CN112251634B - Antibacterial equiaxial nanocrystalline Ti-Cu plate and preparation method thereof - Google Patents
Antibacterial equiaxial nanocrystalline Ti-Cu plate and preparation method thereof Download PDFInfo
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- CN112251634B CN112251634B CN202011051263.7A CN202011051263A CN112251634B CN 112251634 B CN112251634 B CN 112251634B CN 202011051263 A CN202011051263 A CN 202011051263A CN 112251634 B CN112251634 B CN 112251634B
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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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
- A61C7/12—Brackets; Arch wires; Combinations thereof; Accessories therefor
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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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
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/04—Nanocrystalline
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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
- Y02P10/20—Recycling
Abstract
The invention provides an antibacterial equiaxial nanocrystalline Ti-Cu plate and a preparation method thereof, wherein the titanium alloy comprises the following chemical components (in percentage by weight): cu: 2-6; the balance of Ti. The preparation method of the titanium alloy plate comprises the following steps: smelting in a vacuum consumable electrode furnace to obtain a raw material ingot; grinding the cast ingot, and then performing cogging forging and finish forging at the temperature of more than 1000 ℃ to obtain a plate blank; the plate blank is quickly cooled after being kept at 800-1000 ℃ for a period of time, and the plate obtains an ultrafine nano lath structure; after quenching, roughly rolling the plate blank at the temperature of 700-850 ℃, and obtaining the superfine nano-lath tissue plate by hot rolling the accumulated deformation more than or equal to 90%; after hot rolling, the plate is finely rolled at 650-750 ℃, the structure of the plate obtained after processing is equiaxial crystal grains, the size is less than 500nm, and the crystal grains do not generate coarsening and growth within 3 hours of aging at 550 ℃ and below.
Description
Technical Field
The invention relates to the field of titanium alloy processing and preparation, in particular to an antibacterial equiaxial nanocrystalline Ti-Cu plate and a preparation method thereof.
Background
Titanium alloy is a metal with excellent biological safety, has low density, elastic modulus close to that of human skeleton and high strength, so that titanium and its alloy are widely applied to the medical and health field, especially the oral and orthopedic repair field, such as bracket, belt loop, orthodontic arch wire, implant for anchorage, artificial joint (μm, knee, shoulder, ankle, elbow, wrist, finger joint, etc.), bone wound product (intramedullary nail, steel plate, screw, etc.), spinal column orthopedic internal fixation system, etc.
The titanium alloy has been applied in the medical field for nearly 70 years, various titanium alloy grades are layered, updating iteration is gradually unable to keep up with the needs of people for higher medical quality, and the contradiction between the defects of the existing titanium alloy and the needs of people is more and more prominent. Firstly, titanium alloys are good in biocompatibility and do not cause damage to the human body, but at the same time provide a harmless environment for the growth of harmful microorganisms. With the wide application of medical titanium alloy, the serious complication of postoperative infection also becomes a problem which is more and more concerned and needs to be solved urgently. Secondly, the medical titanium alloy has another advantage of low density and elastic modulus close to that of a human body, but when the medical titanium alloy is used as a force-bearing implant, such as an artificial hip joint handle, the implant failure caused by fracture failure often occurs, great pain is brought to a patient, and heavy spirit and economic burden are caused. Therefore, the realization that the implant material is lighter, stronger and healthier becomes a new important proposition which is more suitable for actual and future needs.
Disclosure of Invention
The invention aims to provide an antibacterial equiaxial nanocrystalline Ti-Cu plate and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an antibacterial equiaxial nanocrystalline Ti-Cu plate comprises the following chemical components in percentage by weight: cu: 2 to 6 (preferably 3.5 to 4.5), and the balance Ti.
The preparation process of the high-strength antibacterial titanium alloy plate comprises the following steps:
the method comprises the following steps: smelting for multiple times by adopting a vacuum consumable furnace to obtain a raw material ingot. Grinding the cast ingot, and then performing cogging forging and finish forging at the temperature of more than 1000 ℃ to obtain a plate blank;
step two: the plate blank is kept at 800-1000 ℃ for a period of timet= (1.5-2.5)Dmin, wherein D is the effective thickness (in mm) of the sample;
step three: and (3) quickly cooling the slab after the heat preservation of the slab is finished, wherein the cooling rate delta T/T ranges from 150 to 350 ℃/s. The plate blank obtains a superfine nano lath structure;
step four: the superfine nano lath structure plate blank is subjected to rough rolling at the temperature of 700-850 ℃, and the accumulated deformation of hot rolling is more than or equal to 90 percent, so that a superfine nano lath structure plate is obtained;
step five: and (3) performing finish rolling on the superfine nano-lath tissue plate at the temperature of 650-750 ℃ to obtain a plate with a target size.
The microstructure and the performance of the antibacterial equiaxial nanocrystalline Ti-Cu plate are as follows:
(1) the antibacterial equiaxial nanocrystalline Ti-Cu plate is equiaxial grains, the size of the antibacterial equiaxial nanocrystalline Ti-Cu plate is less than 500nm, and the grains are not coarsened and grown within 3 hours of aging at 550 ℃ or below.
(2) When the copper content is in the preferable range, the tensile strength of the antibacterial equiaxial nanocrystalline Ti-Cu plate (the thickness is less than 6 mm) reaches 800-900MPa, and the elongation is higher than 15%.
The invention has the beneficial effects that:
(1) the microscopic structure of the antibacterial equiaxed nanocrystalline Ti-Cu plate provided by the invention is ultrafine equiaxed grains, and the antibacterial equiaxed nanocrystalline Ti-Cu plate has high structure thermal stability.
(2) The antibacterial equiaxial nanocrystalline Ti-Cu plate provided by the invention can obviously improve the comprehensive mechanical property of the titanium alloy material.
Drawings
FIG. 1 the metallographic microstructure of the material obtained in example 3.
Detailed Description
The present application will now be illustrated and explained by means of several groups of specific examples and comparative examples, which should not be taken to limit the scope of the present application.
Example (b): examples 1 to 6 show alloys that were smelted according to the ranges of chemical compositions provided by the present invention, and the contents of Cu elements were gradually increased, and the corresponding manufacturing processes were also appropriately adjusted within the ranges of technical parameters specified in the present invention, as shown in tables 1 and 2.
Comparative example: the chemical compositions of the comparative examples 1-2 are lower than the lower limit of the chemical composition range provided by the invention, and the heating temperature of the heat treatment of the plate blank of the comparative example 3 is lower than the lower limit of the heating temperature range provided by the invention; the heat treatment holding time of the plate blank of the comparative example 4 is lower than the lower limit of the heat holding time range provided by the invention; comparative example 5 the cooling rate of the heat-treated slab was higher than the upper limit of the cooling rate range provided by the present invention. The hot-drawing temperature of comparative example 6 is higher than the upper limit of the hot-drawing temperature range provided by the present invention; the deformation amount of comparative example 7 is lower than the deformation amount range provided by the present invention; the hot-drawing temperatures of comparative examples 8 and 9 were lower than the lower limit of the hot-drawing temperature range provided by the present invention. Comparative example 10 is a conventional grade 2 pure titanium plate with nanocrystalline structure prepared by ECAP process, see tables 3 and 4.
Table 1 examples chemical composition, heat treatment process
Description of the drawings: d is the effective thickness of the sample (in mm)
TABLE 2 example Hot working Process and Final dimensions
Table 3 comparative example chemical composition, heat treatment process
Description of the drawings: d is the effective thickness of the sample (in mm)
Table 4 comparative example hot working process and final dimensions
1. Hardness test
The hardness of the materials of the examples and comparative examples were tested. The Vickers hardness of the annealed material samples was measured using an HTV-1000 type durometer. Before testing, the sample surface was polished. The sample was a thin sheet with dimensions of 10 mm diameter and 2 mm thickness. The test loading force is 9.8N, the pressurizing duration is 15 s, and the hardness value is automatically calculated by measuring the diagonal length of the indentation through computer hardness analysis software. The final hardness values were averaged over 15 points and three replicates were selected for each set of samples, the specific results are shown in table 5.
2. Tensile Property test
The room temperature tensile mechanical properties of the comparative and example materials were tested using an Instron model 8872 tensile tester at a tensile rate of 0.5 mm/min. Before testing, the material is processed into standard tensile samples, three parallel samples are taken from each group of heat treatment samples, the mechanical properties obtained by the experiment comprise tensile strength and elongation, and the specific results are shown in table 5.
3. Grain size statistics
The method comprises the steps of carrying out phase volume fraction statistics on samples before and after fatigue by adopting an Electron Back Scattering Diffraction (EBSD) analysis system of a scanning electron microscope, wherein the sample preparation method comprises the steps of firstly carrying out mechanical polishing on the samples to obtain a flat and smooth surface, then placing the samples in electrolyte (6% perchloric acid, 30% butanol and 64% methanol) for electrolytic polishing for 20 s at the temperature of minus 25 ℃, and removing surface stress. When EBSD collects data, the working voltage of a scanning electron microscope is 20 kV, the current is 18nA, the step length is selected to be 0.2 μm, the resolution of the scanning range is more than 80%, Channel 5 software is adopted to analyze the grain size, and the specific result is shown in Table 6.
TABLE 5 mechanical properties of the materials of the examples and comparative examples
TABLE 6 texture characteristics of the materials of the examples and comparative examples and the change in texture after 1h incubation at different temperatures
As can be seen from the results of tables 5 and 6, examples 1 to 6 are equiaxed nanocrystalline structures, which make them have high strength, good plasticity and high hardness. Within the Cu content range specified in the invention, as the Cu content is increased, the grain size of the material is gradually reduced, the strength and the hardness of the material are improved, and the elongation is gradually reduced.
As can be seen from the results of tables 5 and 6, comparative examples 1 and 2 have poor mechanical properties and do not have equiaxed nanocrystalline structures because the Cu content is out of the range provided by the present invention. The technological parameter ranges of the comparative examples 3-8, such as heat treatment, rough rolling, finish rolling and the like, are not in the range provided by the invention, the final mechanical property is poor, and an equiaxial nanocrystalline structure is not obtained.
From the results in table 6, it can be seen that examples 1 to 6 have good thermal stability of the structure during aging at 550 ℃ and below, and the grain size does not change significantly after aging. While comparative example 10 exhibited significant coarsening and growth of grains.
The above description is only for the purpose of illustrating embodiments of the present application and is not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by the contents of the specification and the drawings of the present application or are directly or indirectly applied to other related technical fields, are also included in the scope of the present application.
Claims (4)
1. An antibacterial equiaxial nanocrystalline Ti-Cu plate is characterized by comprising the following chemical components in percentage by weight: cu: 2-6; the balance of Ti;
the specific preparation steps of the plate are as follows:
the method comprises the following steps: smelting for multiple times by adopting a vacuum consumable furnace to obtain a raw material ingot; after the cast ingot is polished, the cast ingot is processed into a slab through cogging forging and finish forging at the temperature of more than 1000 ℃;
step two: the plate blank is kept at 800-1000 ℃ for a period of timet= (1.5-2.5)Dmin, wherein D is the effective thickness of the sample and the unit is millimeter mm;
step three: rapidly cooling the plate blank after the heat preservation is finished, wherein the cooling rate is 150-350 ℃/s; the plate blank obtains a superfine nano lath structure;
step four: the superfine nano lath structure plate blank is subjected to rough rolling at the temperature of 700-850 ℃, and the accumulated deformation of hot rolling is more than or equal to 90 percent to obtain a superfine nano lath structure plate;
step five: and (3) performing finish rolling on the superfine nano-lath tissue plate at the temperature of 650-750 ℃ to obtain a plate with a target size.
2. The antibacterial equiaxed nanocrystalline Ti-Cu plate according to claim 1, wherein the copper content in the plate is Cu: 3.5 to 4.5.
3. The antibacterial equiaxed nanocrystalline Ti-Cu plate according to claim 1, characterized in that: the structure of the plate obtained after thermal deformation processing is equiaxial crystal grains, the size is less than 500nm, and the crystal grains are not coarsened and grown within 3 hours of aging at 550 ℃ and below.
4. The antibacterial equiaxed nanocrystalline Ti-Cu plate according to claim 1, characterized in that: the tensile strength of the prepared antibacterial titanium alloy plate with the thickness of less than 6 mm is 800-900MPa, and the elongation is higher than 15%.
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