CN111979541B - Titanium alloy with Ti-Nb alloy coating and preparation method and application thereof - Google Patents
Titanium alloy with Ti-Nb alloy coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN111979541B CN111979541B CN202010851535.5A CN202010851535A CN111979541B CN 111979541 B CN111979541 B CN 111979541B CN 202010851535 A CN202010851535 A CN 202010851535A CN 111979541 B CN111979541 B CN 111979541B
- Authority
- CN
- China
- Prior art keywords
- coating
- powder
- alloy
- titanium alloy
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention relates to a titanium alloy with a Ti-Nb alloy coating, and a preparation method and application thereof. The Ti-Nb coating is attached to the titanium alloy substrate; the titanium alloy matrix is a nickel-rich shape memory alloy and is an austenite phase; the near surface of the Ti-Nb coating does not contain Ni elements, the microstructure of the coating contains (Ti, Nb) phases, and the (Ti, Nb) phases are beta-Ti structures. The Ti-Nb coating is prepared on the titanium alloy matrix in a coaxial powder feeding and laser cladding mode. The coating has low tissue dilution rate and excellent biocompatibility, is in good metallurgical bonding with a base material, and has microhardness of 470 +/-12.5 HV. The preparation process is simple and controllable, and the obtained product has excellent performance and low cost and is convenient for large-scale application. Meanwhile, the material designed and prepared by the invention is particularly suitable for being used as a biomedical material and a high-temperature-resistant and corrosion-resistant material.
Description
Technical Field
The invention relates to a titanium alloy with a Ti-Nb alloy coating, and a preparation method and application thereof, and belongs to the technical field of surface treatment.
Background
Titanium alloys are widely used in aerospace, automotive, military, life and biomedical applications due to their low elastic modulus, high corrosion resistance, high frictional wear resistance, high damping and excellent biocompatibility. Among them, more prominently, nitinol has a special shape memory effect and superelasticity, and it is a clinically very good implant material. However, when implanted for a long period of time, toxic nickel ions are released, and the corrosion resistance and the frictional wear resistance of the surface of the implant are lowered. These problems have led to some limitations in the use of nitinol in biomedical materials.
The surface property and quality of biomedical materials generally have a qualitative influence on the biocompatibility of the materials, and an ideal surface coating has a special surface structure and property, and has strong bonding strength with a substrate, excellent mechanical compatibility and biocompatibility. For many years, excellent scientists have made many efforts on the problems, but the nickel-titanium alloy has the excellent performance of the nickel-titanium alloy, solves the problem of application defects, and considers the preparation cost, thereby bringing many challenges to the scientists.
In recent years, Ti-Nb alloy with a certain niobium content has shape memory effect and superelasticity, has more excellent corrosion resistance and excellent mechanical biocompatibility, and can be applied to the field of biomedicine instead of nickel-titanium alloy. However, niobium is extremely expensive, which limits its use on a large scale and its complete replacement for nitinol.
The laser cladding technology is a new surface modification and repair technology. The coaxial powder feeding type working principle is that powder is fed out through a nozzle under the protection of gas, laser is coaxially scanned, and a multi-channel multilayer cladding coating can be prepared through one-step forming. It can obviously improve the wear-resisting, corrosion-resisting, heat-resisting, oxidation-resisting and electric properties of the surface of the base layer so as to achieve the purpose of surface modification or repair. The method has the advantages of small fusion depth of the base material, metallurgical combination of the coating and the matrix, more suitable cladding materials, large and efficient particle size and content change, low cost and the like, so the method has very wide application prospect of the laser cladding technology. Few to date have thought to surface modify titanium alloys with their excellent superelasticity and biocompatibility.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the clinical defects of the existing titanium alloy, the titanium alloy with the Ti-Nb alloy coating, the preparation method and the application thereof are provided, and the problem of surface strengthening of the long-term implantation of the biomedical implant is solved. Meanwhile, the invention also solves the problems of cracks and uneven surface of the Ti-Nb coating.
The invention relates to a titanium alloy with a Ti-Nb alloy coating; a titanium alloy base material; the Ti-Nb coating is attached to the substrate; the matrix is a nickel-rich shape memory alloy and is an austenite phase; the Ti-Nb coating does not contain Ni atoms, the microstructure of the coating mainly contains (Ti, Nb) phases, and the (Ti, Nb) phases are beta-Ti structures.
The invention relates to a titanium alloy with a Ti-Nb alloy coating; the atomic ratio of Nb in the Ti-Nb coating is 15-35%, preferably 20-30%, and more preferably 23%; the balance being Ti.
As a preferred scheme, the invention relates to a titanium alloy with a Ti-Nb alloy coating; the titanium alloy is nickel titanium alloy.
The invention relates to a titanium alloy with a Ti-Nb alloy coating; the bonding interface of the coating and the base material is compact and flat, metallurgical bonding is realized, and the surface of the coating is smooth and compact; the hardness of the coating is 470 +/-12.5 HV. The non-overlapped area of the coating is 1-3 um crystal grains and a large amount of nanocrystalline, and the crystal grains in the overlapped area are larger and mainly are 3-10 um crystal grains.
The invention relates to a titanium alloy with a Ti-Nb alloy coating; the thickness of the single-layer cladding coating is 1.0-1.5 mm.
The invention relates to a titanium alloy with a Ti-Nb alloy coating; and forming a Ti-Nb alloy coating on the surface of the nickel base by laser cladding.
The invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; taking a titanium alloy with a clean and dry surface as a base material; taking Ti and Nb element mixed powder as a raw material; coating the Ti and Nb element mixed powder on a base material by laser cladding to obtain a product; during laser cladding, the laser power is controlled to be 250-450W, preferably 350-400W, the laser power is 1.6-3.6mm/s, preferably 2.0-3.0mm/s, the spot diameter is 2.0mm, the lap joint rate is 30-60%, preferably 50%, and the powder feeding rate is 0.08-0.15g/s, preferably 0.1 g/s. As a preferred scheme, the cladding path is one-way cladding, and the laser returns. The coating surface is remelted once. And g codes are recorded, and the whole process is controlled by a computer.
The invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; the titanium alloy with clean and dry surface is obtained by the following treatment method: firstly, polishing a titanium alloy substrate by a water mill to be flat, then respectively soaking the surface of the substrate with cotton in deionized water, acetone, deionized water and absolute ethyl alcohol, and cleaning surface stains strictly according to the sequence.
The invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; the atomic ratio of Nb in the Ti/Nb element mixed powder is 15 to 35%, preferably 20 to 30%, and more preferably 23%; the balance being Ti.
The invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; the Ti and Nb element mixed powder is prepared by the following steps:
the invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; furthermore, the particle size of the titanium powder is 53-125 μm, the oxygen content is less than or equal to 0.18 wt%, the average particle size is 83 μm, the particle size of the niobium powder is 50-120 μm, the average particle size is 77 μm, and the oxygen content is less than or equal to 0.32%.
The invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; the Ti and Nb element powder is irregular Ti and Nb element powder. Titanium powder and niobium powder are taken according to the distribution of a design group, and the powder is strictly placed in argon gas in a protective atmosphere to prevent oxygen from being introduced. And, the materials are mixed for 9 hours, so as to achieve the effect of uniformly mixing the powder.
The invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; the powder is fed by adopting a coaxial powder feeding mode.
The preparation process used in the invention has low requirements on the flowability of the powder.
The coating preparation process can adopt a full-automatic mode or a semi-automatic mode. Note that the following operations are strictly followed: firstly, before laser cladding, opening a gas cylinder and then feeding powder; after the experiment, the powder feeding is stopped first and then the gas cylinder is closed. Second, if the experiment is stopped halfway, it is necessary to shut off the laser and reopen the chamber.
The invention relates to a preparation method of a titanium alloy with a Ti-Nb alloy coating; obtaining a plurality of Ti-Nb alloy coatings with 1-3 layers through laser cladding; the total thickness of the Ti-Nb alloy coating is 1.0-3.0 mm.
As a general technical concept, the invention also provides application of the Ti-Nb alloy coating laser-clad on the surface of the upper titanium alloy in biomedical treatment, and the specific application comprises a human rib embracing device, a bracket, bone nails, a vascular clamp and a dental appliance. Meanwhile, the material designed and prepared by the invention can also be used as a high-temperature-resistant and corrosion-resistant material. Due to the characteristics of the material designed and prepared by the invention, the material can be used as biomedical materials, aerospace industrial materials and automobile industrial materials.
According to the invention, Ti-Nb alloy coating is formed on the surface of the nickel-titanium alloy by mixing Ti and Nb element mixed powder and laser cladding, the bonding interface of the coating and a matrix material is compact and flat, good metallurgical bonding is realized, the coating is compact, the crystal grains are fine, and the surface of the coating is flat. The coating has the characteristics of superelasticity, high strength, abrasion and wear resistance, corrosion resistance and the like, can effectively prevent the release of nickel ions, improves the biocompatibility of the nickel-titanium alloy, and is not easy to fall off in the application of superelasticity and shape memory of the nickel-titanium alloy.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) the Ti-Nb alloy material meets the biocompatibility, improves the wear resistance and the corrosion resistance, and successfully prevents the release of nickel ions; the Ti and Nb mixed powder material has low oxygen content and simple preparation method, and the coating mainly contains a beta-Ti phase and is in good metallurgical bonding with the base material.
(2) The coating is prepared by adopting a laser cladding technology, the quality of the coating can be controlled by controlling laser process parameters (laser power, laser scanning rate, laser spot size, lap joint rate, powder feeding rate and the like), and the surface texture and mechanical property of the coating can be regulated and controlled by selecting different layers of coatings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without any inventive step.
Fig. 1 is a spectrum obtained by scanning an element mixed powder obtained in the first embodiment of the present invention with an energy spectrometer.
FIG. 2 is a schematic diagram of the overall gold phase of the coating layer according to an embodiment of the present invention.
FIG. 3 is a scanning electron microscope image of the bonding interface between the coating and the substrate in the product according to the embodiment of the invention.
FIG. 4 is a diagram of the gold phase of the interface between the coating and the substrate in the product manufactured by the second embodiment of the present invention.
FIG. 5 is a scanning electron microscope image of the bonding interface between the coating and the substrate in the product manufactured by the second embodiment of the present invention.
FIG. 6 is a metallographic photograph of the surface of a coating prepared according to the second example of the present invention.
Detailed Description
The present invention will now be illustrated by the following preferred examples, which should not be construed as limiting the scope of the invention.
Example one
Taking materials according to the following atomic ratio: 77% of irregular-shaped titanium powder and 23% of irregular-shaped niobium powder. The average particle size of the niobium powder is smaller than that of the titanium powder, the particle size of the titanium is 53-125 mu m, the average particle size is 83 mu m, the particle size of the niobium powder is 50-120 mu m, and the average particle size is 77 mu m. It is carried out strictly in a hypoxic glove box and is filled with a protective gas, for example argon, as used in the present invention. To prevent oxygen ingress during mixing, the powder was strictly sealed in a glove box and mixed in the blender for a common 9 hours. After the powder mixing is finished, a small amount of powder is taken from the glove box for scanning electron microscope analysis and is matched with energy spectrometer analysis, so that the uniform distribution of the Ti powder and the Nb powder can be found (shown in figure 1), and the result of the energy spectrometer is approximate to the material mixing ratio.
Nickel-rich NiTiAfter the alloy substrate is polished by a water grinder, the surface of the substrate is cleaned by medical cotton dipped with deionized water → acetone → deionized water → absolute ethyl alcohol respectively. Then the chamber is placed in a chamber of a laser metal deposition device, the chamber is vacuumized by a vacuum pump, the chamber is filled with argon, and a low-oxygen environment is kept. Placing the mixed powder of Ti and Nb elements in a powder feeder and waiting for powder feeding. Setting laser process parameters: the laser power is 350W, the laser speed is 3.0mm/s, the spot diameter is 2mm, the lap joint rate is 70 percent, and the powder feeding speed is 0.1 g/s. And then eight single-layer Ti-Nb alloy coatings are subjected to laser cladding, the cladding path is one-way cladding, the laser returns to the original point in an empty mode, and the whole process is intelligently controlled by a computer. The base material of certain thickness is kept, the laser cladding appearance is cut along the cross section, the chemical corrosion goes out the grain boundary after the polishing, 2000 meshes are gone up in the abrasive paper, and the polishing solution configuration is OPS: h 2 O 2 Adding a small amount of water for polishing, namely 9: 1; the corrosion liquid is prepared into HF HNO 3 :HO 2 The corrosion time is 15s, the corrosion time is not long, and otherwise, the sample preparation is needed again due to over corrosion. And (3) performing metallographic phase photographing under an optical microscope to obtain a metallographic phase photograph (as shown in figure 2) of the Ti-Nb alloy coating, and then representing the bonding interface of the coating and the base material by using a scanning electron microscope (as shown in figure 3). The surface of the laser cladding single-layer Ti-Nb coating can be found to be smooth. The nickel atoms diffuse to the coating and then gradually disappear less. The microhardness analysis of the coating is carried out, under the condition that the load is 200g and the holding time is 10s, the microhardness of the Ti-Nb coating in the heat affected zone of the base material is maximum and reaches 500.28HV, the surface hardness of the coating is 430.01HV and is about one time of the base material, and the microhardness of the base material is 235.14 HV. The corrosion resistance of the NiTi alloy with the Ti-Nb alloy coating is higher than that of the NiTi alloy without the coating, and the nickel ion release rate of the NiTi alloy with the Ti-Nb alloy coating is much lower.
Example two
The powder ratio, the powder mixing condition, the substrate surface treatment condition and the laser cladding condition are the same as those of the first embodiment, except that the laser process parameters are set: the laser power is 400W, the laser speed is 3.0mm/s, the spot diameter is 2mm, the lap joint rate is 50 percent, and the powder feeding speed is 0.1 g/s. And then carrying out laser cladding on eight single-layer Ti-Nb alloy coatings, wherein the cladding path is one-way cladding, the laser returns to the original point in an idle mode, and the whole process is controlled intelligently by a computer. And (3) reserving a base material with a certain thickness, cutting the laser cladding sample along the cross section, grinding and polishing the laser cladding sample, and then chemically corroding a grain boundary, wherein the treatment process is the same as the first embodiment. And (3) obtaining a metallographic photograph (as shown in figure 4) of a bonding interface of the Ti-Nb alloy coating and the NiTi base material by photographing a metallographic structure under an optical microscope, and representing the bonding interface of the coating and the base material by using a scanning electron microscope (as shown in figure 5). In particular, nickel atoms diffuse into the coating and then gradually decay less. The surface of the coating is metallographic (as shown in fig. 6), and the surface of the laser cladding Ti-Nb coating is smooth and flat. The microhardness analysis of the coating is carried out, under the condition of loading of 200g and keeping for 10s, the microhardness of the Ti-Nb coating in the heat affected zone of the base material is the maximum and reaches 580HV, the surface hardness of the coating is 470.09HV which is one time of the base material, and the microhardness of the base material is 235.14 HV. The Ti-Nb coated titanium alloy is soaked in a simulated human body fluid for ten days, and no toxic nickel ions are released. The Ti-Nb coated titanium alloy and the uncoated titanium alloy are respectively subjected to electrochemical corrosion in a human body simulation solution for two hours, and the corrosion current of the Ti-Nb coated titanium alloy is lower, the corrosion potential is higher, and the Ti-Nb coated titanium alloy is proved to have better corrosion resistance.
EXAMPLE III
The powder ratio, the powder mixing condition, the substrate surface treatment and the laser cladding condition are the same as those of the first embodiment, except that the laser process parameters are set: the laser power is 350W, the laser speed is 3.0mm/s, the spot diameter is 2mm, the lap joint rate is 50 percent, and the powder feeding speed is 0.1 g/s. And then cladding sixteen layers of Ti-Nb alloy coatings by laser, and cladding one layer by one layer. The cladding path is one-way cladding, and the laser returns to the original point. And (3) stopping powder feeding when the technological parameters are unchanged, remelting the laser surface once, and intelligently controlling by using a computer in the whole process. And (3) reserving a base material with a certain thickness, cutting the laser cladding sample along the cross section, grinding and polishing, and then chemically corroding to form a grain boundary, wherein the treatment process is the same as that of the first embodiment. And (3) obtaining a metallographic photograph of a bonding interface of the Ti-Nb alloy coating and the NiTi base material by photographing a metallographic structure under an optical microscope, and representing the bonding interface of the coating and the base material by using a scanning electron microscope. In particular, nickel atoms diffuse onto the coating and then gradually disappear, leaving no nickel atoms on the surface of the coating. The surface of the coating is metallographic, and the surface of the laser cladding Ti-Nb coating is smooth and flat. The microhardness analysis of the coating is carried out, under the condition of loading of 200g and keeping for 10s, the microhardness of the Ti-Nb coating in the heat affected zone of the base material is the largest, which reaches 550.20HV, the surface hardness of the coating is 482.5HV which is more than one time of the base material, and the microhardness of the base material is 235.14 HV. The Ti-Nb coated titanium alloy is soaked in a simulated human body fluid for ten days, and no toxic nickel ions are released. The titanium alloy with the Ti-Nb alloy coating and the titanium alloy without the Ti-Nb alloy coating are subjected to electrochemical corrosion in a human body simulation solution for two hours respectively, and the corrosion current of the titanium alloy with the Ti-Nb alloy coating is lower, the corrosion potential is higher, and the titanium alloy with the Ti-Nb alloy coating and the titanium alloy without the Ti-Nb alloy coating are proved to have better corrosion resistance. The coating has higher corrosion resistance and higher friction and wear resistance.
Example four
The powder proportioning, the powder mixing condition, the substrate surface treatment and the laser cladding condition are the same as those of the first embodiment, except that the laser surface remelting parameters are set: the laser power is 400W, the laser speed is 3.0mm/s, the spot diameter is 2mm, and the lap joint rate is 50%. Then laser cladding three layers of Ti-Nb alloy coatings, cladding one layer by one layer and remelting the surface once. And (4) carrying out intelligent control by a computer in the whole process. The samples were wire cut. The surface of the sample is clean and smooth. And after cross section grinding and polishing, chemical corrosion is carried out to obtain a grain boundary, and the processing process is the same as that of the first embodiment. The metallographic structure of the remelting zone is photographed under an optical microscope, and the structural morphology of the remelting zone is represented by a scanning electron microscope. The microhardness of the surface of the base material is analyzed, under the condition of loading of 200g and keeping for 10s, the microhardness is as high as 580.26HV and is more than one time of the body material, and the microhardness of the base material is 235.14 HV. And respectively placing the NiTi alloy with the remelted surface and the untreated NiTi alloy into a human body simulated body fluid, and soaking for ten days to find that the release amount of nickel ions of the NiTi alloy is reduced. The NiTi alloy with the remelted surface and the NiTi alloy with the processed surface are respectively subjected to electrochemical corrosion in a human body simulation solution for two hours, and the corrosion current of the NiTi alloy is lower, the corrosion potential is higher, and the NiTi alloy is proved to have better corrosion resistance.
Comparative example 1
Taking materials according to the following atomic proportions: 77% of irregular-shaped titanium powder and 23% of irregular-shaped niobium powder. The average particle size of the niobium powder is smaller than that of the titanium powder, the particle size of the titanium is 53-125 mu m, the average particle size is 83 mu m, the particle size of the niobium powder is 50-120 mu m, and the average particle size is 77 mu m. Strictly in a hypoxic glove box, and filled with the protective gas argon. To prevent oxygen ingress during mixing, the powder was strictly sealed in a glove box and mixed in the blender for a common 2 hours. After the powder mixing is finished, a small amount of powder is taken out from the glove box for scanning electron microscope analysis and is matched with energy spectrometer analysis, so that the Ti powder and the Nb powder are not uniformly distributed, and one element powder is in an aggregated state. The Ti-Nb alloy coating prepared by the powder has uneven tissue distribution, is mostly pure titanium phase, has reduced mechanical quality and reduced corrosion resistance, and has poorer coating elasticity than the examples.
Comparative example No. two
The powder ratio, the powder mixing condition, the substrate surface treatment and the laser cladding condition are the same as those of the first embodiment, except that the laser process parameters are set: the laser power is 250W, the laser speed is 3.6mm/s, the spot diameter is 2mm, the lap joint rate is 70 percent, and the powder feeding rate is 0.1 g/s. And then carrying out laser cladding on eight single-layer Ti-Nb alloy coatings, wherein the cladding path is one-way cladding, the laser returns to the original point in an idle mode, and the whole process is controlled intelligently by a computer. Note that in order to prevent the occurrence of the dust sticking condition during the experiment, the following operations were strictly followed: before laser cladding, opening a gas cylinder and then feeding powder; after the experiment, the powder feeding is stopped and then the gas cylinder is closed. Secondly, if the experiment process is stopped midway, the laser must be turned off and then the chamber is opened; third, too fast or too slow airflow will cause experimental failure.
And (3) reserving a base material with a certain thickness, cutting the laser cladding sample along the cross section, grinding and polishing the laser cladding sample, and then chemically corroding a grain boundary, wherein the treatment process is the same as the first embodiment. And (3) obtaining a metallographic picture of the Ti-Nb alloy coating under an optical microscope, and representing the bonding interface of the coating and the base material by using a scanning electron microscope. Numerous unmelted particles were present in the sample and the surface quality was poor. And (3) carrying out microhardness analysis on the coating, wherein the microhardness of the Ti-Nb coating in a heat affected zone of the base material is the largest, but the surface hardness distribution of the coating is uneven and has large difference. This is due to insufficient laser energy.
Comparative example No. three
The powder ratio, the powder mixing condition, the substrate surface treatment and the laser cladding condition are the same as those of the first embodiment, except that the laser process parameters are set: the laser power is 450W, the laser speed is 1.6mm/s, the spot diameter is 2mm, the lap joint rate is 70 percent, and the powder feeding rate is 0.1 g/s. And then eight single-layer Ti-Nb alloy coatings are subjected to laser cladding, the cladding path is one-way cladding, the laser returns to the original point in an empty mode, and the whole process is intelligently controlled by a computer. And (3) reserving a base material with a certain thickness, cutting the laser cladding sample along the cross section, grinding and polishing the laser cladding sample, and then chemically corroding a grain boundary, wherein the treatment process is the same as the first embodiment. And (3) obtaining a metallographic picture of the Ti-Nb alloy coating under an optical microscope, and representing the bonding interface of the coating and the base material by using a scanning electron microscope. But the crack is deep lapped, or propagates along the weld line, or is deeper than the coating. Too high an energy density can cause the nickel of the substrate to be carried into the coating, and segregation of the nickel-rich phase will occur during solidification, eventually resulting in a reduction in the corrosion resistance of the sample.
Comparative example No. four
Taking materials according to the following atomic ratio: 90% of irregular-shaped titanium powder and 10% of irregular-shaped niobium powder. The average particle size of the niobium powder is smaller than that of the titanium powder, the particle size of the titanium is 53-125 mu m, the average particle size is 83 mu m, the particle size of the niobium powder is 50-120 mu m, and the average particle size is 77 mu m. The two element powders are mixed evenly under the protective atmosphere.
After the nickel-rich NiTi alloy substrate is polished by a water mill, the surface of the substrate is cleaned by medical cotton dipped in deionized water → acetone → deionized water → absolute ethyl alcohol respectively. Then the chamber is placed in a chamber of a laser metal deposition device, the chamber is vacuumized by a vacuum pump, the chamber is filled with argon, and a low-oxygen environment is kept. Placing the mixed powder of Ti and Nb elements in a powder feeder and waiting for powder feeding. Setting laser process parameters: the laser power is 350W, the laser speed is 3.0mm/s, the spot diameter is 2mm, the lap joint rate is 50 percent, and the powder feeding speed is 0.1 g/s. And then eight single-layer Ti-Nb alloy coatings are subjected to laser cladding, the cladding path is one-way cladding, the laser returns to the original point in an empty mode, and the whole process is intelligently controlled by a computer. And (3) reserving a base material with a certain thickness, cutting the laser cladding sample along the cross section, and chemically corroding a grain boundary after grinding and polishing, as in the first embodiment. And (3) obtaining a metallographic picture of the Ti-Nb alloy coating under an optical microscope, and representing the bonding interface of the coating and the base material by using a scanning electron microscope. The nickel atoms diffuse into the coating and then gradually decrease. The tensile test results show that the coating has no superelasticity. Electrochemical corrosion tests prove that the corrosion resistance of the coating is lower than that of other samples.
Claims (8)
1. A titanium alloy with a Ti-Nb alloy coating; the method is characterized in that: a titanium alloy base material; the Ti-Nb coating is attached to the substrate; the matrix is a nickel-rich shape memory alloy and is an austenite phase; the Ti-Nb coating does not contain Ni atoms, the microstructure of the coating contains a (Ti, Nb) phase, and the (Ti, Nb) phase is a beta-Ti structure;
the atomic ratio of Nb in the Ti-Nb coating is 15-35%, and the balance is Ti;
the Ti-Nb coating is prepared by the following scheme:
taking a titanium alloy with a clean and dry surface as a base material; taking Ti and Nb element mixed powder as a raw material; titanium powder and niobium powder are taken according to the distribution of a design group, the powder is strictly placed in argon gas in a protective atmosphere to prevent oxygen from being introduced, and the materials are mixed for 9 hours to achieve the effect of uniformly mixing the powder; obtaining uniformly mixed powder; then the
Coating the Ti and Nb element mixed powder on a base material by laser cladding to obtain a product; during laser cladding, the laser power is controlled to be 350-400W, the scanning speed is 2.0-3.0mm/s, the overlapping rate is 30-70%, the spot diameter is 2mm, and the powder feeding speed is 0.08-0.15 g/s.
2. A titanium alloy with a Ti-Nb alloy coating according to claim 1; the method is characterized in that: the titanium alloy is nickel titanium alloy.
3. A titanium alloy with a Ti-Nb alloy coating according to claim 1; the method is characterized in that: the bonding interface of the coating and the substrate material is compact and flat, metallurgical bonding is realized, and the surface of the coating is smooth and compact; the hardness of the coating is 470 +/-12.5 HV; the size of the non-overlapping area of the coating is less than or equal to 3um, and the size of the crystal grains in the overlapping area is greater than 3um and less than or equal to 10 um.
4. A titanium alloy with a Ti-Nb alloy coating according to claim 1; the method is characterized in that: the thickness of the single-layer cladding coating is 1.0-1.5 mm.
5. A titanium alloy with a Ti-Nb alloy coating according to claim 1; the method is characterized in that: the titanium alloy with clean and dry surface is obtained by the following treatment method: firstly, polishing a titanium alloy substrate by a water mill to be flat, and then respectively soaking the deionized water, acetone, deionized water and absolute ethyl alcohol in cotton to wipe the surface of the substrate.
6. A titanium alloy with a Ti-Nb alloy coating according to claim 1; the method is characterized in that: the atomic ratio of Nb in the Ti and Nb element mixed powder is 20-30 percent; the balance being Ti;
the Ti and Nb element mixed powder is prepared by the following steps:
titanium powder and niobium powder are distributed according to a design group; and uniformly mixing under a protective atmosphere to obtain Ti and Nb element mixed powder.
7. A titanium alloy with a Ti-Nb alloy coating according to claim 1; the method is characterized in that:
the Ti and Nb element powder is irregular Ti and Nb element mixed powder;
before laser cladding, opening a gas cylinder and then feeding powder; during laser cladding, powder is fed in a coaxial powder feeding mode; and after laser cladding is finished, stopping powder feeding and then closing the gas cylinder.
8. Use of a titanium alloy with a Ti-Nb alloy coating according to any of claims 1-5; the method is characterized in that: the application comprises the application of the composite material as at least one of biomedical materials, aerospace industrial materials and automobile industrial materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010851535.5A CN111979541B (en) | 2020-08-21 | 2020-08-21 | Titanium alloy with Ti-Nb alloy coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010851535.5A CN111979541B (en) | 2020-08-21 | 2020-08-21 | Titanium alloy with Ti-Nb alloy coating and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111979541A CN111979541A (en) | 2020-11-24 |
| CN111979541B true CN111979541B (en) | 2022-09-27 |
Family
ID=73444149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010851535.5A Active CN111979541B (en) | 2020-08-21 | 2020-08-21 | Titanium alloy with Ti-Nb alloy coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111979541B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113846245B (en) * | 2021-09-01 | 2022-10-11 | 南京航空航天大学 | 3D printing Ti-Nb alloy with composite structure and preparation method thereof |
| CN114561622B (en) * | 2022-01-14 | 2024-04-26 | 西安理工大学 | Gradient structure Ti-Nb alloy film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696480A (en) * | 2009-11-04 | 2010-04-21 | 天津科技大学 | Nickel-free biomedical titanium alloy Ti-Nb-Zr material and preparation method thereof |
| CN108359972A (en) * | 2018-02-12 | 2018-08-03 | 大连海事大学 | Ni-Ti-Nb Alloy by Laser cladding coatings and preparation method thereof |
| CN111005019A (en) * | 2019-11-07 | 2020-04-14 | 中南大学 | Method for preparing TiC/TiB wear-resistant coating in situ through laser cladding |
| CN111074265A (en) * | 2019-12-18 | 2020-04-28 | 江苏大学 | Laser cladding anti-cavitation coating and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6409852B1 (en) * | 1999-01-07 | 2002-06-25 | Jiin-Huey Chern | Biocompatible low modulus titanium alloy for medical implant |
| US9828655B2 (en) * | 2015-09-04 | 2017-11-28 | Kind Fahd University of Petroleum and Minerals | Titanium alloys for biomedical applications and fabrication methods thereof |
-
2020
- 2020-08-21 CN CN202010851535.5A patent/CN111979541B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696480A (en) * | 2009-11-04 | 2010-04-21 | 天津科技大学 | Nickel-free biomedical titanium alloy Ti-Nb-Zr material and preparation method thereof |
| CN108359972A (en) * | 2018-02-12 | 2018-08-03 | 大连海事大学 | Ni-Ti-Nb Alloy by Laser cladding coatings and preparation method thereof |
| CN111005019A (en) * | 2019-11-07 | 2020-04-14 | 中南大学 | Method for preparing TiC/TiB wear-resistant coating in situ through laser cladding |
| CN111074265A (en) * | 2019-12-18 | 2020-04-28 | 江苏大学 | Laser cladding anti-cavitation coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Ni-free superelastic binary Ti-Nb Coatings obtained by Dc magnetron co-sputtering";S.Achache et.al;《Surface & Coatings Technology》;20150511;第275卷;第1-2节背景和试验部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111979541A (en) | 2020-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111979541B (en) | Titanium alloy with Ti-Nb alloy coating and preparation method and application thereof | |
| Prakash et al. | Processing and characterization of novel biomimetic nanoporous bioceramic surface on β-Ti implant by powder mixed electric discharge machining | |
| CN113652642B (en) | Gradient ceramic high-entropy alloy coating and preparation method thereof | |
| CN110938816B (en) | Laser cladding SiC nanoparticle reinforced Ti (C, N) ceramic coating and application thereof | |
| CN105458271B (en) | A kind of titanium alloy composite material coated with composite coating and its preparation method and application | |
| Mthisi et al. | Tribological behaviour of laser synthesized Ti-Al 2 O 3 coatings on Ti-6Al-4V alloy | |
| CN109706503B (en) | Antibacterial wear-resistant coating on surface of titanium substrate and preparation method | |
| CN108559942A (en) | A method of preparing black ceramic layer on zirconium-base alloy surface | |
| Shri et al. | Surface characterization of TiNi deformed by high-pressure torsion | |
| CN105256174A (en) | Biotic bone composite material and preparing method thereof | |
| Gemelli et al. | Thermal characterization of commercially pure titanium for dental applications | |
| Ogawa et al. | Effect of Nb Addition on Oxide Formation on Ti–xNb Alloys | |
| EP3936633A1 (en) | Treatment method for zirconium alloy and application | |
| Marchenko et al. | Reaction synthesis of gradient coatings by annealing of three-layer Ti–Ni–Ti nanolaminate magnetron sputtered on the TiNi substrate | |
| CN107805792A (en) | A kind of method for improving biologic medical magnesium surface property and corrosive wear behavior | |
| Dawood et al. | The effects of chemical oxidation on corrosion behavior of Ni-Ti alloy | |
| Sun et al. | Characteristics and in vitro biological assessment of (Ti, O, N)/Ti composite coating formed on NiTi shape memory alloy | |
| Lee | Effect of passivation and surface modification on the dissolution behavior and nano-surface characteristics of Ti-6Al-4V in Hank/EDTA solution | |
| Nasakina et al. | The production of a thin wire of Ti–Nb–Ta–Zr shape memory alloy for medical devices | |
| Zhang et al. | Fabrication of Ta2O5 reinforced Ta-based coatings on Ta substrates by laser cladding | |
| Musadaq et al. | In Vitro Study for Yttrium addition on titanium-15 Molybdenum after Immersion in Simulated Body Fluid | |
| Siegmann et al. | Vacuum plasma sprayed coatings and freestanding parts of Ni-Ti shape memory alloy | |
| JP2000093498A (en) | Bone substitution material and its production | |
| CN115627404B (en) | High-entropy alloy and preparation method of high-wear-resistance corrosion-resistance high-entropy alloy | |
| Fadli et al. | Effect of solid loading and dipping time on microstructure and shear strength of hydroxyapatite coatings deposited via dip coating technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |