CN107663620B - Composite material for preparing metal-based heat-insulating coating - Google Patents
Composite material for preparing metal-based heat-insulating coating Download PDFInfo
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- CN107663620B CN107663620B CN201710812704.2A CN201710812704A CN107663620B CN 107663620 B CN107663620 B CN 107663620B CN 201710812704 A CN201710812704 A CN 201710812704A CN 107663620 B CN107663620 B CN 107663620B
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
Abstract
A composite material for preparing a metal-based heat-insulating coating belongs to the technical field of surface coatings. At least two kinds of powders are included; the main body is Fe-Cr-Nb-B-Si alloy powder, the added second powder component is iron-based amorphous alloy powder, and the iron-based amorphous alloy powder comprises at least one metal element except iron element and at least one non-metal element with the mol percentage content of 5-25%; the metal elements except the iron element in the iron-based amorphous alloy powder are selected from transition groups or/and rare earth. The metal-based composite material provided by the invention can be prepared by adopting a traditional atmospheric plasma spraying method. The metal-based coating prepared by the invention has extremely low thermal conductivity (<1.6W/mK) close to that of a zirconia solid material, and the thermal expansion coefficient is higher than that of the traditional zirconia thermal barrier coating, so that the metal-based coating can be used in the field of medium and low temperature heat resistance or heat insulation protection.
Description
Technical Field
The invention belongs to the field of thermal protection coatings, and particularly relates to a composite material capable of being applied to preparation of a metal-based thermal insulation protection coating.
Background
Currently, the research on surface thermal barrier coatings has mainly focused on ceramic barrier coatings (TBCs) and has been widely used in aeroengines. Typically yttria-stabilized zirconia (YSZ, ZrO) prepared by plasma spray or physical vapor deposition techniques2/6-8Y2O3) The thermal conductivity of the coating can reach below 1W/mK, so that the engine blade is effectively protected and can stably run at high temperature. Compared with the high-temperature working environment of an aeroengine, the working temperature in the cylinder body of the automobile engine is lower, the service temperature of a typical gasoline engine hot end material is usually not more than 500 ℃, and therefore the metal-based material is feasible to prepare the heat-insulating protective coating. Meanwhile, the metal-based material has better toughness and better thermal matching property with the base material, and can effectively make up for the defects of the ceramic coating.
In addition, in recent years, waste heat recycling is also getting more and more attention, a great deal of thermoelectric technology is actively developed, and according to the statistics of the united states energy agency, nearly 6 energy resources are dissipated in the form of waste heat every year, wherein the waste heat generated by an automobile engine accounts for a large proportion, so that some automobile manufacturers are engaged in developing and developing thermoelectric module systems which are arranged in an automobile exhaust pipe and used for waste heat power generation. However, the thermoelectric module is usually connected to the thermoelectric material and the metal layer by diffusion bonding, so that atomic diffusion between them is easily generated, and intermetallic phases are generated under the thermal action, thereby destroying the reliability of the thermoelectric module.
Based on the application requirements, the application provides a composite material for preparing a metal-based heat-insulating protective coating. The existing preparation methods of the coating are many, wherein, Atmospheric Plasma Spraying (APS) has the distinct technical characteristics, including wide spraying material range, the material from low melting point to high melting point can be sprayed, the requirement on the granularity of the sprayed powder is not high, the porosity of the coating is low, and oxide inclusions are few, so the method is one of the effective methods for preparing the metal-based heat-insulating coating.
Through retrieval, at present, no related technical patent report of preparing the iron-based amorphous/amorphous composite heat-insulating coating by using the metal-based composite material and an Atmospheric Plasma Spraying (APS) method is available.
Disclosure of Invention
The invention aims to provide a composite material for preparing a metal-based heat insulation coating with low thermal conductivity.
A composite powder material for producing a metal-based thermal barrier coating, characterized by: at least two kinds of powders are included; the main body is Fe-Cr-Nb-B-Si series alloy powder, and the mole percentage content (or at.%) range of the element components in the Fe-Cr-Nb-B-Si series alloy powder is as follows: 6-8% of Cr; 4-5% of Nb; 5-7% of Si; 18-22% of B; fe and inevitable impurities: the balance; the second powder component is iron-based amorphous alloy powder, and the iron-based amorphous alloy powder comprises at least one metal element (transition group and rare earth) except iron element and at least one non-metal element with the mol percentage content of 5-25%.
The metal elements except the iron element in the iron-based amorphous alloy powder are selected from transition groups or/and rare earth, and the metal elements are selected from: one or more of iron (Fe), chromium (Cr), molybdenum (Mo), cobalt (Co), tungsten (W), niobium (Nb), manganese (Mn) and yttrium (Y).
The nonmetal elements are selected from one or more of boron (B), carbon (C), silicon (Si) and phosphorus (P).
The grain diameter ranges of the Fe-Cr-Nb-B-Si series alloy powder and the iron-based amorphous alloy powder are as follows: 25-70 μm; both powders can be prepared by nitrogen atomization.
The mass ratio of the Fe-Cr-Nb-B-Si alloy powder to the iron-based amorphous alloy powder is 1-1.5.
The amorphous/amorphous composite metal-based heat-insulating coating can be prepared by adopting the composite powder material.
The preparation method of the metal-based heat insulation coating with low thermal conductivity is characterized by comprising the following steps:
step 1, selecting an industrial alloy and a pure metal block as raw materials for preparing two kinds of powder, and finally preparing the two kinds of powder with good sphericity and granularity ranging from 25 to 70 mu m by adopting a nitrogen atomization method;
step 2, mixing two powder materials according to a mass ratio of 1-1.5: 1 preparing and mixing the materials into a composite powder material;
and 3, preparing the iron-based amorphous/amorphous composite coating on the metal matrix from the composite powder obtained in the step 2 by adopting an atmospheric plasma spraying process, wherein the spraying process parameters are as follows: current of 700-750A, argon flow: 35-40L/min, hydrogen flow: 6-8L/min, powder feeding rate: 60-70 g/min, spraying distance: 100 mm.
The metal matrix in the step 3 is preferably an aluminum alloy matrix.
The iron-based amorphous/amorphous composite coating with lower thermal conductivity is prepared by the method.
The low thermal conductivity of the iron-based coating prepared by the atmospheric plasma spraying method is mainly determined by the reasonable allocation of the self components and the two alloy powders. The function is as follows:
amorphous structure characteristics: the atomic sizes of metal elements such as iron, chromium, molybdenum, cobalt, tungsten, niobium, manganese, yttrium and the like are greatly different from those of non-metal elements such as boron, carbon, silicon, phosphorus and the like, and the components have large negative mixing heat, so that the amorphous forming capability of an alloy system can be effectively improved to obtain the amorphous structural characteristic. The structure can increase the scattering effect of the heat transfer medium, inhibit the heat transfer of electrons and phonons and further reduce the overall heat conductivity. In addition, the amorphous structure characteristic can effectively improve the wear resistance and corrosion resistance of the coating.
Amorphous/amorphous composite coating structure: the amorphous structure has a good effect of inhibiting heat transfer, but the amorphous and amorphous composite coating structure of different cluster groups can also increase the scattering effect of a heterogeneous phase interface on phonons and electrons, and the purpose of further reducing the thermal conductivity of the coating is realized.
The overall thermal insulation effect of the metal-based composite coating is mainly obtained by the cooperation of the two powder components themselves and the reasonable arrangement between them, and is not determined by any single element, but is absent and certainly not obtained by only limited experiments.
Compared with the conventional ceramic-based thermal barrier coating, the iron-based thermal barrier coating has the following characteristics:
1. the thermal conductivity is low and can be lower than 1.6W/mK;
2. the thermal conductivity of the composite coating can still be maintained at 2W/mK at 400 ℃;
3. the metal-based coating shows relatively good toughness, and can effectively make up for the defects of the ceramic coating;
4. compared with ceramic-based heat-insulating coating, the metal substrate has better thermal expansion matching property, about 15 multiplied by 10-6The temperature is lower than the temperature, the preparation process is simplified (no bonding layer is needed), and the cost is reduced;
5. the atmospheric plasma spraying process adopted by the invention is simple to operate, the particle size range of the sprayed powder is wide, and the cost is lower compared with other powder spraying methods;
6. the amorphous/amorphous coating prepared by the invention has lower thermal conductivity while keeping better coating microstructure and high hardness, and can be applied to medium and low temperature heat insulation protection.
Drawings
FIG. 1 is an SEM feature morphology of the iron-based alloy composite powder prepared in example 4;
FIG. 2 XRD pattern of amorphous/amorphous composite coating prepared in example 4;
fig. 3 illustrates typical morphology features of the amorphous/amorphous composite coating OM prepared in example 4;
figure 4 differential thermal analysis (DSC) of the amorphous/amorphous composite coating prepared in example 4.
The specific implementation mode is as follows:
the essential features and the significant advantages of the invention are further elucidated below by means of examples, which are by no means limited to the embodiments described.
The method for preparing the iron-based amorphous/amorphous composite coating with lower thermal conductivity comprises the following steps:
1. selecting an industrial grade alloy material as a raw material, respectively preparing alloy powder by a high-pressure nitrogen gas atomization method, and collecting and screening the powder of 40-70 mu m for preparing a composite powder material.
2. Preparing the powder in the step 1 into a heat-insulating coating by adopting an atmospheric plasma spraying method, wherein the spraying process parameters are as follows: current of 700-750A, argon flow: 35-40L/min, hydrogen flow: 6-8L/min, powder feeding rate: 60-70 g/min, spraying distance: 100mm, and the thickness of the coating is 400-500 μm.
The metal matrix in the step 2 is preferably an aluminum alloy matrix, and the matrix material is subjected to pretreatment such as cleaning and sand blasting before spraying.
Example 1
The atomic percentages of elements in main alloy components Fe-Cr-Nb-B-Si in the composite alloy powder are as follows: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance. The second alloy component added is Fe-B-Y, and the atomic percentages of the elements are as follows: b, 22 percent; 6 percent of Y; fe and inevitable impurities: and (4) the balance. The arrangement ratio of alloy 1 to alloy 2 is 1.2
Example 2
The atomic percentages of elements in main alloy components Fe-Cr-Nb-B-Si in the composite alloy powder are as follows: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance. The second alloy component added is Fe-Mo-C-B, and the atomic percentages of the elements are as follows: b, 6 percent; 15 percent of C; 14 percent of Mo; fe and inevitable impurities: and (4) the balance. The set ratio of alloys 1 and 2 was 1.2.
Example 3
The atomic percentages of elements in main alloy components Fe-Cr-Nb-B-Si in the composite alloy powder are as follows: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance. The second alloy component added is Fe-Cr-Mo-C-B, and the atomic percentages of the elements are as follows: b, 6 percent; 15 percent of C; 14 percent of Mo; 15 percent of Cr; fe and inevitable impurities: and (4) the balance. The arrangement ratio of alloy 1 to alloy 2 is 1.5
Example 4
The atomic percentages of elements in main alloy components Fe-Cr-Nb-B-Si in the composite alloy powder are as follows: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance. The second alloy component added is Fe-Cr-Mo-C-B-Y, and the atomic percentages of the elements are as follows: b, 6 percent; 15 percent of C; 14 percent of Mo; 15 percent of Cr; y is 2 percent; fe and inevitable impurities: and (4) the balance. The set ratio of alloys 1 and 2 was 1.2.
Example 5
The atomic percentages of elements in main alloy components Fe-Cr-Nb-B-Si in the composite alloy powder are as follows: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance. The second alloy component added is Fe-Cr-Mo-C-B-Y, and the atomic percentages of the elements are as follows: b, 6 percent; 15 percent of C; 14 percent of Mo; 15 percent of Cr; y is 2 percent; fe and inevitable impurities: and (4) the balance. The set ratio of alloys 1 and 2 was 1.5.
Example 6
The atomic percentages of elements in main alloy components Fe-Cr-Nb-B-Si in the composite alloy powder are as follows: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance. The second alloy component added is Fe-Co-Cr-Mo-C-B-Y, and the atomic percentages of the elements are as follows: b, 6 percent; 15 percent of C; 14 percent of Mo; 15 percent of Cr; y is 2 percent; 7 percent of Co; avoiding impurities: and (4) the balance. The arrangement ratio of alloy 1 to alloy 2 is 1.2
Comparative example 1
The iron-based alloy Fe-Cr-Nb-B-Si powder comprises the following elements in atomic percentage: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance.
Comparative example 2
The atomic percentages of the elements in the Fe-Co-Cr-Mo-C-B-Y powder of the iron-based alloy are as follows: b, 6 percent; 15 percent of C; 14 percent of Mo; 15 percent of Cr; y is 2 percent; 7 percent of Co; avoiding impurities: and (4) the balance.
Comparative example 3
The atomic percentages of elements in main alloy components Fe-Cr-Nb-B-Si in the composite alloy powder are as follows: 6.5 percent of Cr; 4.5 percent of Nb; 5 percent of Si; 20 percent of B; fe and inevitable impurities: and (4) the balance. The second alloy component added is Fe-Cr-Mo-C-B-Y, and the atomic percentages of the elements are as follows: b, 6 percent; 15 percent of C; 14 percent of Mo; 15 percent of Cr; y is 2 percent; fe and inevitable impurities: and (4) the balance. The arrangement ratio of alloys 1 and 2 was 2.0.
XRD, OM, SEM, DSC and microhardness tests are carried out on the coatings prepared by the various examples; carrying out porosity analysis by adopting IMAGE J IMAGE analysis software; the thermal conductivity of the coatings prepared in each example was analyzed using a laser thermal analyzer.
TABLE 1 porosity, DSC, and microhardness results for examples 1-6 and comparative examples 1-3
Table 2 thermal conductivity results for examples and comparative examples
TABLE 3 typical Metal/alloy thermal conductivities (approximate values)
Claims (7)
1. A composite powder material for producing a metal-based thermal barrier coating, characterized by: at least two kinds of powders are included; the main body is Fe-Cr-Nb-B-Si alloy powder, and the molar percentage content ranges of the element components in the Fe-Cr-Nb-B-Si alloy powder are as follows: 6-8% of Cr; 4-5% of Nb; 5-7% of Si; 18-22% of B; fe and inevitable impurities: the balance; the second powder component is iron-based amorphous alloy powder, the iron-based amorphous alloy powder comprises at least one metal element except for iron element and at least one non-metal element with the mol percentage of 5-25%, and the metal element is selected from transition group or/and rare earth.
2. A composite powder material for producing a metal-based thermal barrier coating according to claim 1, wherein: the metal elements other than the iron element in the iron-based amorphous alloy powder are selected from one or more of chromium (Cr), molybdenum (Mo), cobalt (Co), tungsten (W), niobium (Nb), manganese (Mn) and yttrium (Y).
3. A composite powder material for producing a metal-based thermal barrier coating according to claim 1, wherein: the nonmetal elements are selected from one or more of boron (B), carbon (C), silicon (Si) and phosphorus (P).
4. A composite powder material for producing a metal-based thermal barrier coating according to claim 1, wherein: the grain diameter ranges of the Fe-Cr-Nb-B-Si series alloy powder and the iron-based amorphous alloy powder are as follows: 25 to 70 μm.
5. A composite powder material for producing a metal-based thermal barrier coating according to claim 1, wherein: the mass ratio of the Fe-Cr-Nb-B-Si alloy powder to the iron-based amorphous alloy powder is 1-1.5.
6. Use of the composite powder material according to any one of claims 1 to 5 for the preparation of amorphous/amorphous composite metal based thermal barrier coatings.
7. A metal-based thermal barrier coating prepared using the composite powder material of any one of claims 1 to 5.
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| CN110029300B (en) * | 2019-04-01 | 2021-10-08 | 江西省科学院应用物理研究所 | Composite manufacturing method of acid leaching stirrer |
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| CN114000088A (en) * | 2021-11-05 | 2022-02-01 | 华电重工股份有限公司 | Coating for field protection of water wall pipe of power station boiler and preparation method thereof |
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