is coated on the inner surface layer, the intermediate coating B is coated on the intermediate coating A, and the intermediate coating C is coated between the intermediate coating B and the outer surface layer. The inner surface layer is Si3N4the/BN composite ceramic coating. The outer surface layer comprises 50% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide in wt%; 1% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating a and the outer surface layer have the same coating structure. The intermediate coating B and the inner surface layer have the same coating structure. The intermediate coating C is TiC/Si3N4And (4) coating. The connecting layer surface of the inner surface layer and the middle coating layer A is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 20 degrees; the middle coating B is a horizontal coating; the connection layer of the outer surface layer and the middle coating layer C is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 20 degrees and is opposite to the inclination direction of the inner surface layer and the middle coating layer A.
Example 2
Coat in the hot surface of boiler and have the coating structure of five-layer structure, prepare through the mode of spraying deposit and obtain, be internal surface layer, intermediate coat A, intermediate coat B, intermediate coat C, outer surface layer respectively, the internal surface layer is located the boiler and receives the hot surface, outer surface layer is located the coating outwardly, intermediate coat A, intermediate coat B and intermediate coat C be located between internal surface layer and the outer surface layer, intermediate coat A coats on the internal surface layer, intermediate coat B coats on intermediate coat A, intermediate coat C coats intermediate coat B and outer surface layerBetween the surface layers. The inner surface layer is Si3N4a/BN composite ceramic coating. The outer surface layer comprises 55% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide; 1.5% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating a and the outer surface layer have the same coating structure. The intermediate coating B and the inner surface layer have the same coating structure. The intermediate coating C is TiC/Si3N4And (4) coating. The connecting layer surface of the inner surface layer and the middle coating layer A is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 15 degrees; the middle coating B is a horizontal coating; the connection layer surface of the outer surface layer and the middle coating layer C is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 15 degrees and is opposite to the inclination direction of the inner surface layer and the middle coating layer A.
Comparative example 1
The coating with the five-layer structure comprises an inner surface layer, an intermediate coating A, an intermediate coating B, an intermediate coating C and an outer surface layer, wherein the inner surface layer is positioned on a heated surface of a boiler, the outer surface layer is positioned on the outermost layer of the coating, the intermediate coating A, the intermediate coating B and the intermediate coating C are positioned between the inner surface layer and the outer surface layer, the intermediate coating A is coated on the inner surface layer, the intermediate coating B is coated on the intermediate coating A, and the intermediate coating C is coated between the intermediate coating B and the outer surface layer. The inner surface layer is Si3N4the/BN composite ceramic coating. The outer surface layer comprises 55% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide; 1.5% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating a and the outer surface layer have the same coating structure. The intermediate coating B and the inner surface layer have the same coating structure. The intermediate coating C is TiC/Si3N4And (4) coating. Each layer of the coating is of a horizontal structure.
Comparative example 2
The coating with a five-layer structure comprises an inner surface layer, an intermediate coating A, an intermediate coating B, an intermediate coating C and an outer surface layer, wherein the inner surface layer is positioned on a boiler heating surface, and the outer surface layer is positioned on the outermost layer of the coatingThe outer layer, intermediate coat A, intermediate coat B and intermediate coat C be located between interior surface course and the outer surface course, intermediate coat A coats on the interior surface course, intermediate coat B coats on intermediate coat A, intermediate coat C coats between intermediate coat B and the outer surface course. The inner surface layer is Si3N4the/BN composite ceramic coating. The outer surface layer comprises 50% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide; 1% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating a and the outer surface layer have the same coating structure. The intermediate coating B and the inner surface layer have the same coating structure. The intermediate coating C is TiC/Si3N4And (4) coating. The connecting layer surface of the inner surface layer and the middle coating layer A is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 5 degrees; the middle coating B is a horizontal coating; the connection layer surface of the outer surface layer and the middle coating layer C is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 5 degrees and is opposite to the inclination direction of the inner surface layer and the middle coating layer A.
Comparative example 3
The coating with the five-layer structure comprises an inner surface layer, an intermediate coating A, an intermediate coating B, an intermediate coating C and an outer surface layer, wherein the inner surface layer is positioned on a heated surface of a boiler, the outer surface layer is positioned on the outermost layer of the coating, the intermediate coating A, the intermediate coating B and the intermediate coating C are positioned between the inner surface layer and the outer surface layer, the intermediate coating A is coated on the inner surface layer, the intermediate coating B is coated on the intermediate coating A, and the intermediate coating C is coated between the intermediate coating B and the outer surface layer. The inner surface layer is Si3N4the/BN composite ceramic coating. The outer surface layer comprises 50% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide; 1% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating a and the outer surface layer have the same coating structure. The intermediate coating B and the inner surface layer have the same coating structure. The intermediate coating C is TiC/Si3N4And (4) coating. The inner surface layer and the intermediate coating A are connected on the surface of the non-horizontal plane, and compared with the horizontal plane, the inner surface layer and the intermediate coating A are inclinedThe oblique angle is 35 degrees; the middle coating B is a horizontal coating; the connection layer of the outer surface layer and the middle coating layer C is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 35 degrees, and the inclination direction of the connection layer is opposite to that of the inner surface layer and the middle coating layer A.
Comparative example 4
The coating with the five-layer structure comprises an inner surface layer, an intermediate coating A, an intermediate coating B, an intermediate coating C and an outer surface layer, wherein the inner surface layer is positioned on a heated surface of a boiler, the outer surface layer is positioned on the outermost layer of the coating, the intermediate coating A, the intermediate coating B and the intermediate coating C are positioned between the inner surface layer and the outer surface layer, the intermediate coating A is coated on the inner surface layer, the intermediate coating B is coated on the intermediate coating A, and the intermediate coating C is coated between the intermediate coating B and the outer surface layer. The outer surface layer is Si3N4the/BN composite ceramic coating. The inner surface layer comprises 55% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide; 1.5% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating a and the outer surface layer have the same coating structure. The intermediate coating B and the inner surface layer have the same coating structure. The intermediate coating C is TiC/Si3N4And (4) coating. Each layer of the coating is of a horizontal structure.
Comparative example 5
The coating with three-layer structure comprises an inner surface layer, a middle coating and an outer surface layer, wherein the inner surface layer is positioned on a boiler heating surface, the outer surface layer is positioned on the outermost layer of the coating, the middle coating is positioned between the inner surface layer and the outer surface layer, and the outer surface layer is made of Si3N4the/BN composite ceramic coating. The inner surface layer comprises 55% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide; 1.5% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating is TiC/Si3N4And (4) coating.
Comparative example 6
The coating with the five-layer structure is prepared by a spray deposition mode and comprises an inner surface layer, an intermediate coating A,Intermediate coat B, intermediate coat C, outer surface layer, the inner surface layer is located the boiler heating surface, the outer surface layer is located the coating outermost, intermediate coat A, intermediate coat B and intermediate coat C be located between inner surface layer and the outer surface layer, intermediate coat A coats on the inner surface layer, intermediate coat B coats on intermediate coat A, intermediate coat C coats between intermediate coat B and the outer surface layer. The inner surface layer is Si3N4the/BN composite ceramic coating. The outer surface layer comprises 55% of aluminum oxide, 2% of zirconium silicate and 3% of zirconium oxide; 1.5% TiO2，The balance of high-temperature adhesive silica sol 20 percent and the balance of water. The intermediate coating a and the outer surface layer have the same coating structure. The intermediate coating B and the inner surface layer have the same coating structure. The intermediate coating C is TiC/Si3N4And (4) coating. The connecting layer surface of the inner surface layer and the middle coating layer A is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 15 degrees; the middle coating B is a horizontal coating; the connection layer of the outer surface layer and the middle coating layer C is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 15 degrees and is in the same direction with the inclination direction of the inner surface layer and the middle coating layer A.
To verify the good results of the coatings of the present invention, a verification is made by the following comparative examples.
(1) And carrying out a cold-hot alternation high-temperature water vapor corrosion test on the multilayer coating, carrying out cycle test for 15 times by adopting cold-hot alternation and water vapor corrosion at 40-800 ℃, observing the surface state, and displaying the test result:
example 1 the coating showed no cracking in 15 tests; comparative example 1 exhibited cracking at cycle 7; comparative example 2 exhibited cracking at cycle 11; comparative example 3 exhibited cracks at the 9 th time. It can be seen that the multilayer structure of the present invention is more effective in preventing cracks.
(2) The corrosion resistance was tested using the sulfate corrosion test method known in the art, using Na2SO4And K2SO4As corrosion medium, Na in the test2SO4And K2SO4Preparing saturated salt solution according to the mass ratio of 19:1, dipping the saturated salt solution by a brush before an experiment, and uniformly brushing the saturated salt solution on the surface of a sample, wherein the salt coating amount is 2-4mg/m2And in the test, the dried and weighed sample is placed in a muffle furnace for test, the sample is taken out and weighed every 24 hours, and the test is carried out in a circulating mode. And (3) calculating the corrosion degree of the sample by adopting a weight gain method, wherein the test calculation formula is as follows:
W＝((WS+2-WS)/A)-((WS+1-WS)/A)*δ
wherein W is the weight gain of the unit area of the S-th corrosion; wSQuality of the sample before the S-th etching, WS+1Quality after S time salting, WS+2The mass of the second etching is the mass of the second etching; a is the sample surface area, δ is the coefficient after subtracting the water of salt film crystallization, δ is 0.47.
The test subjects of example 1 and comparative examples 4 to 6 were selected, the corrosion test was conducted at 500 ℃, and the weight gain rates of example 1, comparative example 4 and comparative example 5, respectively, were 0.0254mg/cm by linear fitting2,0.0387mg/cm2,0.0439mg/cm2,0.0294mg/cm2It can be seen that the corrosion resistance of the sprayed coating according to the present invention is about 1.5 times, 1.7 times and 1.16 times that of the comparative examples 4 and 5, respectively, and the corrosion resistance effect of the technical solution of the present invention is more prominent.
The above examples are merely illustrative for clearly illustrating the present invention and are not intended to limit the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any obvious variations or modifications which come within the spirit and scope of the invention are desired to be protected by the following claims.

Claims (6)

1. A coating with a multilayer structure for a boiler heating surface is characterized in that the multilayer structure comprises five layers, namely an inner surface layer, a middle coating A, a middle coating B, a middle coating C and an outer surface layer, wherein the inner surface layer is positioned on the boiler heating surface, the outer surface layer is positioned on the outermost layer of the coating, the middle coating A, the middle coating B and the middle coating C are positioned between the inner surface layer and the outer surface layer, the middle coating A is coated on the inner surface layer, the middle coating B is coated on the middle coating A, and the middle coating C is coated between the middle coating B and the outer surface layer;
the connecting layer surface of the inner surface layer and the middle coating layer A is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 10-20 degrees; the middle coating B is a horizontal coating; the connection layer of the outer surface layer and the middle coating layer C is a non-horizontal plane, and compared with the horizontal plane, the inclination angle is 10-20 degrees and is opposite to the inclination direction of the inner surface layer and the middle coating layer A.
2. The coating layer having a multi-layered structure as claimed in claim 1, wherein said inner surface layer is Si3N4the/BN composite ceramic coating.
3. The coating layer having a multi-layered structure according to claim 1, wherein said outer surface layer comprises alumina, zirconium silicate, zirconia, TiO2。
4. Coating with a multilayer structure according to claim 1, characterized in that the intermediate coating A and the outer surface layer have the same coating structure.
5. The coating layer having a multi-layer structure according to claim 1, wherein the intermediate coating layer B and the inner surface layer have the same coating structure.
6. Coating with a multilayer structure according to claim 1, characterized in that the intermediate coating C is TiC/Si3N4And (4) coating.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN205079212U (en) * 2015-10-28 2016-03-09 江苏中科重工股份有限公司 Boiler is used in power station
CN205640982U (en) * 2016-05-18 2016-10-12 中国大唐集团科学技术研究院有限公司 Boiler water wall pipe with abrasionproof explosion -proof ability
JP2018109466A (en) * 2016-12-28 2018-07-12 株式会社Ihi Coating layer and method of forming the same
CN109280875A (en) * 2018-10-12 2019-01-29 中国科学院青岛生物能源与过程研究所 A kind of boiler heating surface corrosion-resistant coating structure
CN210736866U (en) * 2019-06-27 2020-06-12 东方电气集团东方锅炉股份有限公司 Water-cooled wall anticorrosive coating structure of garbage/biomass boiler

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN205079212U (en) * 2015-10-28 2016-03-09 江苏中科重工股份有限公司 Boiler is used in power station
CN205640982U (en) * 2016-05-18 2016-10-12 中国大唐集团科学技术研究院有限公司 Boiler water wall pipe with abrasionproof explosion -proof ability
JP2018109466A (en) * 2016-12-28 2018-07-12 株式会社Ihi Coating layer and method of forming the same
CN109280875A (en) * 2018-10-12 2019-01-29 中国科学院青岛生物能源与过程研究所 A kind of boiler heating surface corrosion-resistant coating structure
CN210736866U (en) * 2019-06-27 2020-06-12 东方电气集团东方锅炉股份有限公司 Water-cooled wall anticorrosive coating structure of garbage/biomass boiler

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