CN116043214A - Metallurgical bonded steel surface composite titanium alloy coating and preparation method thereof - Google Patents
Metallurgical bonded steel surface composite titanium alloy coating and preparation method thereof Download PDFInfo
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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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
- C23C24/106—Coating with metal alloys or metal elements only
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention relates to a metallurgically bonded steel surface composite titanium alloy coating and a preparation method thereof, and the metallurgically bonded steel surface composite titanium alloy coating comprises an intermediate layer and a surface layer which are sequentially arranged from a substrate, wherein the interface is metallurgically bonded, and the formation of Fe-Ti brittle phases and cracks between the titanium alloy coating and steel can be effectively solved by arranging the intermediate layer, and the Fe-Ti brittle phases and cracks are obviously reduced, so that the coating has good compactness, high bonding strength, excellent corrosion resistance and longer service life. Also has larger microhardness and better wear resistance and abrasion corrosion resistance. The invention also provides a preparation method of the coating.
Description
Technical Field
The invention belongs to the technical field of metal corrosion and protection, and particularly relates to a metallurgically bonded steel surface composite titanium alloy coating and a preparation method thereof.
Background
In ocean engineering, due to the specific environment of ocean, a lot of special requirements are imposed on the service materials, and the most critical is the seawater corrosion resistance. Many underwater equipment is often scrapped due to corrosion, and the strength problem of the deep-sea underwater sealed shell structure is the most important for equipment which performs underwater operation for a long time, so that research on materials with high strength, light weight, seawater corrosion resistance and low cost, as well as reasonable structural design and material selection, has become one of key technologies of ocean engineering.
Titanium and titanium alloy have strong seawater and various medium corrosion resistance, and high specific strength, and are ideal materials for ocean engineering. With the development of the titanium industry, the application of titanium materials in underwater engineering is gradually increased, but the application range of the titanium materials is limited due to the fact that the titanium materials are expensive. In the related art, researchers improve the material utilization rate by covering a titanium alloy coating on the surface of a steel or nonmetal material. However, the extremely small dilution ratio and the large difference in thermal expansion coefficient between Fe and Ti cause extremely easy formation of Fe-Ti brittle phases, key holes and cracks in the preparation process of the titanium alloy coating, and therefore, it is necessary to develop a new material and a preparation method thereof to solve the above-mentioned problems.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides a metallurgically bonded steel surface composite titanium alloy coating, which utilizes a laser cladding technology to prepare a transition intermediate layer firstly, and can effectively solve the formation of Fe-Ti brittle phases and cracks between the titanium alloy coating and steel.
The invention also provides a preparation method of the metallurgically bonded steel surface composite titanium alloy coating.
The first aspect of the invention provides a metallurgically bonded steel surface composite titanium alloy coating, the preparation raw materials comprise alloy powder A and alloy powder B, and the alloy powder A comprises at least one of copper alloy powder, nickel alloy powder, niobium alloy powder, molybdenum alloy powder, aluminum alloy powder and magnesium alloy powder; the alloy powder B comprises titanium alloy powder, and the mass ratio of the alloy powder A to the alloy powder B is (2-8): 1, a step of; the metallurgically bonded steel surface composite titanium alloy coating comprises an intermediate layer formed by the alloy powder A and a surface layer formed by the alloy powder B from a substrate;
the titanium alloy powder comprises the following elements in percentage by mass:
Al:5.5％～6.75％；
V:3.5％～4.5％；
Fe:≤0.03％％；
C:≤0.08％％；
O:≤0.20％；
N:≤0.05％；
H:≤0.015％；
the balance being Ti and impurity elements.
The invention relates to one of the technical schemes of metallurgical bonding steel surface composite titanium alloy coating, which has at least the following beneficial effects:
the metallurgical bonding steel surface composite titanium alloy coating comprises an intermediate layer and a surface layer which are sequentially arranged from a substrate, wherein the metallurgical bonding is performed at the interface, and the formation of Fe-Ti brittle phases and cracks between the titanium alloy coating and steel can be effectively solved by arranging the intermediate layer, and the Fe-Ti brittle phases and cracks are obviously reduced, so that the coating has good compactness, high bonding strength, excellent corrosion resistance and longer service life. Also has larger microhardness and better wear resistance and abrasion corrosion resistance.
The metallurgically bonded steel surface composite titanium alloy coating can be prepared by adopting a laser cladding technology, has high degree of automation and short production period, and can be used for preparing metallurgically bonded steel surface composite titanium alloy coating parts with complex shapes.
The metallurgical bonding steel surface composite titanium alloy coating can be prepared without heat treatment, has the advantages of simple preparation flow, low cost, low carbon, environment friendliness and no pollution, and can be applied to industrial production and various working condition environments.
In the metallurgically bonded steel surface composite titanium alloy coating, the coating bonding mode is metallurgically bonding.
According to some embodiments of the invention, the alloy powder A is a copper alloy powder in which, in addition to copper element, O is 0.1% or less, fe is 0.03% or less, and the total amount of impurity elements is 0.08% or less.
According to some embodiments of the invention, the alloy powder a may also be one or a combination of several of the other common engineering application metal alloy powders.
According to some embodiments of the invention, the total thickness of the metallurgically bonded steel surface composite titanium alloy coating is 400-1600 μm.
According to some embodiments of the invention, the thickness of the intermediate layer is 100 μm to 600 μm.
According to some embodiments of the invention, the surface layer has a thickness of 400 μm to 1600 μm.
According to some embodiments of the invention, the metallurgical structure comprises acicular alpha (alpha') phase, fine beta phase, lamellar alpha phase, equiaxed, dendrite and columnar crystals, metallic intermediate phase, and unmelted titanium alloy particles in the metallurgically bonded steel surface composite titanium alloy coating.
The metallurgical structure comprises an acicular alpha (alpha ') phase, a fine beta phase, lamellar alpha phases, equiaxed crystals, dendrites and columnar crystals, a metal intermediate phase and unmelted titanium alloy particles, so that the metallurgical bonding steel surface composite titanium alloy coating prepared by the invention has excellent corrosion resistance, wear resistance, abrasion corrosion resistance, heat resistance, plasticity, toughness and specific strength, and the acicular alpha (alpha') phase, the fine beta phase, the lamellar alpha phases, the equiaxed crystals and dendrites can improve the mechanical properties of the metallurgical bonding steel surface composite titanium alloy coating; the columnar crystal is favorable for inhibiting the formation of defects such as key holes, microcracks and the like in the coating, and the unmelted particles are favorable for inhibiting the crack expansion behavior in the coating, so that the mechanical property of the metallurgically bonded steel surface composite titanium alloy coating is improved.
According to some embodiments of the invention, the content of other individual impurity elements in the alloy powder A is less than or equal to 0.01wt%.
According to some embodiments of the invention, the total amount of impurity elements in the alloy powder A is 0.08wt% or less.
According to some embodiments of the invention, alloy powder a is a rose-red, brass-colored.
According to some embodiments of the invention, the content of other individual impurity elements in the alloy powder B is 0.01wt% or less.
According to some embodiments of the invention, the total amount of impurity elements in the alloy powder B is 0.05wt% or less.
According to some embodiments of the invention, the microhardness of the wear-resistant corrosion-resistant titanium alloy coating is 350HV0.1-700 HV0.1.
According to some embodiments of the invention, the shear strength of the wear-resistant corrosion-resistant titanium alloy coating is 200MPa to 500MPa.
According to some embodiments of the invention, the particle morphology of alloy powder a and alloy powder B includes spherical particles, spheroidal particles, cubic particles, and irregular particles.
When the particle forms of the alloy powder A and the alloy powder B are spherical particles, the particle mobility in the laser cladding process is optimal, and the prepared metallurgical bonding steel surface composite titanium alloy coating has a uniform and compact metallographic structure.
The particle forms of the alloy powder A and the alloy powder B are similar spherical particles, the particles are not easy to adhere, the porosity is low, and key holes are not easy to form in the prepared metallurgical bonding steel surface composite titanium alloy coating, so that the mechanical property of the coating is facilitated.
The particle forms of the alloy powder A and the alloy powder B are cube particles, the particle melting rates are consistent, a continuous and smooth surface is easy to form in the solidification process of the melted powder, and the prepared metallurgical bonding steel surface composite titanium alloy coating has high compactness and a spoon Kong Jishao.
The particle forms of the alloy powder A and the alloy powder B are irregular particles, and the powder of small particles can be filled into the gaps of large particles, so that the powder bulk density is improved, and the surface quality and the strength of the metallurgically bonded steel surface composite titanium alloy coating are improved.
According to some embodiments of the invention, the average particle size of the alloy powder a and the alloy powder B is 30 μm to 300 μm.
The average particle size of the alloy powder A and the alloy powder B is smaller than 30 mu m, which can lead to spheroidization in the fusing process and cause uneven coating thickness; if the particle size is more than 300 mu m, the melting rate of powder is reduced, the solidification rate of a molten pool is increased, and a brittle metal intermediate phase is easily formed in the coating, so that the mechanical property of the composite titanium alloy coating on the steel surface is reduced. Thus, the average particle size range of 30 μm to 300 μm is suitable.
According to some embodiments of the invention, alloy powder a has a melting point of 800 ℃ to 1600 ℃.
In a second aspect, the present invention provides a method for preparing the metallurgically bonded steel surface composite titanium alloy coating, the method comprising: and in an inert atmosphere environment, scanning the surface of the substrate by using the alloy powder A and the alloy powder B sequentially through laser cladding.
The invention relates to a technical scheme in a preparation method of a metallurgical bonded steel surface composite titanium alloy coating, which has at least the following beneficial effects:
the preparation method of the metallurgical bonding steel surface composite titanium alloy coating does not need heat treatment, has simple preparation flow and low cost, can realize industrial production, and can be applied to various working condition environments. Compared with the organic paint corrosion prevention technology, the method realizes low carbon, environmental protection and no pollution.
The preparation method of the metallurgical bonding steel surface composite titanium alloy coating can be prepared by adopting a laser cladding technology, has high degree of automation and short production period, and can prepare titanium alloy coating parts with complex shapes.
According to the preparation method of the metallurgical bonding steel surface composite titanium alloy coating, the transition intermediate layer is prepared by utilizing a laser cladding technology, so that the formation of Fe-Ti brittle phases and cracks between the titanium alloy coating and steel can be effectively solved.
According to some embodiments of the invention, the laser cladding is in a continuous scanning mode, scanning tracks are mutually overlapped, and the track overlapping rate is 20% -80%.
According to some embodiments of the invention, the laser power of the laser cladding is 800-2000W.
According to some embodiments of the invention, the laser scanning rate of the laser cladding is 4mm/s to 32mm/s.
According to some embodiments of the invention, the laser cladding powder feeding mode comprises three-pipe coaxial powder feeding.
According to some embodiments of the invention, the powder feeding rate of the laser cladding is 0.5 r/min-4 r/min.
According to some embodiments of the present invention, a method of preparing a metallurgically bonded steel surface composite titanium alloy coating comprises the steps of:
step one: drying the alloy powder A and the alloy powder B to remove water adsorbed on the surfaces of the powder;
step two: polishing, cleaning and drying the surface of the steel plate to remove surface impurities and defects;
step three: taking a steel plate as a matrix, taking alloy powder B as a coating material, and continuously scanning by using a laser cladding technology to obtain a sample A;
step four: naturally cooling the sample A obtained in the step three to room temperature, and performing polishing, cleaning and drying treatment to obtain an alloy intermediate layer;
Step five: taking the alloy intermediate layer as a matrix, taking alloy powder A as a coating material, and continuously scanning by using a laser cladding technology to obtain a sample B;
step six: and D, naturally cooling the sample B obtained in the step five to room temperature, and performing polishing treatment to obtain the metallurgically bonded steel surface composite titanium alloy coating.
According to some embodiments of the invention, in step two, the steel sheet comprises carbon steel, low alloy steel, stainless steel, and commonly used other grades of engineering application steel.
According to some embodiments of the invention, the steel plate has a thickness of 6mm to 10mm.
According to some embodiments of the invention, the steel plate is preferably Q235 steel.
According to some embodiments of the present invention, the steel sheet is polished with SiC sandpaper, the maximum number of polished SiC sandpaper is 800 mesh, and the polished steel sheet surface has metallic luster and no macroscopic defect.
According to some embodiments of the invention, the polished steel plate can be cleaned by absolute ethyl alcohol with the purity of more than 99.99%, and the cleaned steel plate is immediately dried by an electric hair drier to blow the surface of the steel plate, so that the steel plate is prevented from rusting.
According to some embodiments of the invention, in the third step, the laser cladding technology adopts a three-pipeline coaxial powder feeding mode, and the laser cladding process is carried out in a protective gas environment, wherein the laser cladding process comprises air, nitrogen, argon and helium, and the surface temperature of a molten pool is 1300-1600 ℃.
According to some embodiments of the invention, in the third step, the laser cladding adopts a continuous scanning mode, scanning tracks are mutually overlapped, the track overlapping rate is 20% -70%, the laser power is 800-1400W, the laser scanning rate is 4-32 mm/s, and the powder feeding rate is 0.5-4 r/min.
According to some embodiments of the present invention, in the fourth step, the sample a is polished by using an angle grinder or a steel brush to remove an oxide layer on the surface, and the polished surface has metallic luster; and (3) cleaning the polished surface by using absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier.
According to some embodiments of the present invention, in the fifth step, the laser cladding technology adopts a three-pipe coaxial powder feeding manner, and the laser cladding process is performed in an inert atmosphere environment, including argon and helium; the laser cladding process adopts a continuous scanning mode, the scanning tracks are mutually overlapped, the track overlapping rate is 20% -80%, the laser power is 800-2000W, the laser scanning rate is 4-32 mm/s, and the powder feeding rate is 0.5-4 r/min; the surface temperature of the molten pool is 1500-2000 ℃.
According to some embodiments of the invention, in the fifth step, two laser cladding directions of the titanium alloy powder are provided, one is that the alloy powder B scanning track is parallel to the alloy powder a scanning track, and the other is that the alloy powder B scanning track is perpendicular to the alloy powder a scanning track.
Drawings
FIG. 1 is a digital photograph of the macroscopic morphology of a metallurgically bonded steel surface composite titanium alloy coating prepared in example 1.
FIG. 2 is a digital photograph of the unabrashed macroscopic morphology of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 1.
FIG. 3 is a photograph of the metallographic structure of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 2.
FIG. 4 is a photograph of the post-etch metallographic structure of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 2.
Fig. 5 is an XRD spectrum of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 2.
FIG. 6 is a digital photograph of the macroscopic morphology of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 3.
Fig. 7 is an SEM photograph of a metallurgically bonded steel surface composite titanium alloy coating prepared in example 3.
FIG. 8 is a photograph of the metallographic structure of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 4.
Fig. 9 is a photograph of the metallographic structure of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 4 after etching.
Fig. 10 is an XRD spectrum of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 4.
FIG. 11 is an SEM micrograph of a metallurgically bonded steel surface composite titanium alloy coating prepared according to example 5.
FIG. 12 is an SEM high magnification of a metallurgically bonded steel surface composite titanium alloy coating prepared according to example 5.
FIG. 13 is a photograph of the metallographic structure of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 6.
FIG. 14 is a photograph of the metallographic structure of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 6 after etching.
FIG. 15 is a plot of bath surface temperature during laser cladding of metallurgically bonded steel surface composite titanium alloy coatings prepared in examples 2, 4, 5 and 6.
FIG. 16 is the thickness of the metallurgically bonded steel surface composite titanium alloy coating prepared in examples 2, 4, 5 and 6.
FIG. 17 is a microhardness profile of a metallurgically bonded steel surface composite titanium alloy coating prepared in examples 2, 4, 5 and 6.
FIG. 18 shows the results of corrosion resistance tests for metallurgically bonded steel surface composite titanium alloy coatings prepared in examples 2, 4, 5 and 6, and comparative examples 1 and 2.
Fig. 19 shows shear strength results for example 2, example 4, example 5 and example 6 of a metallurgically bonded steel surface composite titanium alloy coating and method of making the same according to the present invention.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
In some embodiments of the invention, the invention provides a metallurgically bonded steel surface composite titanium alloy coating, the preparation raw material comprises alloy powder A and alloy powder B, and the alloy powder A comprises at least one of copper alloy powder, nickel alloy powder, niobium alloy powder, molybdenum alloy powder, aluminum alloy powder and magnesium alloy powder; the alloy powder B comprises titanium alloy powder, and the mass ratio of the alloy powder A to the alloy powder B is (2-8): 1, a step of; the metallurgical bonding steel surface composite titanium alloy coating comprises an intermediate layer formed by alloy powder A and a surface layer formed by alloy powder B from a substrate;
the titanium alloy powder comprises the following elements in percentage by mass:
Al:5.5％～6.75％；
V:3.5％～4.5％；
Fe:≤0.03％％；
C:≤0.08％％；
O:≤0.20％；
N:≤0.05％；
H:≤0.015％；
the balance being Ti and impurity elements.
It can be understood that the metallurgical bonding steel surface composite titanium alloy coating comprises the middle layer and the surface layer which are sequentially arranged from the substrate, the metallurgical bonding is performed at the interface, and the formation of Fe-Ti brittle phases and cracks between the titanium alloy coating and steel can be effectively solved by arranging the middle layer, and the Fe-Ti brittle phases and cracks are obviously reduced, so that the coating has good compactness, high bonding strength, excellent corrosion resistance and longer service life. Also has larger microhardness and better wear resistance and abrasion corrosion resistance.
It can be further understood that the metallurgically bonded steel surface composite titanium alloy coating can be prepared by adopting a laser cladding technology, has high degree of automation and short production period, and can be used for preparing metallurgically bonded steel surface composite titanium alloy coating parts with complex shapes.
The metallurgical bonding steel surface composite titanium alloy coating can be prepared without heat treatment, has the advantages of simple preparation flow, low cost, low carbon, environment friendliness and no pollution, and can be applied to industrial production and various working condition environments.
It should be emphasized that in the metallurgically bonded steel surface composite titanium alloy coating of the invention, the coating bonding mode is metallurgically bonding.
In some embodiments of the present invention, alloy powder A is a copper alloy powder in which, in addition to copper element, O is 0.1% or less, fe is 0.03% or less, and the total amount of impurity elements is 0.08% or less.
It should be noted that, in some embodiments of the present invention, the alloy powder a may be one or a combination of several of other common engineering application metal alloy powders.
In some embodiments of the invention, the total thickness of the metallurgically bonded steel surface composite titanium alloy coating is 400 μm to 1600 μm.
In some embodiments of the invention, the thickness of the intermediate layer is 100 μm to 600 μm.
In some embodiments of the invention, the thickness of the surface layer is 400 μm to 1600 μm.
In some embodiments of the invention, the metallurgical structure comprises acicular alpha (alpha') phases, fine beta phases, lamellar alpha phases, equiaxed crystals, dendrites and columnar crystals, metallic mesophases, and unmelted titanium alloy particles in the metallurgically bonded steel surface composite titanium alloy coating.
The metallurgical structure comprises an acicular alpha (alpha ') phase, a fine beta phase, lamellar alpha phases, equiaxed crystals, dendrites and columnar crystals, a metal intermediate phase and unmelted titanium alloy particles, so that the metallurgical bonding steel surface composite titanium alloy coating prepared by the invention has excellent corrosion resistance, wear resistance, abrasion corrosion resistance, heat resistance, plasticity, toughness and specific strength, and the acicular alpha (alpha') phase, the fine beta phase, the lamellar alpha phases, the equiaxed crystals and dendrites can improve the mechanical properties of the steel surface composite titanium alloy coating; the columnar crystal is favorable for inhibiting the formation of defects such as key holes, microcracks and the like in the coating, and the unmelted particles are favorable for inhibiting the crack expansion behavior in the coating, so that the mechanical property of the composite titanium alloy coating on the steel surface is improved.
In some embodiments of the present invention, the content of other individual impurity elements in alloy powder A is 0.01wt% or less.
In some embodiments of the present invention, the total amount of impurity elements in alloy powder A is 0.08wt% or less.
In some embodiments of the invention, alloy powder a is rose-red, brass in color.
In some embodiments of the present invention, the content of other individual impurity elements in alloy powder B is 0.01wt% or less.
In some embodiments of the present invention, the total amount of impurity elements in alloy powder B is 0.05wt%.
In some embodiments of the invention, the microhardness of the wear-resistant corrosion-resistant titanium alloy coating is 350HV0.1 to 700HV0.1.
In some embodiments of the invention, the shear strength of the wear resistant corrosion resistant titanium alloy coating is 200MPa to 500MPa.
In some embodiments of the present invention, the particle morphology of alloy powder a and alloy powder B includes spherical particles, spheroidal particles, cubic particles, and irregular particles.
When the particle forms of the alloy powder A and the alloy powder B are spherical particles, the particle mobility in the laser cladding process is optimal, and the prepared metallurgical bonding steel surface composite titanium alloy coating has a uniform and compact metallographic structure.
The particle forms of the alloy powder A and the alloy powder B are similar spherical particles, the particles are not easy to adhere, the porosity is low, and key holes are not easy to form in the prepared metallurgical bonding steel surface composite titanium alloy coating, so that the mechanical property of the coating is facilitated.
The particle forms of the alloy powder A and the alloy powder B are cube particles, the particle melting rates are consistent, a continuous and smooth surface is easy to form in the solidification process of the melted powder, and the prepared metallurgical bonding steel surface composite titanium alloy coating has high compactness and a spoon Kong Jishao.
The particle forms of the alloy powder A and the alloy powder B are irregular particles, and the powder of small particles can be filled into the gaps of large particles, so that the powder bulk density is improved, and the surface quality and the strength of the metallurgically bonded steel surface composite titanium alloy coating are improved.
In some embodiments of the invention, the average particle size of alloy powder A and alloy powder B is from 30 μm to 300 μm.
The average particle size of the alloy powder A and the alloy powder B is smaller than 30 mu m, which can lead to spheroidization in the fusing process and cause uneven coating thickness; if the particle size is more than 300 mu m, the melting rate of powder is reduced, the solidification rate of a molten pool is increased, and a brittle metal intermediate phase is easily formed in the coating, so that the mechanical property of the composite titanium alloy coating on the steel surface is reduced. Thus, the average particle size range of 30 μm to 300 μm is suitable.
In some embodiments of the invention, alloy powder a has a melting point of 800 ℃ to 1600 ℃.
In still other embodiments of the present invention, the present invention provides a method of preparing a metallurgically bonded steel surface composite titanium alloy coating, which can be summarized as follows: and in an inert atmosphere environment, scanning the surface of the substrate by using alloy powder A and alloy powder B sequentially through laser cladding.
It can be understood that the preparation method of the metallurgical bonding steel surface composite titanium alloy coating does not need heat treatment, has simple preparation flow and low cost, can realize industrial production, and can be applied to various working condition environments. Compared with the organic paint corrosion prevention technology, the method realizes low carbon, environmental protection and no pollution.
The preparation method of the metallurgical bonding steel surface composite titanium alloy coating can be prepared by adopting a laser cladding technology, has high degree of automation and short production period, and can prepare titanium alloy coating parts with complex shapes.
It can be appreciated that the preparation method of the metallurgical bonding steel surface composite titanium alloy coating utilizes the laser cladding technology to prepare the transition intermediate layer, and can effectively solve the formation of Fe-Ti brittle phase and cracks between the titanium alloy coating and steel.
In some embodiments of the invention, laser cladding takes the form of continuous scanning, with the scanning tracks overlapping each other with a track overlap ratio of 20% to 80%.
In some embodiments of the invention, the laser cladding has a laser power of 800-2000W.
In some embodiments of the invention, the laser scan rate of the laser cladding is 4mm/s to 32mm/s.
In some embodiments of the invention, the laser cladding powder feeding mode comprises three-pipe coaxial powder feeding.
In some embodiments of the invention, the powder feeding rate of the laser cladding is 0.5 r/min-4 r/min.
In some embodiments of the present invention, a method of preparing a metallurgically bonded steel surface composite titanium alloy coating comprises the steps of:
step one: drying the alloy powder A and the alloy powder B to remove water adsorbed on the surfaces of the powder;
step two: polishing, cleaning and drying the surface of the steel plate to remove surface impurities and defects;
step three: taking a steel plate as a matrix, taking alloy powder B as a coating material, and continuously scanning by using a laser cladding technology to obtain a sample A;
step four: naturally cooling the sample A obtained in the step three to room temperature, and performing polishing, cleaning and drying treatment to obtain an alloy intermediate layer;
Step five: taking the alloy intermediate layer as a matrix, taking alloy powder A as a coating material, and continuously scanning by using a laser cladding technology to obtain a sample B;
step six: and D, naturally cooling the sample B obtained in the step five to room temperature, and performing polishing treatment to obtain the metallurgically bonded steel surface composite titanium alloy coating.
In some embodiments of the invention, in step two, the steel sheet comprises carbon steel, low alloy steel, stainless steel, and commonly used other grades of engineering application steel.
In some embodiments of the invention, the steel sheet has a thickness of 6mm to 10mm.
In some embodiments of the invention, the steel plate is preferably Q235 steel.
In some embodiments of the present invention, the steel sheet is polished with SiC sandpaper having a maximum polishing mesh of 800 mesh, and the polished steel sheet surface has metallic luster and no macroscopic defects.
In some embodiments of the invention, absolute ethyl alcohol with purity of more than 99.99% can be used for cleaning the polished steel plate, and the cleaned steel plate is immediately dried on the surface by an electric hair drier, so that the steel plate is prevented from rusting.
In some embodiments of the present invention, in the third step, the laser cladding technology adopts a three-pipe coaxial powder feeding mode, and the laser cladding process is performed in a protective gas environment, including air, nitrogen, argon and helium, and the surface temperature of the molten pool is 1300-1600 ℃.
In some embodiments of the invention, in the third step, laser cladding adopts a continuous scanning mode, scanning tracks are mutually overlapped, the track overlapping rate is 20% -70%, the laser power is 800-1400W, the laser scanning rate is 4-32 mm/s, and the powder feeding rate is 0.5-4 r/min.
In the fourth step, the sample A is polished by an angle grinder or a steel brush to remove an oxide layer on the surface, and the polished surface has metallic luster; and (3) cleaning the polished surface by using absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier.
In some embodiments of the present invention, in the fifth step, the laser cladding technology adopts a three-pipe coaxial powder feeding manner, and the laser cladding process is performed in an inert atmosphere environment, including argon and helium; the laser cladding process adopts a continuous scanning mode, the scanning tracks are mutually overlapped, the track overlapping rate is 20% -80%, the laser power is 800-2000W, the laser scanning rate is 4-32 mm/s, and the powder feeding rate is 0.5-4 r/min; the surface temperature of the molten pool is 1500-2000 ℃.
In some embodiments of the present invention, in the fifth step, there are two laser cladding directions of the titanium alloy powder, one is that the alloy powder B scan trajectory is parallel to the alloy powder a scan trajectory, and one is that the alloy powder B scan trajectory is perpendicular to the alloy powder a scan trajectory.
The technical solution of the present invention will be better understood by combining the following specific embodiments.
In the following examples and comparative examples, the titanium alloy powder contains the following elements in mass percent: about 6% of Al; v is about 4%; fe is less than or equal to 0.03 percent; c is less than or equal to 0.08 percent; o is less than or equal to 0.20 percent; n is less than or equal to 0.05 percent; h is less than or equal to 0.015 percent; the balance being Ti and impurity elements.
In the copper alloy powder, besides copper element, O is less than or equal to 0.1 percent, fe is less than or equal to 0.03 percent, and the total amount of impurity elements is less than or equal to 0.08 percent.
Example 1
The embodiment prepares a metallurgical bonding steel surface composite titanium alloy coating, which specifically comprises the following steps:
drying spherical titanium alloy powder with the mass ratio of 2:1 and the particle size of 100 mu m and spherical copper alloy powder with the particle size of 125 mu m to remove water adsorbed on the surface of the powder;
carrying out grinding and polishing treatment on a Q235 steel plate with the thickness of 6mm by using SiC abrasive paper, wherein the maximum grinding and polishing number of the SiC abrasive paper is 800 meshes, and the surface of the ground and polished Q235 steel plate has metallic luster and has no macroscopic defect;
washing the polished Q235 steel plate by absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the surface of the washed Q235 steel plate by an electric hair drier;
continuously scanning by using Q235 steel plates as a matrix and copper alloy powder as a coating material in an argon environment by using a laser cladding technology of coaxial powder feeding of three pipelines, wherein scanning tracks are mutually overlapped, the overlap ratio is 40%, the laser power is 1000W, the laser scanning speed is 10mm/s, and the powder feeding speed is 1.5r/min, so that a sample A is obtained;
When the sample A is naturally cooled to room temperature, polishing the sample A by using an angle grinder or a steel brush to remove an oxide layer on the surface, cleaning the polished surface by using absolute ethyl alcohol with the purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier to obtain a copper alloy intermediate layer;
continuously scanning by using a laser cladding technology of coaxial powder feeding of three pipelines in an argon environment by taking a copper alloy interlayer as a matrix and titanium alloy powder as a cladding material, wherein a titanium alloy powder scanning track is parallel to the copper alloy powder scanning track, the titanium alloy powder scanning tracks are mutually overlapped, the overlap ratio is 40%, the laser power is 1000W, the laser scanning speed is 10mm/s, and the powder feeding speed is 1.5r/min, so that a sample B is obtained;
and (3) after the sample B is naturally cooled to room temperature, polishing the sample B by using an angle grinder or a steel brush to remove an oxide layer on the surface, wherein the polished surface has metallic luster, and the metallurgically bonded steel surface composite titanium alloy coating is obtained.
Referring to fig. 1, the surface quality of the copper alloy interlayer of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 1 of the present invention is good, and no cracks and defects exist. Referring to fig. 2, the metallurgically bonded steel surface composite titanium alloy coating prepared in example 1 of the present invention has good surface quality and no cracks and defects.
Example 2
The embodiment prepares a metallurgical bonding steel surface composite titanium alloy coating, which specifically comprises the following steps:
drying spherical titanium alloy powder with the particle size of 125 mu m and spherical copper alloy powder with the particle size of 125 mu m in a mass ratio of 3:1 to remove water adsorbed on the surface of the powder;
carrying out grinding and polishing treatment on a Q235 steel plate with the thickness of 10mm by using SiC abrasive paper, wherein the maximum grinding and polishing number of the SiC abrasive paper is 800 meshes, and the surface of the ground and polished Q235 steel plate has metallic luster and has no macroscopic defect;
washing the polished Q235 steel plate by absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the surface of the washed Q235 steel plate by an electric hair drier;
continuously scanning by using Q235 steel plates as a matrix and copper alloy powder as a coating material in an argon environment by using a laser cladding technology of coaxial powder feeding of three pipelines, wherein scanning tracks are mutually overlapped, the overlap ratio is 50%, the laser power is 1200W, the laser scanning speed is 8mm/s, and the powder feeding speed is 1.5r/min, so that a sample A is obtained;
when the sample A is naturally cooled to room temperature, polishing the sample A by using an angle grinder or a steel brush to remove an oxide layer on the surface, cleaning the polished surface by using absolute ethyl alcohol with the purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier to obtain a copper alloy intermediate layer;
Continuously scanning by using a laser cladding technology of coaxial powder feeding of three pipelines in an argon environment by taking a copper alloy interlayer as a matrix and titanium alloy powder as a cladding material, wherein a titanium alloy powder scanning track is parallel to the copper alloy powder scanning track, the titanium alloy powder scanning tracks are mutually overlapped, the overlap ratio is 40%, the laser power is 1400W, the laser scanning speed is 8mm/s, and the powder feeding speed is 1.5r/min, so that a sample B is obtained;
and (3) after the sample B is naturally cooled to room temperature, polishing the sample B by using an angle grinder or a steel brush to remove an oxide layer on the surface, wherein the polished surface has metallic luster, and the metallurgically bonded steel surface composite titanium alloy coating is obtained.
Cutting, grinding, polishing and etching the metallurgically bonded steel surface composite titanium alloy coating prepared in the embodiment, observing the bonding morphology of the sections, and obtaining metallographic structure photos as shown in fig. 3 and 4.
Referring to fig. 3, 4 and 5, the metallurgically bonded steel surface composite titanium alloy coating prepared in example 2 of the present invention realizes metallurgical bonding, a keyhole appears at the Ti-Cu interface of the coating, no crack appears, and a needle-like alpha (alpha') phase, a fine beta phase, a lamellar alpha phase, an equiaxed crystal, dendrites and columnar crystals are formed in the coating; XRD spectrum characteristic peaks show the presence of Fe (PDF No. 00-006-0696), alpha-Ti (PDF No. 04-002-5207), beta-Ti (PDF No. 97-004-4391), cu (PDF No. 00-004-0836) and other phases, such as CuTi (PDF No. 97-062-9381), cuTi 2 (PDFno.00-015-0717)、AlCu 3 (PDF no.00-028-0005)、Al 2 Cu(PDF no.00-002-1309)、(Al 0.5 Ti 0.5 )Cu(PDF no.97-005-7720)、Ti(Fe 0.51 Al 0.49 ) 2 (PDF no.01-075-7820)。
Example 3
The embodiment prepares a metallurgical bonding steel surface composite titanium alloy coating, which specifically comprises the following steps:
drying spherical titanium alloy powder with the mass ratio of 4:1 and the particle size of 150 mu m and spherical copper alloy powder with the particle size of 180 mu m to remove water adsorbed on the surface of the powder;
carrying out grinding and polishing treatment on a Q235 steel plate with the thickness of 10mm by using SiC abrasive paper, wherein the maximum grinding and polishing number of the SiC abrasive paper is 800 meshes, and the surface of the ground and polished Q235 steel plate has metallic luster and has no macroscopic defect;
washing the polished Q235 steel plate by absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the surface of the washed Q235 steel plate by an electric hair drier;
continuously scanning by using Q235 steel plates as a matrix and copper alloy powder as a coating material in an argon environment by using a laser cladding technology of coaxial powder feeding of three pipelines, wherein scanning tracks are mutually overlapped, the overlap ratio is 30%, the laser power is 1000W, the laser scanning speed is 8mm/s, and the powder feeding speed is 1.5r/min, so that a sample A is obtained;
when the sample A is naturally cooled to room temperature, polishing the sample A by using an angle grinder or a steel brush to remove an oxide layer on the surface, cleaning the polished surface by using absolute ethyl alcohol with the purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier to obtain a copper alloy intermediate layer;
Continuously scanning by using a laser cladding technology of coaxial powder feeding of three pipelines in an argon environment by taking a copper alloy interlayer as a matrix and titanium alloy powder as a cladding material, wherein a titanium alloy powder scanning track is perpendicular to the copper alloy powder scanning track, the titanium alloy powder scanning tracks are mutually overlapped, the overlap ratio is 40%, the laser power is 1000W, the laser scanning speed is 10mm/s, and the powder feeding speed is 1.5r/min, so that a sample B is obtained;
and (3) after the sample B is naturally cooled to room temperature, polishing the sample B by using an angle grinder or a steel brush to remove an oxide layer on the surface, wherein the polished surface has metallic luster, and the metallurgically bonded steel surface composite titanium alloy coating is obtained.
Referring to fig. 6, the metallurgically bonded steel surface composite titanium alloy coating prepared in example 3 of the present invention was not metallurgically bonded at the laser start position, and a complete coating surface was formed after several passes of scanning. The metallurgically bonded steel surface composite titanium alloy coating prepared in this example was cut, ground and polished, and the bonding morphology of the sections was observed, and the SEM photograph obtained was shown in fig. 7. Referring to fig. 7, the metallurgically bonded steel surface composite titanium alloy coating prepared in example 3 of the present invention achieves metallurgical bonding, unmelted titanium alloy particles are present in the coating, and keyhole is present at ti—cu interface.
Example 4
The embodiment prepares a metallurgical bonding steel surface composite titanium alloy coating, which specifically comprises the following steps:
drying spherical titanium alloy powder with the particle size of 60 mu m and spherical copper alloy powder with the particle size of 50 mu m according to the mass ratio of 4.5:1 to remove water adsorbed on the surface of the powder;
carrying out grinding and polishing treatment on a Q235 steel plate with the thickness of 10mm by using SiC abrasive paper, wherein the maximum grinding and polishing number of the SiC abrasive paper is 800 meshes, and the surface of the ground and polished Q235 steel plate has metallic luster and has no macroscopic defect;
washing the polished Q235 steel plate by absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the surface of the washed Q235 steel plate by an electric hair drier;
continuously scanning by using Q235 steel plates as a matrix and copper alloy powder as a coating material in an argon environment by using a laser cladding technology of coaxial powder feeding of three pipelines, wherein scanning tracks are mutually overlapped, the overlap ratio is 50%, the laser power is 1200W, the laser scanning speed is 10mm/s, and the powder feeding speed is 1.5r/min, so that a sample A is obtained;
when the sample A is naturally cooled to room temperature, polishing the sample A by using an angle grinder or a steel brush to remove an oxide layer on the surface, cleaning the polished surface by using absolute ethyl alcohol with the purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier to obtain a copper alloy intermediate layer;
Continuously scanning by using a laser cladding technology of coaxial powder feeding of three pipelines in an argon environment by taking a copper alloy interlayer as a matrix and titanium alloy powder as a cladding material, wherein a titanium alloy powder scanning track is perpendicular to the copper alloy powder scanning track, the titanium alloy powder scanning tracks are mutually overlapped, the overlap ratio is 50%, the laser power is 1000W, the laser scanning speed is 8mm/s, and the powder feeding speed is 1.5r/min, so that a sample B is obtained; and (3) after the sample B is naturally cooled to room temperature, polishing the sample B by using an angle grinder or a steel brush to remove an oxide layer on the surface, wherein the polished surface has metallic luster, and the metallurgically bonded steel surface composite titanium alloy coating is obtained.
Cutting, grinding, polishing and etching the metallurgical bonding steel surface composite titanium alloy coating prepared in the embodiment, observing the bonding morphology of the section, and obtaining metallographic structure photos as shown in fig. 8 and 9.
Referring to fig. 8, 9 and 10, the metallurgically bonded steel surface composite titanium alloy coating prepared in example 4 of the present invention realizes metallurgical bonding, has few lock holes and no cracks, has a large number of lock holes in the copper interlayer, and forms needle-like alpha (alpha') Phase, fine beta phase, lamellar alpha phase, equiaxed crystals, dendrites and columnar crystals, unmelted titanium alloy particles; XRD spectrum characteristic peaks show the presence of Fe (PDF No. 00-006-0696), alpha-Ti (PDF No. 04-002-5207), beta-Ti (PDF No. 97-004-4391), cu (PDF No. 00-004-0836) and other phases, such as CuTi (PDFNo.97-062-9381), cuTi 2 (PDF no.00-015-0717)、AlCu 3 (PDF no.00-028-0005)、Al 2 Cu(PDF no.00-002-1309)、(Al 0.5 Ti 0.5 )Cu(PDF no.97-005-7720)、Ti(Fe 0.51 Al 0.49 ) 2 (PDFno.01-075-7820)。
Example 5
The embodiment prepares a metallurgical bonding steel surface composite titanium alloy coating, which specifically comprises the following steps:
drying spherical titanium alloy powder with the particle size of 200 mu m and spherical copper alloy powder with the particle size of 250 mu m in a mass ratio of 5.5:1 to remove water adsorbed on the surface of the powder;
carrying out grinding and polishing treatment on a Q235 steel plate with the thickness of 10mm by using SiC abrasive paper, wherein the maximum grinding and polishing number of the SiC abrasive paper is 800 meshes, and the surface of the ground and polished Q235 steel plate has metallic luster and has no macroscopic defect;
washing the polished Q235 steel plate by absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the surface of the washed Q235 steel plate by an electric hair drier; continuously scanning by using Q235 steel plates as a matrix and copper alloy powder as a coating material in an argon environment by using a laser cladding technology of coaxial powder feeding of three pipelines, wherein scanning tracks are mutually overlapped, the overlap ratio is 60%, the laser power is 1200W, the laser scanning speed is 8mm/s, and the powder feeding speed is 1.5r/min, so that a sample A is obtained;
when the sample A is naturally cooled to room temperature, polishing the sample A by using an angle grinder or a steel brush to remove an oxide layer on the surface, cleaning the polished surface by using absolute ethyl alcohol with the purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier to obtain a copper alloy intermediate layer;
Continuously scanning by using a laser cladding technology of coaxial powder feeding of three pipelines in an argon environment by taking a copper alloy interlayer as a matrix and titanium alloy powder as a cladding material, wherein a titanium alloy powder scanning track is perpendicular to the copper alloy powder scanning track, the titanium alloy powder scanning tracks are mutually overlapped, the overlap ratio is 55%, the laser power is 1200W, the laser scanning speed is 8mm/s, and the powder feeding speed is 1.5r/min, so that a sample B is obtained;
and (3) after the sample B is naturally cooled to room temperature, polishing the sample B by using an angle grinder or a steel brush to remove an oxide layer on the surface, wherein the polished surface has metallic luster, and the metallurgically bonded steel surface composite titanium alloy coating is obtained.
The metallurgically bonded steel surface composite titanium alloy coating prepared in this example was cut, ground and polished, and the bonding morphology of the sections was observed, and SEM photographs obtained are shown in fig. 11 and 12.
Referring to fig. 11 and 12, the metallurgically bonded steel surface composite titanium alloy coating prepared in example 5 of the present invention achieves metallurgical bonding without keyhole and crack, unmelted titanium alloy particles are present in the coating, dendrites and columnar crystals are formed in the coating.
Example 6
The embodiment prepares a metallurgical bonding steel surface composite titanium alloy coating, which specifically comprises the following steps:
Drying spherical titanium alloy powder with the mass ratio of 7:1 and the particle size of 120 mu m and spherical copper alloy powder with the particle size of 150 mu m to remove water adsorbed on the surface of the powder;
carrying out grinding and polishing treatment on a Q235 steel plate with the thickness of 10mm by using SiC abrasive paper, wherein the maximum grinding and polishing number of the SiC abrasive paper is 800 meshes, and the surface of the ground and polished Q235 steel plate has metallic luster and has no macroscopic defect;
washing the polished Q235 steel plate by absolute ethyl alcohol with purity of more than 99.99%, and immediately drying the surface of the washed Q235 steel plate by an electric hair drier;
continuously scanning by using Q235 steel plates as a matrix and copper alloy powder as a coating material in an argon environment by using a laser cladding technology of coaxial powder feeding of three pipelines, wherein scanning tracks are mutually overlapped, the overlap ratio is 50%, the laser power is 1200W, the laser scanning speed is 10mm/s, and the powder feeding speed is 1.5r/min, so that a sample A is obtained;
when the sample A is naturally cooled to room temperature, polishing the sample A by using an angle grinder or a steel brush to remove an oxide layer on the surface, cleaning the polished surface by using absolute ethyl alcohol with the purity of more than 99.99%, and immediately drying the cleaned surface by using an electric hair drier to obtain a copper alloy intermediate layer;
continuously scanning by using a laser cladding technology of coaxial powder feeding of three pipelines in an argon environment by taking a copper alloy interlayer as a matrix and titanium alloy powder as a cladding material, wherein a titanium alloy powder scanning track is perpendicular to the copper alloy powder scanning track, the titanium alloy powder scanning tracks are mutually overlapped, the overlap ratio is 50%, the laser power is 1400W, the laser scanning speed is 8mm/s, and the powder feeding speed is 1.5r/min, so that a sample B is obtained;
And (3) after the sample B is naturally cooled to room temperature, polishing the sample B by using an angle grinder or a steel brush to remove an oxide layer on the surface, wherein the polished surface has metallic luster, and the metallurgically bonded steel surface composite titanium alloy coating is obtained.
The metallurgical bonding steel surface composite titanium alloy coating prepared in the embodiment is cut, ground, polished and etched, the bonding morphology of the section is observed, and the obtained metallographic structure photo is shown in fig. 13 and 14.
Referring to fig. 13 and 14, the metallurgically bonded steel surface composite titanium alloy coating prepared in example 6 of the present invention was metallurgically bonded without cracks, and needle-like alpha (alpha') phase, fine beta phase, lamellar alpha phase, equiaxed crystal, dendrite and columnar crystal, unmelted titanium alloy particles were formed in the coating.
Comparative example 1
The comparative example prepared a wear-resistant corrosion-resistant Q235/titanium coating, the raw materials and the rest steps of the preparation method were the same as those of example 6, except that the surface of Q235 was not clad with a copper interlayer, and the surface of the Q235 steel plate was polished with titanium alloy powder directly.
Comparative example 2
The comparative example is a Q235 steel plate, the polishing treatment is carried out by using SiC sand paper, the maximum polishing number of the SiC sand paper is 2000 meshes, and the surface of the polished Q235 steel plate has mirror finish and has no macroscopic defect, so that the polished Q235 steel plate is used for the subsequent comparative experiment.
To test the properties of the metallurgically bonded steel surface composite titanium alloy coating of the invention, the following experiments were performed: 1. molten pool surface temperature test in laser cladding process
The surface temperature of the molten pool in the laser cladding process of the embodiment 2, the embodiment 4, the embodiment 5 and the embodiment 5 is tested by using a calibrated single-point thermal infrared thermometer, and the result is shown in a graph 15, wherein the change range of the surface temperature of the molten pool is 1636-1808 ℃, and the surface temperature of the molten pool of the embodiment 2 is the highest, which indicates that the surface temperature of the molten pool can be influenced by the laser cladding process parameters.
2. Coating thickness test
The coating thicknesses of examples 2, 4, 5 and 6 were measured using a coating thickness gauge, and as a result, as shown in fig. 16, the coating thickness of example 4 was maximum (1106.1 μm), the coating thickness of example 5 was minimum (1049.1 μm), indicating that the powder feeding rate and the laser power are major factors affecting the coating thickness, and that an increase in the powder feeding rate and the laser power could cause an increase in the coating thickness.
3. Microhardness test
The microhardness of examples 2, 4, 5 and 6 was measured using a vickers hardness tester, using an HV indenter, with a test force of 100gf, a force holding time of 10s, and a spacing between test points of 50 μm, and as a result, as shown in fig. 17, the metallurgically bonded steel surface composite titanium alloy coating had a hardness higher than that of the Q235 matrix, and the process parameters were the main factors affecting the microhardness of the coating, and the microhardness of example 5 was up to 515.04HV0.1, indicating that the metallurgically bonded steel surface composite titanium alloy coating prepared in example 5 had better wear resistance and abrasion corrosion resistance.
4. Corrosion resistance test
The corrosion resistance of example 2, example 4, example 5, example 6, comparative example 1 and comparative example 2 was tested in a NaCl solution with a mass fraction of 3.5wt.% using an electrochemical workstation, and as a result, as shown in fig. 18, the metallurgically bonded steel surface composite titanium alloy coatings prepared in example 2, example 4, example 5 and example 6 at room temperature had good corrosion resistance, which was significantly superior to those of comparative example 1 and comparative example 2, indicating that the metallurgically bonded steel surface composite titanium alloy coatings prepared in the present invention can play a good corrosion protection role.
XRD characterization of the surfaces of example 4, example 5 and example 6 after corrosion resistance testing, the phase composition of the metallurgically bonded steel surface composite titanium alloy coating prepared in example 4, example 5 and example 6 was unchanged, in terms of α -Ti (PDF No. 04-002-5207), β -Ti (PDF No. 97-004-4391), cu (PDF No. 00-004-0836), cuTi (PDF No. 97-062-9381) and CuTi 2 (PDF No. 00-015-0717) is the main.
5. Shear Strength test
The shear strength of example 2, example 4, example 5 and example 6 was measured according to the GB/T6396-2008 composite steel plate mechanical and technological performance test method by using a universal tester, and the result is shown in FIG. 19, wherein the shear strength of example 2 is minimum (167.4 MPa), the shear strength of example 5 is maximum (335.3 MPa), which shows that the powder feeding rate and the laser power are the main factors influencing the coating thickness, and the higher the shear strength means the better the bonding degree of the composite titanium alloy coating on the metallurgically bonded steel surface.
In summary, the metallurgically bonded steel surface composite titanium alloy coating and the preparation method thereof provided by the invention are used for effectively protecting marine engineering equipment steel by limiting the technical scheme, are applied to the technical field of metal corrosion and protection, have longer service life through metallurgically bonding, have simple preparation flow, low cost and short production cycle, can be used for preparing metallurgically bonded steel surface composite titanium alloy coating parts with complex shapes, can be industrially produced, and can be applied to various working condition environments.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The metallurgical bonding steel surface composite titanium alloy coating is characterized in that the preparation raw materials comprise alloy powder A and alloy powder B, wherein the alloy powder A comprises at least one of copper alloy powder, nickel alloy powder, niobium alloy powder, molybdenum alloy powder, aluminum alloy powder and magnesium alloy powder; the alloy powder B comprises titanium alloy powder, and the mass ratio of the alloy powder A to the alloy powder B is (2-8): 1, a step of; the metallurgically bonded steel surface composite titanium alloy coating comprises an intermediate layer formed by the alloy powder A and a surface layer formed by the alloy powder B from a substrate;
The titanium alloy powder comprises the following elements in percentage by mass:
Al:5.5％～6.75％；
V:3.5％～4.5％；
Fe:≤0.03％％；
C:≤0.08％％；
O:≤0.20％；
N:≤0.05％；
H:≤0.015％；
the balance being Ti and impurity elements.
2. The metallurgically bonded steel surface composite titanium alloy coating of claim 1 wherein alloy powder a is a copper alloy powder wherein O is no more than 0.1%, fe is no more than 0.03%, and the total amount of impurity elements is no more than 0.08%.
3. The metallurgically bonded steel surface composite titanium alloy coating according to claim 1 or 2 wherein the thickness of the intermediate layer is 100-600 μm.
4. The metallurgically bonded steel surface composite titanium alloy coating according to claim 1 or 2 wherein the thickness of the surface layer is 400-1600 μm.
5. The metallurgically bonded steel surface composite titanium alloy coating according to claim 1 or 2, wherein in the metallurgically bonded steel surface composite titanium alloy coating, the metallographic structure comprises acicular alpha (alpha') phase, fine beta phase, lamellar alpha phase, equiaxed crystal, dendrite and columnar crystal, metal intermediate phase and unmelted titanium alloy particles, the coating microhardness reaches 350-700hv0.1, and the shear strength is 200-500 MPa.
6. A method of preparing a metallurgically bonded steel surface composite titanium alloy coating according to any one of claims 1 to 5, wherein the method is: and in an inert atmosphere environment, scanning the surface of the substrate by using the alloy powder A and the alloy powder B sequentially through laser cladding.
7. The method of claim 6, wherein the laser cladding has a laser power of 800 to 2000W.
8. The method of claim 6, wherein the laser cladding has a laser scan rate of 4mm/s to 32mm/s.
9. The method of claim 6, wherein the laser cladding powder feeding mode comprises three-pipe coaxial powder feeding.
10. The method of claim 6, wherein the laser cladding has a powder feed rate of 0.5r/min to 4r/min.
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| CN113512724A (en) * | 2021-06-22 | 2021-10-19 | 中山大学 | Corrosion-resistant titanium steel composite material containing copper-molybdenum alloy layer and preparation method thereof |
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