CN108247042B - Ni-coated Al-coated Fe-based amorphous alloy composite powder and preparation method and application thereof - Google Patents

Ni-coated Al-coated Fe-based amorphous alloy composite powder and preparation method and application thereof Download PDF

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CN108247042B
CN108247042B CN201810079700.2A CN201810079700A CN108247042B CN 108247042 B CN108247042 B CN 108247042B CN 201810079700 A CN201810079700 A CN 201810079700A CN 108247042 B CN108247042 B CN 108247042B
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CN108247042A (en
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姜超平
刘王强
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Changan University
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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
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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Abstract

The invention discloses Ni-coated Al-coated Fe-based amorphous alloy composite powder, which consists of a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core. The invention also discloses a preparation method of the Ni-coated Al-coated Fe-based amorphous alloy composite powder, and the method performs ball milling treatment on the Fe-based amorphous alloy powder and the Ni-coated Al powder to obtain the composite powder. The invention also discloses a method for preparing a coating by applying the Ni-coated Al-coated Fe-based amorphous alloy composite powder to carry out plasma spraying. The composite powder structure of the invention is more stable, improves the melting state and the spreading deformation capability of the Fe-based amorphous alloy, and improves the bonding effect between Fe-based amorphous alloy powders. The preparation method of the invention improves the uniformity of the composite powder. The coating prepared by the invention has the advantages of compact structure, low porosity and strong corrosion resistance.

Description

Ni-coated Al-coated Fe-based amorphous alloy composite powder and preparation method and application thereof
Technical Field
The invention belongs to the technical field of surface material preparation, and particularly relates to Ni-coated Al-coated Fe-based amorphous alloy composite powder and a preparation method and application thereof.
Background
The Fe-based amorphous alloy is an alloy with an amorphous structure, is in a metastable state in thermodynamics, and has excellent mechanical property, magnetic property and corrosion resistance. The Fe-based amorphous alloy coating prepared by the plasma spraying method has high strength, hardness and corrosion resistance due to the unique structure phase, and is widely concerned. However, in the plasma spraying process, because the spreading and deforming capacity of the Fe-based amorphous alloy powder particles on the substrate is limited, the Fe-based amorphous alloy powder particles are nested and superposed with each other, a layered structure containing pores is formed by stacking, and the porosity of the coating is increased. And the pores in the layered structure of the coating form corrosion channels, so that the corrosion resistance of the Fe-based amorphous alloy coating is greatly reduced, and the application of the Fe-based amorphous alloy coating is seriously influenced.
In plasma spraying technology, the porosity of the coating is often reduced by increasing the spraying speed of the powder particles, increasing the temperature of the sprayed substrate to improve the heated and melted state of the powder particles, and reducing the effect of the ambient atmosphere on the high-temperature sprayed particles. However, the methods promote the transition of the Fe-based amorphous alloy from a metastable state to a steady state, so that the amorphous content in the formed Fe-based amorphous alloy coating is remarkably reduced, and the corrosion resistance of the Fe-based amorphous alloy coating is further reduced. Researches have been made on forming a composite coating by plasma spraying of composite powder formed by mechanically mixing Fe-based amorphous alloy powder and other powders, but the Fe-based amorphous alloy powder and other powders in the composite powder are non-uniformly mixed, so that the interior of the composite coating is easily oxidized and decarburized, and the performance of the composite coating is seriously influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing Ni-coated Al-coated Fe-based amorphous alloy composite powder aiming at the defects of the prior art. The composite powder consists of a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, has a stable structure, improves the melting state and the spreading deformation capacity of the Fe-based amorphous alloy, and improves the bonding effect between the Fe-based amorphous alloy powder.
In order to solve the technical problems, the invention adopts the technical scheme that: the Ni-coated Al-coated Fe-based amorphous alloy composite powder is characterized by consisting of a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, wherein the mass content of the Ni-coated Al powder in the composite powder is 5-20%, and the mass content of the Fe-based amorphous alloy powder is 80-95%.
The Ni-coated Al-coated Fe-based amorphous alloy composite powder is characterized in that the Ni-coated Al powder contains Ni90Al10The grain diameter is 1-30 μm; the component of the Fe-based amorphous alloy powder is Fe62.8Ni13.6Cr9.9Mo8.6Si1. 9C2.3B0.9The particle size is 15-50 μm.
In addition, the invention also provides a preparation method of the Ni-coated Al-coated Fe-based amorphous alloy composite powder, which is characterized by comprising the following specific steps of: respectively drying the Ni-coated Al powder and the Fe-based amorphous alloy powder, then uniformly mixing to form mixed powder, and then placing the mixed powder into a planetary ball mill for ball milling treatment to obtain the Ni-coated Al-coated Fe-based amorphous alloy composite powder.
The method is characterized in that the grinding balls adopted in the ball milling treatment are 316 stainless steel balls with the diameter of 8mm and the diameter of 12mm, the mass ratio of the 316 stainless steel balls with the diameter of 8mm to the 316 stainless steel balls with the diameter of 12mm is 2:1, and the ball milling tank adopted in the ball milling treatment is an MC high-wear-resistance nylon tank with the volume of 100 mL.
The method is characterized in that the mass ratio of the grinding balls to the mixed powder in the ball milling treatment process is 10: 1-15: 1.
The method is characterized in that the rotation speed of the ball milling treatment is 120 r/min-240 r/min, the time is 3 h-4 h, and the ball milling is stopped for 5min after each ball milling for 30min in the process of the ball milling treatment.
The invention also provides a method for preparing a coating by coating the Fe-based amorphous alloy composite powder with the Ni-coated Al, which is characterized by comprising the following steps of:
drying Ni-coated Al-coated Fe-based amorphous alloy composite powder;
secondly, polishing the substrate by using sand paper, then cleaning the substrate by using absolute ethyl alcohol or acetone, and then carrying out sand blasting treatment to ensure that the roughness Ra of the surface of the substrate is 9.6-12 mu m; the substrate is made of steel;
thirdly, spraying the dried Ni-coated Al-coated Fe-based amorphous alloy composite powder in the first step onto the surface of the matrix subjected to sand blasting treatment in the second step by adopting a plasma spraying process to obtain a Ni-coated Al-coated Fe-based amorphous alloy coating; and high-pressure air compressed by an air compressor is adopted to cool the back surface of the base body in the spraying process.
The method is characterized in that the parameters of the plasma spraying process in the third step are as follows: the arc voltage is 50V, the arc current is 600A, the argon flow is 80L/min, the hydrogen flow is 6L/min, the moving speed of the plasma spray gun is 30mm/s, and the spraying distance is 110 mm.
The method is characterized in that the thickness of the Ni-coated Al-coated Fe-based amorphous alloy coating obtained in the third step is 240-600 mu m.
Compared with the prior art, the invention has the following advantages:
1. the Ni-coated Al-coated Fe-based amorphous alloy composite powder consists of an Fe-based amorphous alloy powder core and an Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, and the Ni-coated Al powder and the Fe-based amorphous alloy powder have strong wetting characteristics, so that the Ni-coated Al-coated Fe-based amorphous alloy powder formed by the Ni-coated Al powder and the Fe-based amorphous alloy powder has a stable structure and is not easy to fall off and deform, and when the Ni-coated Al shell on the outer layer of the Ni-coated Al-coated Fe-based amorphous alloy powder undergoes aluminothermic reaction, the released heat promotes the Fe-based amorphous alloy powder to melt, improves the melting state and the spreading deformation capacity on a substrate, promotes the formation of micro-area metallurgical bonding between the Fe-based amorphous alloy powder, and further improves the bonding effect between the Fe-based amorphous alloy powder.
2. According to the invention, the heat released by thermite reaction is controlled by controlling the adding amount of the Ni-coated Al powder in the Ni-coated Al-coated Fe-based amorphous alloy composite powder, so that the transition of the Fe-based amorphous alloy from a metastable state to a stable state due to high temperature is reduced, the remarkable reduction of the Fe-based amorphous content is avoided, and the stable performance of the Ni-coated Al-coated Fe-based amorphous alloy powder is ensured.
3. According to the invention, the Ni-coated Al powder and the Fe-based amorphous alloy powder are uniformly mixed and then subjected to ball milling treatment, so that the Ni-coated Al powder is uniformly distributed and coated around the Fe-based amorphous alloy powder particles, the Ni-coated Al-coated Fe-based amorphous alloy composite powder is obtained, and meanwhile, the amorphous stable state of the Fe-based amorphous alloy powder is ensured, and the method is simple and efficient.
4. The invention uses Ni-coated Al powder to coat Fe-based amorphous alloy powder to prepare a coating, and intermetallic compound Ni generated by thermit reaction of the Ni-coated Al powder3Al and NiAl are filled in the pores and cracks of the Ni-coated Al-coated Fe-based amorphous alloy coating, so that the compactness of the coating structure is improved, the porosity of the composite coating is further reduced, and the corrosion resistance of the Ni-coated Al-coated Fe-based amorphous alloy coating is enhanced.
5. According to the invention, the Ni-coated Al powder is used for coating the Fe-based amorphous alloy powder to prepare the coating, so that the oxidation and decarburization phenomena of the Fe-based amorphous alloy powder in the coating caused by overhigh temperature in the plasma spraying process are avoided, and the overall performance of the coating is improved.
6. According to the invention, the Ni-coated Al-coated Fe-based amorphous alloy coating is prepared by plasma spraying, micro-area metallurgical bonding is also formed between the Ni-coated Al powder and the Fe-based amorphous alloy powder in the spraying process, the bonding in the prepared composite coating and between the coating and the substrate is tighter, the overall performance of the coating is further improved, and the service life is prolonged.
7. The Ni element in the Ni-coated Al-coated Fe-based amorphous alloy coating obtained by the invention can form a stable and compact passive film in the corrosion process, and is coated on the surface of the coating, so that the corrosion rate of the composite coating is reduced, and the corrosion resistance of the coating is further improved.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1a is an SEM photograph of Fe-based amorphous alloy powder of example 1 of the present invention.
FIG. 1b is an SEM picture of Ni-clad Al powder of example 1 of the present invention.
Fig. 2a is an XRD pattern of Fe-based amorphous alloy powder of example 1 of the present invention.
FIG. 2b is an XRD pattern of Ni-clad Al powder of example 1 of the present invention.
FIG. 3a is an overall SEM image of the Ni-coated Al-coated Fe-based amorphous alloy composite powder prepared in example 1 of the present invention.
FIG. 3b is a SEM image of the cross-section of the Ni-coated Al-coated Fe-based amorphous alloy composite powder prepared in example 1 of the present invention.
FIG. 4a is a SEM image of the low-magnification cross-sectional morphology of the Ni-coated Al-coated Fe-based amorphous alloy coating prepared in example 5 of the invention.
FIG. 4b is a SEM image of the high-power cross-sectional morphology of the Ni-coated Al-coated Fe-based amorphous alloy coating prepared in example 5 of the invention.
FIG. 5a is a SEM image of the cross section of the Ni-coated Al-coated Fe-based amorphous alloy coating prepared in example 5 of the invention.
Figure 5b is the EDS spectrum of grey black material 1 in figure 5 a.
Figure 5c is an EDS spectrum of the off-white substance 2 of figure 5 a.
FIG. 6 is a TEM image of the Ni-coated Al-coated Fe-based amorphous alloy coating prepared in example 5 of the present invention.
FIG. 7a is a SEM image of the low-magnification cross-sectional morphology of the Fe-based amorphous alloy coating prepared in comparative example 1 of the invention.
FIG. 7b is a SEM image of the high-power cross-sectional morphology of the Fe-based amorphous alloy coating prepared in comparative example 1 of the invention.
Fig. 8 is XRD patterns of the Ni-clad Al-coated Fe-based amorphous alloy coating prepared in example 5 of the present invention and the Fe-based amorphous alloy coating prepared in comparative example 1.
Fig. 9 is a polarization graph of the Ni-clad Al-coated Fe-based amorphous alloy coating prepared in example 5 of the present invention and the Fe-based amorphous alloy coating prepared in comparative example 1.
FIG. 10a is an SEM image of the Ni-coated Al-coated Fe-based amorphous alloy coating prepared in example 5 of the invention after corrosion test.
FIG. 10b is an SEM image of the Fe-based amorphous alloy coating prepared in comparative example 1 of the present invention after a corrosion test.
Detailed Description
The Ni-clad Al-coated Fe-based amorphous alloy composite powder and the method for preparing the same according to the present invention are described in detail in examples 1 to 4.
Example 1
The Ni-coated Al-coated Fe-based amorphous alloy composite powder comprises a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, wherein the Ni-coated Al powder in the composite powder comprises Ni90Al10The grain diameter is 1-30 μm, the mass content is 5 percent, and the component of the Fe-based amorphous alloy powder is Fe62.8Ni13.6Cr9.9Mo8.6Si1.9C2.3B0.9The grain diameter is 15-50 μm, and the mass content is 95%.
The preparation method of the Ni-clad Al-coated Fe-based amorphous alloy composite powder of the embodiment specifically comprises the following steps: respectively drying the Ni-coated Al powder and the Fe-based amorphous alloy powder for 3h at the temperature of 80 ℃, and then weighing 1g of Ni-coated Al powder and 19g of Fe-based amorphous alloy powder to be uniformly mixed to form mixed powder; respectively drying 316 stainless steel grinding balls with the diameters of 8mm and 12mm at 150 ℃ for 4h, and then weighing 134g of 316 stainless steel grinding balls with the diameters of 8mm and 66g of 316 stainless steel grinding balls with the diameters of 12mm, and uniformly mixing to form mixed grinding balls; placing the mixed powder and the mixed grinding ball into a 100mL MC high-wear-resistance nylon tank, covering the MC high-wear-resistance nylon tank tightly by using a sealing ring and a cover, then installing the MC high-wear-resistance nylon tank in a planetary ball mill, carrying out ball milling treatment for 3 hours at the rotating speed of 240r/min, and taking out the MC high-wear-resistance nylon tank after the ball milling is finished until the temperature of the MC high-wear-resistance nylon tank is restored to room temperature to obtain Ni-coated Al-coated Fe-based amorphous alloy composite powder; and in the process of ball milling treatment, the ball milling is stopped for 5min after 30 min.
FIG. 1a is a morphology diagram of the Fe-based amorphous alloy powder of this embodiment, and it can be seen from FIG. 1a that the Fe-based amorphous alloy powder of this embodiment is spherical and has a smooth surface, and the particle size range is 15 μm to 50 μm.
FIG. 1b is a morphology chart of the Ni-coated Al powder of this example, and it can be seen from FIG. 1b that the particle size of the Ni-coated Al powder of this example is 1 μm to 30 μm.
Fig. 2a is an XRD pattern of the Fe-based amorphous alloy powder of this example, and as can be seen from fig. 2a, the Fe-based amorphous alloy powder of this example shows a diffuse scattering peak at a diffraction angle of 2 θ (°) of 45 °, and contains a crystallization peak, and the amorphous phase content measured in the powder is 51.3%, indicating that the powder is an amorphous alloy powder with an inclusion of a crystallization phase.
Fig. 2b is an XRD pattern of the Ni-coated Al powder of this example, and it can be seen from fig. 2b that the Ni-coated Al powder of this example is a powder consisting of a Ni crystalline phase and an Al crystalline phase.
Fig. 3a is an SEM image of the overall morphology of the Ni-clad Al-coated Fe-based amorphous alloy composite powder prepared in this example, and it can be seen from fig. 3a that the surface of the Ni-clad Al-coated Fe-based amorphous alloy powder prepared in this example is not smooth, but still maintains a good spherical morphology and has good fluidity.
Fig. 3b is an SEM image of the cross-sectional morphology of the Ni-clad Al-coated Fe-based amorphous alloy composite powder prepared in this embodiment, and it can be seen from fig. 3b that, in the Ni-clad Al-coated Fe-based amorphous alloy composite powder prepared in this embodiment, the Ni-clad Al powder is coated on the surface of the Fe-based amorphous alloy, the coating layer is complete but not uniform enough, and the thickness of the coating layer is 1 μm to 3 μm.
The results of the element content distribution on the surface and cross section of the Ni-clad Al-clad Fe-based amorphous alloy composite powder in fig. 3a and 3b are shown in table 1 below.
Table 1 surface of Ni-clad Al-coated Fe-based amorphous alloy composite powder prepared in example 1
And analyzing the element content distribution result by cross section energy spectrum
Figure BDA0001560635000000071
Figure BDA0001560635000000081
As can be seen from the surface element weight percentages in table 1, the surface of the Ni-coated Al-coated Fe-based amorphous alloy composite powder prepared in this example is substantially composed of Ni and Al elements, and contains a small amount of Fe and other elements, which indicates that the outer shell layer of the Ni-coated Al-coated Fe-based amorphous alloy composite powder is mainly composed of Ni-coated Al, and as can be seen from the surface element weight percentages in table 1, the cross section of the Ni-coated Al-coated Fe-based amorphous alloy powder prepared in this example is mainly composed of Fe and other elements, does not contain Al elements, which indicates that the core of the Ni-coated Al-coated Fe-based amorphous alloy composite powder is mainly composed of Fe-based amorphous alloy particles.
Example 2
The Ni-coated Al-coated Fe-based amorphous alloy composite powder comprises a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, wherein the Ni-coated Al powder in the composite powder comprises Ni90Al10The grain diameter is 1-30 μm, the mass content is 10 percent, and the component of the Fe-based amorphous alloy powder is Fe62.8Ni13.6Cr9.9Mo8.6Si1.9C2.3B0.9The grain diameter is 15-50 μm, and the mass content is 90%.
The preparation method of the Ni-clad Al-coated Fe-based amorphous alloy composite powder of the embodiment specifically comprises the following steps: respectively drying the Ni-coated Al powder and the Fe-based amorphous alloy powder for 3h at the temperature of 80 ℃, and then weighing 2g of Ni-coated Al powder and 18g of Fe-based amorphous alloy powder to be uniformly mixed to form mixed powder; respectively drying 316 stainless steel grinding balls with the diameters of 8mm and 12mm at 150 ℃ for 4h, and then weighing 134g of 316 stainless steel grinding balls with the diameters of 8mm and 66g of 316 stainless steel grinding balls with the diameters of 12mm, and uniformly mixing to form mixed grinding balls; placing the mixed powder and the mixed grinding ball into a 100mL MC high-wear-resistance nylon tank, covering the MC high-wear-resistance nylon tank tightly by using a sealing ring and a cover, then installing the MC high-wear-resistance nylon tank in a planetary ball mill, carrying out ball milling treatment for 4 hours at the rotating speed of 120r/min, and taking out the MC high-wear-resistance nylon tank after the ball milling is finished until the temperature of the MC high-wear-resistance nylon tank is recovered to the room temperature to obtain Ni-coated Al-coated Fe-based amorphous alloy composite powder; and in the process of ball milling treatment, the ball milling is stopped for 5min after 30 min.
Example 3
The Ni-coated Al-coated Fe-based amorphous alloy composite powder comprises a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, wherein the Ni-coated Al powder in the composite powder comprises Ni90Al10The grain diameter is 1-30 mu m, the mass content is 15 percent, and the component of the Fe-based amorphous alloy powder is Fe62.8Ni13.6Cr9.9Mo8.6Si1.9C2.3B0.9The grain diameter is 15-50 μm, and the mass content is 85%.
The preparation method of the Ni-clad Al-coated Fe-based amorphous alloy composite powder of the embodiment specifically comprises the following steps: respectively drying the Ni-coated Al powder and the Fe-based amorphous alloy powder for 3h at the temperature of 80 ℃, and then weighing 3g of Ni-coated Al powder and 17g of Fe-based amorphous alloy powder to be uniformly mixed to form mixed powder; drying 316 stainless steel grinding balls with the diameter of 8mm and the diameter of 12mm for 4 hours at the temperature of 150 ℃, and then weighing 160g of 316 stainless steel grinding balls with the diameter of 8mm and 80g of 316 stainless steel grinding balls with the diameter of 12mm to be uniformly mixed to form mixed grinding balls; placing the mixed powder and the mixed grinding ball in a 100mL MC high-wear-resistance nylon tank, covering the MC high-wear-resistance nylon tank tightly by using a sealing ring and a cover, then installing the MC high-wear-resistance nylon tank in a planetary ball mill, carrying out ball milling treatment for 3.5 hours at the rotating speed of 180r/min, and taking out the MC high-wear-resistance nylon tank after the ball milling is finished until the temperature of the MC high-wear-resistance nylon tank is recovered to the room temperature to obtain Ni-coated Al-coated Fe-based amorphous alloy composite powder; and in the process of ball milling treatment, the ball milling is stopped for 5min after 30 min.
Example 4
The Ni-coated Al-coated Fe-based amorphous alloy composite powder comprises a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, wherein the Ni-coated Al powder in the composite powder comprises Ni90Al10The grain diameter is 1-30 μm, the mass content is 20 percent, and the component of the Fe-based amorphous alloy powder is Fe62.8Ni13.6Cr9.9Mo8.6Si1.9C2.3B0.9The grain diameter is 15-50 μm, and the mass content is 80%.
The preparation method of the Ni-clad Al-coated Fe-based amorphous alloy composite powder of the embodiment specifically comprises the following steps: respectively drying the Ni-coated Al powder and the Fe-based amorphous alloy powder for 3h at the temperature of 80 ℃, and then weighing 4g of Ni-coated Al powder and 16g of Fe-based amorphous alloy powder to be uniformly mixed to form mixed powder; drying 316 stainless steel grinding balls with the diameter of 8mm and the diameter of 12mm for 4 hours at the temperature of 150 ℃, and then weighing 200g of 316 stainless steel grinding balls with the diameter of 8mm and 100g of 316 stainless steel grinding balls with the diameter of 12mm to be uniformly mixed to form mixed grinding balls; placing the mixed powder and the mixed grinding ball into a 100mL MC high-wear-resistance nylon tank, covering the MC high-wear-resistance nylon tank tightly by using a sealing ring and a cover, then installing the MC high-wear-resistance nylon tank in a planetary ball mill, carrying out ball milling treatment for 4 hours at the rotating speed of 240r/min, and taking out the MC high-wear-resistance nylon tank after the ball milling is finished until the temperature of the MC high-wear-resistance nylon tank is restored to room temperature to obtain Ni-coated Al-coated Fe-based amorphous alloy composite powder; and in the process of ball milling treatment, the ball milling is stopped for 5min after 30 min.
The method of preparing a coating by coating a Ni-clad Al-based amorphous alloy composite powder according to the present invention is described in detail in examples 5 to 8, wherein the Ni-clad Al-based amorphous alloy composite powders used in examples 5, 6, 7 and 8 are prepared in examples 1, 2, 3 and 4, respectively.
Example 5
The method for preparing the coating by coating the Fe-based amorphous alloy composite powder with the Ni-coated Al comprises the following steps of:
step one, drying the Ni-coated Al-coated Fe-based amorphous alloy composite powder for 3h at the temperature of 80 ℃;
polishing 45# steel by using 800# abrasive paper to remove surface rusts, cleaning by using absolute ethyl alcohol to remove surface stains and organic matters, and performing sand blasting treatment to ensure that the roughness Ra of the 45# steel substrate surface is 10.8 mu m;
thirdly, spraying the dried Ni-coated Al-coated Fe-based amorphous alloy composite powder in the first step onto the surface of the No. 45 steel subjected to sand blasting in the second step by adopting a plasma spraying process to obtain a Ni-coated Al-coated Fe-based amorphous alloy coating with the thickness of 300 mu m; in the spraying process, high-pressure air compressed by an air compressor is adopted to cool the back surface of the 45# steel; the parameters of the plasma spraying process are as follows: the arc voltage is 50V, the arc current is 600A, the argon flow is 80L/min, the hydrogen flow is 6L/min, the moving speed of the plasma spray gun is 30mm/s, and the spraying distance is 110 mm.
Fig. 4a is a SEM image of the low-power cross-sectional morphology of the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in this embodiment, and it can be seen from fig. 4a that the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in this embodiment has a compact structure and is well bonded with the substrate.
Fig. 4b is a SEM image of a high-power cross-sectional morphology of the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in this embodiment, and as can be seen from fig. 4b, the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in this embodiment has a typical layered structure, good bonding between layers, a small number of unmelted particles and microcracks in the coating, and the coating has good density, and the porosity of the coating is determined to be 1.02%.
Fig. 5a is a cross-sectional SEM image of the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in this embodiment, the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in this embodiment has a dense structure, and the coating has a layered structure composed of a gray black substance 1 and an off-white substance 2, where the off-white substance 2 surrounds the gray black substance 1 and the layers are tightly bonded to each other.
Fig. 5b is an EDS spectrum of the gray black material 1 of fig. 5a, and the results of the content distribution of each element in the gray black material 1 are shown in table 2 below.
Table 2 example 5 preparation of grey black in Ni-clad Al-clad Fe-based amorphous alloy coating
Distribution of contents of elements in Mass 1
Figure BDA0001560635000000111
As can be seen from fig. 5b and table 2, the gray black substance 1 in the Ni-clad Al-coated Fe-based amorphous alloy coating prepared in this example is substantially composed of Fe, Cr, and Si elements, indicating that the main component of the gray black substance 1 is Fe-based alloy material.
Fig. 5c is an EDS spectrum of the off-white substance 2 of fig. 5a, and the results of the content distribution of each element in the off-white substance 2 are shown in table 3 below.
Table 3 example 5 preparation of grey white substance in Ni-clad Al-coated Fe-based amorphous alloy coating
Distribution of contents of elements in Mass 2
Figure BDA0001560635000000121
As can be seen from fig. 5c and table 3, the grayish white substance 2 in the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in this embodiment is mainly a Ni-based material, the Ni-based material layer tightly surrounds the Fe-based material layer, micro-zone metallurgical bonding is achieved between the layers, and other elements are dispersed therein.
FIG. 6 is a TEM image of the Fe-based amorphous alloy coating coated with Ni-coated Al prepared in this example, and it can be seen from FIG. 6 that the Fe-based amorphous alloy coating coated with Ni-coated Al in this example is composed of two parts, an amorphous phase and a crystallized phase, and the diffraction electron pattern selected for the amorphous phase part at the upper left corner indicates that the amorphous phase exists in the coating, and the amorphous phase is the main phase structure of the coating; the electronic diffraction pattern selected from the crystallized phase part at the lower right corner shows that the crystallized phase in the coating has small grain size and is basically nanocrystalline.
Comparative example 1
The method for preparing the coating by using the Fe-based amorphous alloy powder comprises the following steps:
step one, drying Fe-based amorphous alloy powder for 3h at the temperature of 80 ℃;
step two, firstly polishing the 45# steel by using 800# abrasive paper to remove surface rusts, then cleaning by using absolute ethyl alcohol to remove surface stains and organic matters, and then carrying out sand blasting treatment to ensure that the roughness Ra of the 45# steel surface is 10.8 mu m;
thirdly, spraying the dried Fe-based amorphous alloy powder in the first step onto the surface of the No. 45 steel subjected to sand blasting in the second step by adopting a plasma spraying process to obtain a Fe-based amorphous alloy coating with the thickness of 300 mu m; in the spraying process, high-pressure air compressed by an air compressor is adopted to cool the back surface of the 45# steel; the parameters of the plasma spraying process are as follows: the arc voltage is 50V, the arc current is 600A, the argon flow is 80L/min, the hydrogen flow is 6L/min, the moving speed of the plasma spray gun is 30mm/s, and the spraying distance is 110 mm.
FIG. 7a is a SEM image of the low-magnification cross-sectional morphology of the Fe-based amorphous alloy coating prepared in the comparative example, and it can be seen from FIG. 7a that the Fe-based amorphous alloy coating prepared without adding Ni-coated Al powder has obvious pore defects, the coating structure is not compact, and an obvious interface exists between the coating and the substrate, indicating that the coating and the substrate are poorly bonded.
FIG. 7b is a SEM image of the high-magnification cross-sectional morphology of the Fe-based amorphous alloy coating prepared in the comparative example, and it can be seen from FIG. 7b that the Fe-based amorphous alloy coating prepared without adding Ni-coated Al powder has a large number of unmelted particles, cracks and large-sized pore defects, the overall structure of the coating is not dense, and the porosity of the coating is determined to be 6.69%.
Fig. 8 is XRD patterns of the Ni-clad Al-coated Fe-based amorphous alloy coating prepared in example 1 and the Fe-based amorphous alloy coating prepared in comparative example 1, where the scanning angle is 2(θ) 20 ° to 90 °, and it can be seen from fig. 8 that the kind of the crystallization phase of the Ni-clad Al-coated Fe-based amorphous alloy coating is different from that of the Fe-based amorphous alloy coating, and Ni and Al elements in the Ni-clad Al-coated Fe-based amorphous alloy coating are Ni and Al elements in the Ni-clad Al-coated Fe-based amorphous alloy coating3The existence of Al form indicates that the Al powder wrapped by Ni has thermite reaction during the plasma spraying process, so that NThe i-coated Al-coated Fe-based amorphous alloy composite powder is tightly combined with the 45# steel substrate, so that a Ni-coated Al-coated Fe-based amorphous alloy coating with a compact structure is generated, and the corrosion resistance of the coating is improved; the difference between the amorphous content of the Ni-coated Al-coated Fe-based amorphous alloy coating and the amorphous content of the Fe-based amorphous alloy coating is small, which shows that the Ni-coated Al-coated Fe-based amorphous alloy composite powder is heated to form the coating and then is rapidly cooled in the plasma spraying process, so that the transition of the Fe-based amorphous alloy from a metastable state to a stable state and the oxidation and decarburization of the Fe-based amorphous alloy powder due to high temperature are avoided, the obvious reduction of the Fe-based amorphous content in the coating is avoided, and the corrosion resistance of the Ni-coated Al-coated Fe-based amorphous alloy coating is ensured.
The corrosion resistance of the Ni-coated Al-coated Fe-based amorphous alloy coating prepared in the example 1 and the corrosion resistance of the Fe-based amorphous alloy coating prepared in the comparative example 1 are respectively measured by an electrochemical corrosion method, and the specific measurement process is as follows: a ZAHNER IM6e type three-electrode test system is adopted, wherein a saturated calomel electrode is used as a reference electrode, a 1cm multiplied by 1cm platinum sheet is used as an auxiliary electrode, 3.5 wt% NaCl solution is used as a corrosion medium, a lead and the surface of a sample which does not participate in the test are sealed by paraffin, a 1cm multiplied by 1cm exposed area is left for electrochemical test, a polarization curve of each coating is determined by potentiodynamic scanning, the scanning speed is set to be 5mV/min, the measurement interval is set to be-1V, after the sample is soaked in the NaCl solution for 5min, the measurement is started when the self-corrosion current is stable, the self-corrosion current density is obtained by a Tafel linear extrapolation method, and the result is shown in figure 9.
Fig. 9 is a polarization curve diagram of the Ni-clad Al-coated Fe-based amorphous alloy coating prepared in example 1 and the Fe-based amorphous alloy coating prepared in comparative example 1, and it can be seen from fig. 9 that the Ni-clad Al-coated Fe-based amorphous alloy coating has a higher self-corrosion potential than the Fe-based amorphous alloy coating, and the passivation region of the Ni-clad Al-coated Fe-based amorphous alloy coating is more gradual, which indicates that the Ni-clad Al-coated Fe-based amorphous alloy coating has better corrosion resistance, and the dense structure of the coating and the increase of the Ni content in the coating enable the coating to form a more stable passivation film, preventing the coating from being further corroded.
The Ni-coated Al-coated Fe-based amorphous alloy coating prepared in the example 1 and the Fe-based amorphous alloy coating prepared in the comparative example 1 are respectively subjected to corrosion tests, and the specific process is as follows: cutting the sample into a cuboid with the size of 1cm multiplied by 0.2cm, sealing other five surfaces with epoxy resin or paraffin, only keeping one surface of the coating, then placing the sealed sample in 3.5 wt% NaCl solution for soaking and corroding, taking out the sample for drying after 120h of soaking and corroding, and carrying out electron microscope scanning.
Fig. 10a is an SEM image of the Ni-clad Al-coated Fe-based amorphous alloy coating prepared in example 1 after a corrosion test, and it can be seen from fig. 10a that after the Ni-clad Al-coated Fe-based amorphous alloy coating prepared in example 1 is corroded for 120h, corrosion products appear on the surface of the coating, and the corrosion products are mainly generated at non-fused particles and at places where the microstructure is not dense.
Fig. 10b is an SEM image of the Fe-based amorphous alloy coating prepared in comparative example 1 after the corrosion test, and it can be seen from fig. 10b that after the Fe-based amorphous alloy coating prepared without adding Ni-clad Al powder is corroded for 120h, a large amount of corrosion products appear on the coating surface, the corrosion products are mainly generated at the non-fused particles and the microstructure non-dense places, and the area of the corrosion products is about 3 times that of the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in example 1 of the present invention.
Comparing fig. 10a and fig. 10b, it can be seen that corrosion mainly occurs at the non-fused particles and the microstructure of the coating is not dense, and the void defect can provide a channel for a corrosion medium to enter the coating, and since the Ni-clad Al-clad Fe-based amorphous alloy coating prepared in example 1 has a microstructure denser than that of the Fe-based amorphous alloy coating prepared in comparative example 1, after 120h corrosion, the corrosion product is far less than that of the latter, indicating that the coating has better corrosion resistance than the Fe-based amorphous alloy coating prepared in comparative example 1.
Example 6
The method for preparing the coating by coating the Fe-based amorphous alloy composite powder with the Ni-coated Al comprises the following steps of:
step one, drying the Ni-coated Al-coated Fe-based amorphous alloy composite powder for 3h at the temperature of 80 ℃;
polishing the Q235 steel by using 800# abrasive paper to remove surface rusts, cleaning by using absolute ethyl alcohol to remove surface stains and organic matters, and performing sand blasting treatment to enable the roughness Ra of the surface of the Q235 steel to be 12 microns;
thirdly, spraying the dried Ni-coated Al-coated Fe-based amorphous alloy composite powder in the first step onto the surface of the Q235 steel subjected to sand blasting treatment in the second step by adopting a plasma spraying process to obtain a Ni-coated Al-coated Fe-based amorphous alloy coating with the thickness of 240 microns; in the spraying process, high-pressure air compressed by an air compressor is adopted to cool the back surface of the Q235 steel; the parameters of the plasma spraying process are as follows: the arc voltage is 50V, the arc current is 600A, the argon flow is 80L/min, the hydrogen flow is 6L/min, the moving speed of the plasma spray gun is 30mm/s, and the spraying distance is 110 mm.
Example 7
The method for preparing the coating by coating the Fe-based amorphous alloy composite powder with the Ni-coated Al comprises the following steps of:
step one, drying the Ni-coated Al-coated Fe-based amorphous alloy composite powder for 3h at the temperature of 80 ℃;
step two, polishing the T8 steel by using 800# abrasive paper to remove surface rusts, cleaning by using acetone to remove surface stains and organic matters, and then performing sand blasting treatment to enable the roughness Ra of the surface of the T8 steel to be 11.2 mu m;
thirdly, spraying the dried Ni-coated Al-coated Fe-based amorphous alloy composite powder in the first step onto the surface of the T8 steel subjected to sand blasting treatment in the second step by adopting a plasma spraying process to obtain a Ni-coated Al-coated Fe-based amorphous alloy coating with the thickness of 360 microns; in the spraying process, high-pressure air compressed by an air compressor is adopted to cool the back surface of the T8 steel; the parameters of the plasma spraying process are as follows: the arc voltage is 50V, the arc current is 600A, the argon flow is 80L/min, the hydrogen flow is 6L/min, the moving speed of the plasma spray gun is 30mm/s, and the spraying distance is 110 mm.
Example 8
The method for preparing the coating by coating the Fe-based amorphous alloy composite powder with the Ni-coated Al comprises the following steps of:
step one, drying the Ni-coated Al-coated Fe-based amorphous alloy composite powder for 3h at the temperature of 80 ℃;
polishing 316L stainless steel by using 800# abrasive paper to remove surface rusts, cleaning by using acetone to remove surface stains and organic matters, and performing sand blasting treatment to enable the roughness Ra of the 316L stainless steel surface to be 9.6 mu m;
thirdly, spraying the dried Ni-coated Al-coated Fe-based amorphous alloy composite powder in the first step onto the surface of the 316L stainless steel subjected to sand blasting treatment in the second step by adopting a plasma spraying process to obtain a Ni-coated Al-coated Fe-based amorphous alloy coating with the thickness of 600 mu m; in the spraying process, high-pressure air compressed by an air compressor is adopted to cool the back surface of the 316L stainless steel; the parameters of the plasma spraying process are as follows: the arc voltage is 50V, the arc current is 600A, the argon flow is 80L/min, the hydrogen flow is 6L/min, the moving speed of the plasma spray gun is 30mm/s, and the spraying distance is 110 mm.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (9)

  1. The Ni-coated Al-coated Fe-based amorphous alloy composite powder is characterized by consisting of a Fe-based amorphous alloy powder core and a Ni-coated Al powder shell coated outside the Fe-based amorphous alloy powder core, wherein the mass content of the Ni-coated Al powder in the composite powder is 5-20%, and the mass content of the Fe-based amorphous alloy powder is 80-95%.
  2. 2. The Ni-coated Al-coated Fe-based amorphous alloy composite powder of claim 1, wherein the Ni-coated Al powder comprises Ni90Al10The grain diameter is 1-30 μm; the component of the Fe-based amorphous alloy powder is Fe62.8Ni13.6Cr9. 9Mo8.6Si1.9C2.3B0.9Granule of Chinese medicineThe diameter is 15-50 μm.
  3. 3. A method for preparing the Ni-clad Al-clad Fe-based amorphous alloy composite powder according to claim 1 or 2, which comprises the following specific steps: respectively drying the Ni-coated Al powder and the Fe-based amorphous alloy powder, then uniformly mixing to form mixed powder, and then placing the mixed powder into a planetary ball mill for ball milling treatment to obtain the Ni-coated Al-coated Fe-based amorphous alloy composite powder.
  4. 4. The method as claimed in claim 3, wherein the grinding balls used in the ball milling treatment are 316 stainless steel balls with the diameter of 8mm and the diameter of 12mm, the mass ratio of the 316 stainless steel balls with the diameter of 8mm to the 316 stainless steel balls with the diameter of 12mm is 2:1, and the ball milling tank used in the ball milling treatment is an MC high-wear-resistance nylon tank with the volume of 100 mL.
  5. 5. The method according to claim 3, wherein the mass ratio of the grinding balls to the mixed powder in the ball milling treatment is 10: 1-15: 1.
  6. 6. The method according to claim 3, wherein the rotation speed of the ball milling treatment is 120 r/min-240 r/min, the time is 3 h-4 h, and the ball milling treatment is stopped for 5min after each 30min ball milling.
  7. 7. A method for preparing a coating by using the Ni-clad Al-clad Fe-based amorphous alloy composite powder according to claim 1 or 2, comprising the steps of:
    drying Ni-coated Al-coated Fe-based amorphous alloy composite powder;
    secondly, polishing the substrate by using sand paper, then cleaning the substrate by using absolute ethyl alcohol or acetone, and then carrying out sand blasting treatment to ensure that the roughness Ra of the surface of the substrate is 9.6-12 mu m; the substrate is made of steel;
    thirdly, spraying the dried Ni-coated Al-coated Fe-based amorphous alloy composite powder in the first step onto the surface of the matrix subjected to sand blasting treatment in the second step by adopting a plasma spraying process to obtain a Ni-coated Al-coated Fe-based amorphous alloy coating; and high-pressure air compressed by an air compressor is adopted to cool the back surface of the base body in the spraying process.
  8. 8. The method of claim 7, wherein the parameters of the plasma spraying process in step three are: the arc voltage is 50V, the arc current is 600A, the argon flow is 80L/min, the hydrogen flow is 6L/min, the moving speed of the plasma spray gun is 30mm/s, and the spraying distance is 110 mm.
  9. 9. The method according to claim 7, wherein the Ni-clad Al-clad Fe-based amorphous alloy coating obtained in the third step has a thickness of 240 μm to 600 μm.
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