CN112813432B - Preparation method of metallic matrix amorphous coating - Google Patents
Preparation method of metallic matrix amorphous coating Download PDFInfo
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- CN112813432B CN112813432B CN202011629202.4A CN202011629202A CN112813432B CN 112813432 B CN112813432 B CN 112813432B CN 202011629202 A CN202011629202 A CN 202011629202A CN 112813432 B CN112813432 B CN 112813432B
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- 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
- C23C18/16—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 reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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Abstract
The invention provides a preparation method of a metal matrix amorphous coating, which comprises the following steps: chemically plating amorphous powder to generate a layer of gold on the surface of the amorphous powderPreparing amorphous metal composite powder from the metal layer, wherein the electric conductivity range of the metal layer is 9.93 to 106~6.3*107s/m; uniformly paving the amorphous metal composite powder on the surface of a metal matrix, and paving a layer of metal foil on the surface of the amorphous metal composite powder layer to generate a workpiece to be welded; and carrying out resistance cladding on the workpiece to be welded so as to weld the amorphous metal composite powder layer on the surface of the metal matrix. Compared with the traditional amorphous coating preparation method, the amorphous coating prepared by the invention has the advantages of low crystallization rate, high amorphous content, small heat influence on a matrix, high bonding strength of amorphous powder and a metal matrix, few coating defects, good compactness, simple and easy preparation method, less material consumption and low cost, and is convenient to popularize and apply in related industrial fields.
Description
Technical Field
The invention relates to the field of amorphous coating preparation, in particular to a preparation method of a metal matrix amorphous coating.
Background
The amorphous alloy has the characteristics of high strength, high hardness, good toughness, wear resistance, corrosion resistance and the like. Meanwhile, the magnetic material also has good high magnetic permeability and good magnetism and other excellent material properties, so that the magnetic material is widely concerned. Since it is difficult to prepare bulk amorphous coating at present, the application of amorphous alloy is generally expanded by preparing amorphous coating on the surface of metal substrate.
At present, the main methods for preparing the amorphous alloy coating on the surface of the metal matrix comprise laser cladding and thermal spraying, but have more or less defects. The coating prepared by thermal spraying has the defects of low bonding strength with a metal substrate, a large amount of pores in the coating and the like. The laser cladding is to melt the amorphous alloy by irradiating the laser beam with high energy density, the high temperature in the cladding process can cause the burning loss of easily oxidized simple substance elements such as Si and B, so that the amorphous content is greatly reduced, the defects of holes and cracks, easiness in cracking, uneven structure, poor comprehensive corrosion and wear resistance and the like are easy to occur, and the laser beam with high energy density can directly cause the change of the structure and the performance of the matrix.
The technical problem to be solved by the invention is to provide a method for preparing an amorphous coating, which has the advantages of few defects, good compactness, high amorphous content, small heat influence on a matrix, simplicity and easiness, and can be industrially produced, aiming at the defects of the existing method for preparing the amorphous coating.
Disclosure of Invention
The invention aims to provide a preparation method of an amorphous coating of a metal matrix, which aims to solve the problems of low bonding strength, low compactness, low amorphous content and poor comprehensive corrosion and wear resistance of the method for preparing the amorphous alloy coating on the surface of the metal matrix in the prior art.
The invention provides a preparation method of a metal matrix amorphous coating, which comprises the following steps:
carrying out chemical plating on amorphous powder, and generating a metal layer on the surface of the amorphous powder after the chemical plating to prepare amorphous metal composite powder, wherein the conductivity of the metal layer is 9.93 x 106~6.3*107s/m;
Uniformly paving the amorphous metal composite powder on the surface of a metal matrix, and paving a layer of metal foil on the surface of the amorphous metal composite powder layer to generate a workpiece to be welded;
and carrying out resistance cladding on the workpiece to be welded so as to enable the amorphous metal composite powder layer to be cladded on the surface of the metal matrix.
The preparation method of the metal matrix amorphous coating provided by the invention has the following beneficial effects:
compared with the traditional amorphous coating preparation method, the amorphous coating prepared by the invention has the advantages of low amorphous crystallization rate, high amorphous content, small heat influence on a matrix, high bonding strength of amorphous powder and a metal matrix, few coating defects, simple and easy preparation method, less material consumption and low cost, and is convenient to popularize and apply in related industrial fields.
The amorphous powder has the performances of high wear resistance, corrosion resistance and the like, and the metal layer with high conductivity is chemically plated on the surface of the amorphous powder, so that the resistance of the amorphous powder can be reduced, the resistance heat generated in the subsequent welding process is reduced, the heat of the resistance heat is very low, the heat influence on a matrix is small, and the amorphous crystallization rate is favorably reduced; and then welding the amorphous metal composite powder on the surface of the metal matrix by using a resistance cladding technology to form a wear-resistant corrosion-resistant coating, wherein the bonding performance of the metal thin layer plated on the surface of the amorphous powder and the metal matrix is good, so that the bonding strength of the amorphous powder and the metal matrix is enhanced, and the compactness of the amorphous powder on the metal matrix can be good through the rolling action of the electrode wheel by using the resistance cladding technology.
In addition, the preparation method of the metal matrix amorphous coating provided by the invention can also have the following additional technical characteristics:
further, the amorphous powder is subjected to chemical plating to generate a metal layer on the surface of the amorphous powder, so that the amorphous metal composite powder is prepared, wherein the conductivity range of the metal layer is 9.93-106~6.3*107The step of s/m comprises:
and pouring the amorphous powder into a plating solution, keeping the constant temperature and continuously stirring, fishing out and drying for later use after a layer of compact high-conductivity metal plated layer is generated on the surface of the amorphous powder, and thus obtaining the amorphous metal composite powder.
Further, the step of resistance cladding the workpiece to be welded to clad the amorphous metal composite powder layer on the surface of the metal matrix comprises:
and turning on a power supply, adjusting the welding pressure, the welding speed and the welding current of the resistance cladding machine, placing the workpiece to be welded between two electrode wheels of the resistance cladding machine, and welding the amorphous metal composite powder layer on the surface of the metal matrix by rolling the surface of the workpiece to be welded.
Further, the amorphous powder is subjected to chemical plating to generate a metal layer on the surface of the amorphous powder, so that the amorphous metal composite powder is prepared, wherein the conductivity range of the metal layer is 9.93-106~6.3*107Before the step of s/m, the preparation method further comprises the following steps:
and carrying out pretreatment of oil removal, sensitization and activation on the amorphous powder.
Further, before the step of uniformly spreading the amorphous metal composite powder on the surface of the metal matrix and then spreading a layer of metal foil on the surface of the amorphous metal composite powder layer to generate the workpiece to be welded, the preparation method further comprises the following steps:
pretreating the surface of the metal substrate: and (3) polishing the metal matrix by using sand paper, and cleaning by using acetone to remove an oxide film and oil stain impurities on the surface.
Further, after the step of resistance cladding the workpiece to be welded to clad the amorphous metal composite powder layer on the surface of the metal matrix, the preparation method further comprises:
and removing the metal foil on the surface of the amorphous metal composite powder layer.
Furthermore, the particle size of the amorphous powder is 10-100 μm.
Further, the plating solution is a metal salt solution.
Further, the resistance cladding machine comprises a medium-frequency inverter, an alternating-current frequency converter, a single-phase alternating current or a transverse and longitudinal resistance cladding machine, the pulse current frequency of the resistance cladding machine is 10-1000 HZ, the pulse current is 1-10 kA, the welding pressure is 1-100 kN, and the welding speed is 0.1-10 m/min.
Further, the metal foil is a stainless steel sheet or a nickel-based foil.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a circuit diagram of a method for forming an amorphous coating on a metal substrate according to an embodiment of the present invention;
FIG. 2 is an optical microscope photograph of the iron-based amorphous/copper composite powder after copper plating;
FIG. 3 is a scanning electron microscope image of the iron-based amorphous coating after copper plating;
FIG. 4 is a TEM bright field of a copper-plated amorphous coating;
fig. 5 is a graph of the HRTEM state and FFT transition for region B of fig. 4.
Detailed Description
In order to make the objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. Several embodiments of the invention are presented in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
As shown in fig. 1 to 5, an embodiment of the present invention provides a method for preparing an amorphous coating on a metal substrate, including steps S101 to S103:
s101: carrying out chemical plating on amorphous powder, and generating a metal layer on the surface of the amorphous powder after the chemical plating to prepare amorphous metal composite powder, wherein the electric conductivity range of the metal layer is 9.93 x 106~6.3*107s/m。
The amorphous powder can be amorphous powder of different series and types, is not limited in shape, and has the granularity of 10-100 mu m.
The metal layer can be made of iron, cobalt, chromium and the like, and the resistivity of the metal layer is 1.65 x 10-8~9.78*10-8(Ω · m) is a high conductivity material.
Chemically plating the amorphous powder to generate a metal layer on the surface of the amorphous powder to prepare amorphous metal composite powder, wherein the metal isThe conductivity of the layer ranged from 9.93 x 106~6.3*107The step of s/m comprises:
pouring the amorphous powder into a plating solution, keeping constant temperature and continuously stirring, taking out and drying for later use after a layer of compact high-conductivity metal plating layer is generated on the surface of the amorphous powder, and thus obtaining the amorphous metal composite powder, wherein the plating solution is a metal salt solution, can be a copper salt solution such as CuSO4, CuCl2 or Cu (NO3)2, and can also be a nickel salt solution, a silver salt solution and the like.
Performing chemical plating on the amorphous powder to generate a metal layer on the surface of the amorphous powder to prepare the amorphous metal composite powder, wherein the electric conductivity range of the metal layer is 9.93 to 106~6.3*107Before the step of s/m, the preparation method further comprises the following steps:
and carrying out pretreatment of oil removal, sensitization and activation on the amorphous powder.
S102: and uniformly paving the amorphous metal composite powder on the surface of the metal matrix, and paving a layer of metal foil on the surface of the amorphous metal composite powder layer to generate a workpiece to be welded.
The thickness of the amorphous metal composite powder is 100-1500 mu m, the metal foil is a high-melting-point metal foil such as a stainless steel sheet or a nickel-based foil, the metal matrix can be alloy plates of different types and different types, such as a 304 stainless steel plate, a 45 steel plate, an aluminum alloy plate and the like, the plate width is 5-500 mm, the thickness is 5-100 mm, and the plate length is not limited.
Before the step of uniformly paving the amorphous metal composite powder on the surface of the metal matrix and paving a layer of metal foil on the surface of the amorphous metal composite powder layer to generate a workpiece to be welded, the preparation method further comprises the following steps:
pretreating the surface of the metal substrate: and (3) polishing the metal matrix by using sand paper, and cleaning by using acetone to remove an oxide film and oil stain impurities on the surface.
S103: and carrying out resistance cladding on the workpiece to be welded so as to enable the amorphous metal composite powder layer to be cladded on the surface of the metal matrix.
The resistance cladding of the workpiece to be welded is carried out, so that the amorphous metal composite powder layer is clad on the surface of the metal matrix, and the method comprises the following steps:
and turning on a power supply, adjusting the welding pressure, the welding speed and the welding current of the resistance cladding machine, placing the workpiece to be welded between two electrode wheels of the resistance cladding machine, and welding the amorphous metal composite powder layer on the surface of the metal matrix by rolling the surface of the workpiece to be welded. The rolling process of the electrode wheel can ensure that the compactness of the amorphous metal composite powder on the metal matrix is good.
The resistance cladding machine comprises a medium-frequency inverter, an alternating-current frequency converter, a single-phase alternating current or a transverse and longitudinal resistance cladding machine, the pulse current frequency of the resistance cladding machine is 10-1000 HZ, the pulse current is 1-10 kA, the welding pressure is 1-100 kN, and the welding speed is 0.1-10 m/min.
After the step of performing resistance cladding on the workpiece to be welded to enable the amorphous metal composite powder layer to be cladded on the surface of the metal matrix, the preparation method further comprises the following steps:
and removing the metal foil on the surface of the amorphous metal composite powder layer.
The technology for preparing the amorphous coating by resistance cladding is a cladding method which is characterized in that a workpiece to be welded is arranged between two disc-shaped electrodes, after electrification, current flows through the contact surfaces of the laid amorphous powder and the amorphous powder and a metal matrix to generate resistance heat, so that the amorphous powder and the metal matrix reach a melting or plastic state, and meanwhile, the amorphous powder is pressed and rolled, so that the amorphous powder is continuously and tightly welded on the surface of the metal matrix.
Some specific implementations of this embodiment further include:
(1) amorphous powder pretreatment: and carrying out oil removal, sensitization and activation treatment on the amorphous powder.
(2) Chemical plating process: pouring the pretreated amorphous powder into a plating solution, keeping constant temperature and continuously stirring, and fishing out and drying for later use after a compact metal layer is generated on the amorphous surface.
(3) Surface pretreatment of a metal substrate: and (3) polishing the metal substrate by using sand paper, and cleaning the metal substrate by using acetone to remove impurities such as an oxide film, oil stains and the like on the surface.
(4) Preparation of a welding sample: and uniformly paving the chemically plated amorphous/metal composite powder on the surface of the alloy matrix in a certain thickness, and paving a layer of high-melting-point metal foil on the surface of the powder layer to serve as a welding sample as a whole for protecting an electrode of resistance cladding equipment.
(5) Resistance cladding: and (4) switching on a power supply, adjusting to proper welding pressure, welding speed and welding current, placing the sample prepared in the step (4) below an electrode wheel, and welding the amorphous alloy mixed powder on the surface of the alloy substrate along with the rotation of the electrode wheel.
(6) And (3) post-treatment: removing the metal foil on the surface of the coating.
In summary, the preparation method of the metal matrix amorphous coating provided by the invention has the beneficial effects that: compared with the traditional amorphous coating preparation method, the amorphous coating prepared by the invention has the advantages of low amorphous crystallization rate, high amorphous content, small heat influence on a matrix, high bonding strength of amorphous powder and a metal matrix, few coating defects, simple and easy preparation method, less material consumption and low cost, and is convenient to popularize and apply in related industrial fields.
The amorphous powder has the performances of high wear resistance, corrosion resistance and the like, and the metal layer with high conductivity is chemically plated on the surface of the amorphous powder, so that the resistance of the amorphous powder can be reduced, the resistance heat generated in the subsequent welding process is reduced, the heat of the resistance heat is very low, the heat influence on a matrix is small, and the amorphous crystallization rate is favorably reduced; and then welding the amorphous metal composite powder on the surface of the metal matrix by using a resistance cladding technology to form a wear-resistant corrosion-resistant coating, wherein the bonding performance of the metal thin layer plated on the surface of the amorphous powder and the metal matrix is good, so that the bonding strength of the amorphous powder and the metal matrix is enhanced, and the compactness of the amorphous powder on the metal matrix can be good through the rolling action of the electrode wheel by using the resistance cladding technology.
Example 2
Fe-based amorphous powder is prepared on the surface of 304 stainless steel, the prepared amorphous powder comprises Fe-Co-Cr-Mo-C-B-Y, the granularity is about 50 mu m, the amorphous powder is spherical powder, and the plating solution is copper sulfate solution.
Firstly, putting 300-400 meshes of Fe-based amorphous powder into NaOH solution for degreasing, then taking out, pouring the prepared sensitizing solution into the Fe-based amorphous powder subjected to degreasing treatment, fully stirring for 30min, filtering and drying after the powder is completely settled, and obtaining the sensitized Fe-based amorphous powder.
And pouring the prepared activating solution into the sensitized Fe-based amorphous powder, fully stirring for 10min, filtering after the powder is completely settled, and cleaning for 3 times by using distilled water after filtering to obtain the activated Fe-based amorphous powder, wherein the activating solution is 2g/L of AgNO3 solution.
Pouring the activated Fe-based amorphous powder into a prepared copper sulfate solution, ensuring a constant temperature environment of 60 ℃ in water bath, simultaneously starting an electric stirrer to stir, adding a proper NaOH solution to adjust the pH value to be alkaline, starting a copper plating reaction until no bubbles are generated when bubbles are generated in the plating solution, finishing the reaction, settling and filtering after the reaction is finished, cleaning for 3 times by using distilled water, and drying to form Fe-based amorphous/copper composite powder, wherein an optical microscope picture of the Fe-based amorphous/copper composite powder is shown in figure 2, and the surface of the powder is coated with a copper film.
Polishing 304 stainless steel with the thickness of 2mm, the width of 25mm and the length of 150mm by 400-mesh abrasive paper, and then cleaning by acetone to remove impurities such as an oxide film, oil stains and the like on the surface; and (3) spreading the copper-plated Fe-based amorphous/copper composite powder on the surface of a metal matrix, wherein the spreading thickness is 0.5mm, and simultaneously spreading a metal foil with the thickness of 50 mu m on the Fe-based amorphous/copper composite powder layer to form a workpiece to be welded, wherein the metal matrix is a 304 stainless steel plate, and the metal foil is a 304 stainless steel sheet.
Placing a workpiece to be welded between two electrode wheels, starting a power supply, using an HBF intermediate frequency cladding machine, adjusting welding currents 24A and 27A, adjusting welding pressure to be 0.4MPa, and adjusting the ratio of welding time to rest time to be 5: and 1, welding the Fe-based amorphous/copper composite powder layer on the surface of the metal matrix to generate an amorphous coating on the surface of the metal matrix, tearing off the metal foil after welding, and preparing the Fe-based amorphous coating by a resistance cladding method, wherein a scanning electron microscope image of the Fe-based amorphous coating is shown in figure 3, the Fe-based amorphous coating and the metal matrix have good interface, and no obvious defect exists in the coating.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The preparation method of the metal matrix amorphous coating is characterized by comprising the following steps of:
carrying out chemical plating on the amorphous powder to generate a metal layer on the surface of the amorphous powder to prepare the amorphous metal composite powder, wherein the electric conductivity range of the metal layer is 9.93 x 106~6.3*107s/m;
Uniformly paving the amorphous metal composite powder on the surface of a metal matrix, and paving a layer of metal foil on the surface of the amorphous metal composite powder layer to generate a workpiece to be welded;
performing resistance cladding on the workpiece to be welded so as to weld the amorphous metal composite powder layer on the surface of the metal matrix;
performing chemical plating on the amorphous powder to generate a metal layer on the surface of the amorphous powder to prepare the amorphous metal composite powder, wherein the electric conductivity range of the metal layer is 9.93 to 106~6.3*107The step of s/m comprises:
pouring the amorphous powder into a plating solution, keeping a constant temperature and continuously stirring, taking out and drying for later use after a layer of compact high-conductivity metal plated layer is generated on the surface of the amorphous powder, and thus obtaining amorphous metal composite powder;
performing chemical plating on the amorphous powder to generate a metal layer on the surface of the amorphous powder to prepare the amorphous metal composite powder, wherein the electric conductivity range of the metal layer is 9.93 to 106~6.3*107Before the step of s/m, the preparation method further comprises the following steps:
and carrying out pretreatment of oil removal, sensitization and activation on the amorphous powder.
2. The method for preparing the amorphous coating on the metal matrix according to claim 1, wherein the step of resistance cladding the workpiece to be welded so that the amorphous metal composite powder layer is clad on the surface of the metal matrix comprises the following steps:
and turning on a power supply, adjusting the welding pressure, the welding speed and the welding current of the resistance cladding machine, placing the workpiece to be welded between two electrode wheels of the resistance cladding machine, and welding the amorphous metal composite powder layer on the surface of the metal matrix by rolling the surface of the workpiece to be welded.
3. The method for preparing the amorphous coating on the metal substrate according to claim 1, wherein before the step of uniformly spreading the amorphous metal composite powder on the surface of the metal substrate and then spreading a layer of metal foil on the surface of the amorphous metal composite powder layer to generate the workpiece to be welded, the method further comprises:
pretreating the surface of the metal substrate: and (3) polishing the metal matrix by using sand paper, and cleaning by using acetone to remove an oxide film and oil stain impurities on the surface.
4. The method for preparing the amorphous coating on the metal matrix according to claim 1, wherein after the step of resistance cladding the workpiece to be welded so that the amorphous metal composite powder layer is clad on the surface of the metal matrix, the method further comprises:
and removing the metal foil on the surface of the amorphous metal composite powder layer.
5. The method for preparing the amorphous coating on the metal substrate according to claim 1, wherein the particle size of the amorphous powder is 10-100 μm.
6. The method for preparing the amorphous coating on the metal substrate according to claim 1, wherein the plating solution is a metal salt solution.
7. The method for preparing the amorphous coating on the metal substrate according to claim 2, wherein the resistance cladding machine comprises a medium-frequency inverter, an alternating-current inverter, a single-phase alternating current or a transverse and longitudinal resistance cladding machine, the pulse current frequency of the resistance cladding machine is 10-1000 HZ, the pulse current is 1-10 kA, the welding pressure is 1-100 kN, and the welding speed is 0.1-10 m/min.
8. The method for preparing the amorphous coating on the metal matrix as claimed in claim 1, wherein the metal foil is a stainless steel sheet or a nickel-based foil.
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