CN113046680B - In-situ oxidation modification method for surface of nickel-titanium alloy material - Google Patents
In-situ oxidation modification method for surface of nickel-titanium alloy material Download PDFInfo
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- CN113046680B CN113046680B CN202110257432.0A CN202110257432A CN113046680B CN 113046680 B CN113046680 B CN 113046680B CN 202110257432 A CN202110257432 A CN 202110257432A CN 113046680 B CN113046680 B CN 113046680B
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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Abstract
According to the method for modifying the surface of the nickel-titanium alloy material through in-situ oxidation, a compact and stable oxide protective film is formed on the inner surface of the thin-wall thin-diameter long tube of the NiTi memory alloy by controlling the oxygen partial pressure, the oxidation temperature and the oxidation time of the oxidation atmosphere in a heat treatment furnace, so that the oxidation resistance of the NiTi memory alloy material is obviously improved. The oxide crystal structure is rutile-phase TiO2, and the oxidized and modified thin-wall and thin-diameter long NiTi memory alloy tube has good corrosion resistance, wear resistance and biocompatibility, and can be directly applied to the field of medical instruments such as bone substitute materials. The invention adopts a low oxygen partial pressure oxidation method, can inhibit the oxidation of Ni, effectively avoids the condition that an oxidation film prepared in air or oxygen atmosphere contains Ni element in the prior art, and does not have the problems of phase change temperature change of the alloy and reduction of shape memory performance caused by the rise of oxidation temperature.
Description
Technical Field
The invention relates to the field of alloy material processing, in particular to a method for modifying the surface of a nickel-titanium alloy material by in-situ oxidation.
Background
The NiTi shape memory alloy has unique shape memory effect, pseudo elasticity, low elastic modulus and good corrosion resistance, and has wide application in the medical field. NiTi shape memory alloys have been used to make a variety of human implants such as cardiovascular stents, scoliosis correction rods, compression staples, and bone-focusing devices.
However, it also faces two major problems in clinical applications: firstly, the alloy contains nearly 50 percent (atomic fraction) of Ni, and the release of Ni ions inevitably occurs after long-term implantation, thereby causing the safety problem; secondly, the alloy is inert material without bioactivity, and when the alloy is used as a bone substitute material, the alloy cannot be directly combined with bone, so that stress cannot be continuously transferred, and an implant is easy to loosen after being impacted and corroded to cause implant failure. TiO2 2 Ceramics have been demonstrated to have excellent corrosion resistanceThe material has good wear resistance and biocompatibility, and is an ideal material for modifying the surface of the NiTi shape memory alloy.
The oxide film prepared in the air or oxygen atmosphere contains more or less Ni element, and the high temperature oxidation method is generally adopted in the prior art to reduce the content of the Ni element. Although increasing the oxidation temperature can reduce the Ni content in the oxide film, increasing the oxidation temperature changes the transformation temperature of the alloy and decreases the shape memory properties, which is detrimental to its application as an implant.
Disclosure of Invention
The invention provides a method for modifying the surface of a thin-wall thin-diameter long pipe of nickel-titanium alloy by in-situ oxidation, aiming at the defects of the prior art. The method accurately controls the in-situ oxidation reaction of the alloy surface by controlling the oxygen partial pressure, the oxidation temperature and the oxidation time in the oxidation atmosphere, and forms rutile-phase TiO on the inner surface of the pipe 2 The oxide protective film obviously improves the oxidation resistance.
The technical scheme of the invention is as follows:
a method for in-situ oxidation modification of the surface of a nickel-titanium alloy material comprises the following steps: s1, manufacturing a NiTi alloy device; s2, performing oil and stain removal pretreatment on the surface of the NiTi alloy device, then loading the NiTi alloy device into a heat treatment furnace, and vacuumizing the heat treatment furnace; s3, introducing oxidizing gas into the heat treatment furnace; the oxidizing gas comprises hydrogen and water vapor, the hydrogen is introduced at the rate of 50-200mL/min, the water vapor is introduced at the same rate, the ratio of the hydrogen to the water vapor is controlled to be 1: 1-1: 1.5, and the pressure is controlled to be 1-5 atmospheric pressures; s4, heating the furnace to 700-1000 ℃ for high-temperature oxidation, wherein the heating rate is 10-30 ℃/min; preserving the heat for 1 to 10 hours after reaching the preset high temperature to ensure that the surface of the sample is oxidized uniformly in situ; s5, cooling the furnace to a preset low temperature, and closing gas to obtain rutile-phase TiO 2 And (5) oxidizing the film.
Further, the manufacturing method of the alloy device of S1 comprises the following steps: a) According to the atomic ratio: ni a Ti 100-a A is more than or equal to 50.5 and less than or equal to 52, pure Ni and pure Ti are subjected to induction melting, and a cast ingot is obtained by a water-cooling copper mold casting method; b) Homogenizing and annealing the ingot, addingThe NiTi alloy thin-wall pipe with the inner diameter of 6.0-7.0 mm and the wall thickness of 0.2-0.5 mm is manufactured.
Further, the processing method of the cast ingot in b) comprises one of hydraulic cogging, turning, linear cutting and core drawing, cold rolling and core pulling, or the combination of a plurality of methods.
Further, the oil and stain removal pretreatment method in S2 comprises cleaning and drying.
Further, in S3, the ratio of hydrogen to water vapor in the oxidizing gas is 1: 1.2-1: 1.3, and the pressure is 2-4 atmospheres.
Further, in S4, the furnace temperature of high-temperature oxidation is 750-850 ℃, the heating rate is 15-20 ℃/min, and the temperature is kept for 5-10 h after reaching the preset temperature.
Further, in the S5, the preset low temperature is room temperature or below 150 ℃.
The invention has the following technical effects:
according to the method for modifying the surface of the nickel-titanium alloy material through in-situ oxidation, a compact and stable oxide protective film is formed on the inner surface of the thin-wall thin-diameter long tube of the NiTi memory alloy by controlling the oxygen partial pressure, the oxidation temperature and the oxidation time of the oxidation atmosphere in a heat treatment furnace, so that the oxidation resistance of the NiTi memory alloy material is obviously improved. TiO with rutile phase oxide crystal structure 2 The oxidized and modified thin-wall and thin-diameter long NiTi memory alloy tube has good corrosion resistance, wear resistance and biocompatibility, and can be directly applied to the field of medical instruments such as bone substitute materials.
The invention adopts a low-oxygen partial pressure oxidation method, can inhibit the oxidation of Ni, effectively avoids the condition that an oxidation film prepared in the air or oxygen atmosphere contains Ni element in the prior art, and does not have the problems of phase change temperature change of the alloy and reduction of shape memory performance caused by the rise of oxidation temperature.
Drawings
FIG. 1a is an SEM secondary electron image of an in-situ oxide on the inner surface of a thin-walled tube made of NiTi alloy and magnified by 500 times;
FIG. 1b is SEM secondary electron image of the in-situ oxide on the inner surface of the thin-walled tube made of NiTi alloy by the method, wherein the SEM secondary electron image is magnified 5000 times;
FIG. 2a is an SEM secondary electron image of an in-situ oxide on the inner surface of a thin-walled tube made of NiTi alloy and magnified by 10000 times;
FIG. 2b is an analysis of the EDS in the red box of FIG. 2 a.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The in-situ oxidation modification method for the inner surface of the thin-wall thin-diameter long tube of the nickel-titanium alloy comprises the following steps:
s1, according to atomic ratio: ni a Ti 100-a And a is more than or equal to 50.5 and less than or equal to 52, carrying out induction melting on pure Ni and pure Ti, and obtaining the cast ingot by a water-cooling copper mold casting method. Then carrying out homogenization annealing on the obtained cast ingot, and processing the cast ingot into a NiTi alloy thin-wall pipe with the inner diameter of 6.0-7.0 mm and the wall thickness of 0.2-0.5 mm;
s2, performing oil and stain removal pretreatment on the surface of the NiTi alloy thin-walled pipe, then loading the pipe into a heat treatment furnace, and vacuumizing the furnace;
s3, introducing oxidizing gas into the heat treatment furnace; wherein the oxidizing gas comprises hydrogen and water vapor, the hydrogen is firstly introduced at the speed of 50-200mL/min, then the water vapor is introduced at the same speed, the ratio of the hydrogen to the water vapor is controlled at 1: 1-1: 1.5, and the pressure is controlled at 1-5 atmospheric pressures;
s4, heating the furnace to 700-1000 ℃ for high-temperature oxidation, wherein the heating rate is 10-30 ℃/min; preserving the heat for 1-10 h after reaching the preset temperature to ensure that the surface of the sample is oxidized uniformly in situ;
s5, cooling the furnace to room temperature or below 150 ℃, and closing gas to obtain rutile-phase TiO 2 And (5) oxidizing the film.
The processing method of the ingot in the step S1 includes, but is not limited to, one of hydraulic cogging, turning, wire cutting and coring, cold rolling and core pulling, or a combination of several methods.
The oil and stain removal pretreatment method in the step S2 comprises cleaning and drying.
In step S3, the ratio of hydrogen to steam in the oxidizing gas is preferably 1: 1.2 to 1: 1.3, and the pressure is preferably 2 to 4 atmospheres.
In the step S4, the furnace temperature of the high-temperature oxidation is preferably 750-850 ℃, the temperature rising rate is preferably 15-20 ℃/min, and the temperature is kept for 5-10 h after reaching the preset temperature.
Example 1:
in the present example, the atomic ratio: ni 51.6 Ti 48.4 (at.%) induction smelting of pure Ni and Ti, and casting in water-cooled copper mould to obtain cast ingot.
(1) Homogenizing the cast ingot, performing hydraulic cogging, and performing hot extrusion, turning, coring, cold rolling, core pulling and cold drawing to obtain a thin-wall tube of the NiTi alloy with the thickness of 6.0 +/-0.2 mm.
(2) A wire cutting method is used for cutting a sample with the thickness of 20mm multiplied by 10mm multiplied by 2mm from the inner surface of a thin-wall tube made of NiTi alloy, the surface of the sample is subjected to oil and stain removal pretreatment, and then the sample is loaded into a heat treatment furnace and is subjected to vacuum pumping treatment.
(3) Preferably, the ratio of hydrogen to water vapor in the oxidizing gas is controlled to 1: 1.3 and the pressure is controlled to 3 atmospheres, and then the oxidizing gas is introduced into the interior of the heat treatment furnace.
(4) Controlling the oxidation temperature at 750 ℃ for high-temperature oxidation, wherein the heating rate is 20 ℃/min, and keeping the temperature for 5h after reaching the preset temperature.
(5) Cooling to room temperature, and closing the gas to obtain rutile-phase TiO 2 And (5) oxidizing the film.
As can be seen from FIGS. 1a, 1b, 2a, and 2b, the above-described method is usedThe inner surface of the NiTi alloy thin-walled tube after treatment forms uniform and stable rutile phase TiO 2 An oxide film. TiO with rutile phase oxide crystal structure 2 The oxidized and modified thin-wall and thin-diameter long NiTi memory alloy tube has good corrosion resistance, wear resistance and biocompatibility, and can be directly applied to the field of medical instruments such as bone substitute materials.
It should be noted that the above-mentioned embodiments enable a person skilled in the art to more fully understand the invention, without restricting it in any way. Therefore, although the present invention has been described in detail with reference to the drawings and examples, it should be understood by those skilled in the art that the present invention may be modified and replaced by other embodiments, and in any case, the technical solutions and modifications thereof without departing from the spirit and scope of the present invention should be covered by the protection scope of the present invention.
Claims (5)
1. A method for modifying the surface of a nickel-titanium alloy material by in-situ oxidation comprises the following steps:
s1, manufacturing a NiTi alloy device;
s2, performing oil and stain removal pretreatment on the surface of the NiTi alloy device, then loading the NiTi alloy device into a heat treatment furnace, and vacuumizing the heat treatment furnace;
s3, introducing oxidizing gas into the heat treatment furnace; the oxidizing gas comprises hydrogen and water vapor, the hydrogen is introduced at the rate of 50-200mL/min, the water vapor is introduced at the same rate, the ratio of the hydrogen to the water vapor is controlled to be 1: 1.2-1: 1.3, and the pressure is controlled to be 2-4 atmospheric pressures;
s4, heating the furnace to 750-850 ℃ for high-temperature oxidation, wherein the heating rate is 15-20 ℃/min; preserving the heat for 5-10 h after reaching the preset high temperature to ensure that the surface of the sample is oxidized uniformly in situ;
s5, cooling the furnace temperature to a preset low temperature, and closing gas to obtain a rutile-phase TiO2 oxidation film;
the manufacturing method of the S1 alloy device comprises the following steps:
a) And according to the atomic ratio: ni a Ti 100-a A is more than or equal to 50.5 and less than or equal to 52, pure Ni and pure Ti are subjected to induction melting, and a cast ingot is obtained by a water-cooling copper mold casting method;
b) And carrying out homogenizing annealing on the cast ingot, and processing into a NiTi alloy thin-wall pipe with the inner diameter of 6.0-7.0 mm and the wall thickness of 0.2-0.5 mm.
2. The method for in-situ oxidation modification of the surface of the nickel-titanium alloy material according to claim 1, wherein: the processing method of the cast ingot in the step b) comprises one of hydraulic cogging, turning, linear cutting and coring, cold rolling and core pulling, or the combination of a plurality of methods.
3. The method for modifying the surface of a nickel-titanium alloy material through in-situ oxidation according to claim 1, wherein the method comprises the following steps: and the oil and stain removal pretreatment method in the S2 comprises cleaning and drying.
4. The method for modifying the surface of a nickel-titanium alloy material through in-situ oxidation according to claim 1, wherein the method comprises the following steps: in S5, the preset low temperature is room temperature.
5. The method for in-situ oxidation modification of the surface of the nickel-titanium alloy material according to claim 1, wherein: in S5, the preset low temperature is below 150 ℃.
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