CN115786747B - Preparation method of medical high-performance antibacterial titanium alloy plate - Google Patents
Preparation method of medical high-performance antibacterial titanium alloy plate Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 121
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005096 rolling process Methods 0.000 claims abstract description 42
- 238000000137 annealing Methods 0.000 claims abstract description 30
- 238000003723 Smelting Methods 0.000 claims abstract description 25
- 238000010275 isothermal forging Methods 0.000 claims abstract description 19
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- 238000005242 forging Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
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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
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- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a preparation method of a medical high-performance antibacterial titanium alloy plate, which comprises the following steps: 1. smelting by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot; 2. removing a riser and defects of a titanium alloy cast ingot, trimming the cast ingot into a cylindrical ingot, annealing the cylindrical ingot, and performing isothermal forging to obtain a grain refining plate blank; 3. carrying out low-temperature annealing treatment on the fine-grain plate blank, then carrying out warm rolling, and carrying out leveling and acid washing to obtain a plate; 4. and wrapping the plates, and performing accumulated rolling to obtain the medical high-performance antibacterial titanium alloy plate. The invention combines vacuum magnetic suspension smelting with isothermal forging of large deformation of two-phase areas, so that the titanium alloy plate has equiaxed ultrafine grain structure, the surface is bright and smooth, the strength and elastic modulus plasticity of the product reach better biomechanical adaptation, the antibacterial performance is stable and durable, and the titanium alloy plate has excellent osseointegration characteristics.
Description
Technical Field
The invention belongs to the technical field of titanium alloy material processing, and particularly relates to a preparation method of a medical high-performance antibacterial titanium alloy plate.
Background
At present, surgical implantation medical instruments such as dental implants, artificial joints and the like are widely applied to various bone trauma and bone defect patients, and the medical materials with the greatest application are still pure titanium and Ti6Al4V titanium alloy. With the recent development of the medical industry, a new batch of low modulus titanium alloys has also been incorporated into the surgical implant international standards, such as: ti-13Nb-13Zr, ti-13Nb-13Zr (ASTM F1713), ti-12Mo-6Zr-2Fe (ASTM F1813), ti-15Mo (ASTM F2066), ti-15Mo-5Zr-3Al (JIS T7401-6), ti-45Nb (AMS 4982), ti-2.5Al-5Mo-5V (VT 16), ti-5Al-2Sn (VT 5-1) and the like, which are widely used for manufacturing various medical instruments such as femoral stems, artificial joints, implants and the like due to lower elastic modulus. However, long-term clinical researches show that the strength of the instrument is low, and medical accidents such as operation failure and the like are frequent because bacterial biofilms are easy to form in complex microenvironments for a long time to cause infection or inflammation. Therefore, in order to solve the technical problems that the existing medical titanium alloy body is easy to be infected, the strength is insufficient and the like, the stress shielding effect between an implant and the body is reduced, the service performance of the existing implantation instrument is further improved and widened, the technological level and the competitiveness of the titanium alloy industry and the medical instrument industry in China are improved, and the medical beta titanium alloy material and the instrument with multiple effects, which have the characteristics of low cost, low modulus, high strength and strong antibacterial property, are realized.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a medical high-performance antibacterial titanium alloy plate aiming at the defects of the prior art. The method combines vacuum magnetic suspension smelting with isothermal forging of large deformation of two-phase areas, so that the titanium alloy plate has an equiaxed ultrafine grain structure, the surface is bright and smooth, the strength and elastic modulus plasticity of the product reach better biomechanical adaptation, the antibacterial performance is stable and durable, the excellent osseointegration characteristic is realized, and the problems that the existing medical titanium alloy body is easy to be infected, insufficient in strength and stress shielding effect are solved
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the medical high-performance antibacterial titanium alloy plate is characterized by comprising the following steps of:
smelting for 2-3 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, removing riser and defects of the titanium alloy ingot obtained in the step one, grinding the ingot into a cylindrical ingot, then annealing the cylindrical ingot at 780-850 ℃ for 1-2 h, and carrying out isothermal forging on the annealed cylindrical ingot by adopting superplastic forming equipment or thermoforming equipment, wherein the forging speed is 0.2-0.3 mm/s, the forging temperature is 650-800 ℃, and the forging deformation is 50-80%, so as to obtain a grain refining plate blank;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 1-5 mm;
step four, wrapping the plates obtained in the step three, and then accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.1-1 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: 10 to 25 percent of Mo, 0.2 to 5 percent of Ag, less than or equal to 0.15 percent of impurity O and the balance of Ti.
Firstly preparing a titanium alloy cast ingot by adopting a vacuum magnetic suspension induction melting furnace, grinding the titanium alloy cast ingot into a cylindrical ingot, annealing the cylindrical ingot to promote homogenization of alloy elements and reduce dendrite segregation, then carrying out isothermal forging, obtaining an ultrafine grain structure by controlling an isothermal forging process to obtain a fine crystallized plate blank, eliminating the processing stress of isothermal forging by low-temperature annealing treatment, continuously carrying out warm rolling and thinning to obtain a plate with the thickness of 1-5 mm, and then wrapping the plate and carrying out cumulative rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.1-1 mm. Finally, the microstructure of the medical high-performance antibacterial titanium alloy plate prepared by the invention is an equiaxed ultrafine grain structure, the surface is bright and smooth, the strength and elastic modulus plasticity of the product reach better biomechanical adaptation, the antibacterial performance is stable and durable, and the medical high-performance antibacterial titanium alloy plate has excellent osseointegration characteristics, so that the titanium alloy has the performances of low modulus, high strength, good antibacterial property, osseointegration capability and the like.
In the preparation process, the characteristics of electromagnetic induction stirring are utilized in vacuum magnetic suspension induction smelting, so that smelting raw materials are not in contact with a crucible or the contact area is small, the stability, the cleanliness and the uniformity of titanium alloy cast ingot components are improved, and the method is particularly suitable for the titanium alloy components consisting of low-melting-point antibacterial elements and refractory alloy elements, so that the product titanium alloy sheet has low modulus, high strength, good antibacterial property and osseointegration performance, is suitable for medical use, and solves the problems of unstable alloy components, crucible pollution and even damage tolerance equipment caused by serious volatilization of the low-melting-point antibacterial elements in the alloy cast ingot prepared by the traditional consumable smelting method, and the problem of mismatch of strength and toughness of the alloy cast ingot caused by unavoidable formation of pores in the alloy cast ingot prepared by the powder metallurgy method.
According to the invention, an isothermal forging process for carrying out large deformation of a two-phase region is adopted, firstly, high-temperature annealing is utilized to soften a titanium alloy cast ingot, meanwhile, the diffusion of alloy elements tends to be uniformly distributed, residual stress is removed, conditions are provided for superplastic large deformation of a subsequent two-phase region, then, the temperature, the deformation rate and the deformation amount of isothermal forging are controlled, and high plastic strain is generated in the alloy by utilizing superplastic forming equipment or thermoforming equipment to increase necessary dislocation density, so that a local structure is changed from a low-angle grain boundary to a high-angle grain boundary, and refined sub-crystals of a large number of deformation structures are formed, thereby obtaining a grain refining slab. The process improves the strength, modulus, plasticity and toughness of the titanium alloy plate by a fine grain strengthening mode, and obtains unique properties which cannot be achieved by a coarse grain structure after the structure of the titanium alloy plate reaches superfine grains or nano crystallization, in particular greatly improves the antibacterial property and the osseointegration capability of the titanium alloy plate.
The medical high-performance antibacterial titanium alloy plate prepared by the invention is beta-type titanium alloy, the Young modulus of the titanium alloy is lower, the strength of the titanium alloy is far higher than that of Ti-Nb-based, ti-Zr-based and Ti-Ta-based titanium alloys, the titanium alloy plate has better biocompatibility, high strength and high plasticity than the traditional medical titanium alloy, and the titanium alloy plate is easy to achieve matching with the elastic modulus of human bones; meanwhile, the titanium alloy effectively inhibits bone atrophy and promotes new bone reconstruction, and particularly after fine crystal reinforcement, the elastic modulus of the titanium alloy is obviously reduced and is closer to that of cortical bone, so that stress shielding caused by the fact that the elastic modulus of the titanium alloy is far greater than that of cortical bone is reduced, the hardness of the titanium alloy is also enhanced, generation of bone joint surface abrasive dust is reduced, and favorable conditions are provided for adhesion, differentiation and proliferation of cells in a body. In addition, the titanium alloy has more particle boundaries, so that a large amount of free electrons are obtained, the titanium alloy has higher activation energy, calcium and phosphorus deposition on the surface of the titanium alloy is promoted, and in-vivo osseointegration is further promoted.
The preparation method of the medical high-performance antibacterial titanium alloy plate is characterized in that the temperature of the low-temperature annealing treatment in the third step is 400-500 ℃ and the heat preservation time is 30-60 min; the pass deformation of warm rolling is 15% -25%. The grain refining plate blank tissue obtained by isothermal forging has a high energy storage to enable the grain refining plate blank tissue to be in a metastable state or an unbalanced tissue state, and the ductility and the thermal stability of materials are reduced, so that the practical application of the materials is severely limited.
The preparation method of the medical high-performance antibacterial titanium alloy plate is characterized in that the material adopted by the sheath in the fourth step is 304L stainless steel plate with the thickness of 1-2 mm, and the total deformation of the accumulated lap rolling is more than 80%. According to the invention, the 304L stainless steel plate which is highly matched with or even better than the titanium alloy plasticity is selected as the sheathing material, and the thickness of the sheathing material is controlled in a combined way, so that the plastic deformation uniformity of the sheet material and the sheathing material in the deformation process of subsequent accumulation and rolling is facilitated, the surface quality of the sheet material is improved, the dimensional accuracy is improved, the anisotropy of the sheet material is reduced, and the situation that the sheathing material is subjected to a large amount of plastic deformation before the sheet material due to the fact that the thickness of the sheathing material is too large and the thickness of the sheathing material is too small, so that the thickness of the sheathing material is excessively reduced is avoided. The invention ensures that the plate obtains larger accumulated deformation by controlling the total deformation of the accumulated rolling to be more than 80 percent so as to effectively refine the structure, improve the strength and avoid uneven grain deformation or rotation caused by insufficient deformation.
The preparation method of the medical high-performance antibacterial titanium alloy plate is characterized in that the tensile strength of the medical high-performance antibacterial titanium alloy plate in the fourth step is 937 MPa-1308 MPa, the yield strength is 919 MPa-1242 MPa, the elastic modulus is 72 GPa-76 GPa, the elongation is 15.5% -21%, and the microhardness HV is 360-430.
Compared with the prior art, the invention has the following advantages:
1. the invention sequentially carries out coping, annealing, isothermal forging, low-temperature fire-spraying treatment, warm rolling and accumulating and rolling after sheath rolling on the titanium alloy cast ingot prepared by vacuum magnetic suspension induction smelting to obtain the medical high-performance antibacterial titanium alloy sheet, and the titanium alloy sheet has an equiaxed ultrafine grain structure, a bright and smooth surface, good biomechanical adaptation degree of product strength and elastic modulus plasticity, stable and durable antibacterial performance and excellent osseointegration characteristic by adopting the vacuum magnetic suspension smelting and combining isothermal forging of large deformation of two phase areas.
2. The medical high-performance antibacterial titanium alloy plate prepared by the invention has the properties of low modulus, high strength, good antibacterial property, osseointegration capacity and the like, and the thickness is 0.1 mm-1 mm, thereby meeting the requirements of titanium alloy implantation medical instruments.
3. The preparation method disclosed by the invention is simple in procedure, low in cost, reusable in residual materials, low in equipment requirement, capable of realizing the preparation of the high-performance antibacterial titanium alloy plate by adopting a common hydraulic press and a rolling mill, high in repeatability and suitable for industrial production, and meets the production requirement of small-batch finished products.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
Fig. 1 is a TEM micro morphology diagram of the medical high performance antibacterial titanium alloy sheet material prepared in example 1 of the present invention.
Fig. 2 is a graph showing room temperature tensile properties of medical high-performance antibacterial titanium alloy sheets prepared in examples 1 to 6 according to the present invention.
FIG. 3 is a bar graph showing cell viability values of medical high-performance antibacterial titanium alloy plates prepared in examples 1-2 and example 4 and example 6 of the present invention after culturing for 1, 3 and 5 days with comparative samples.
Detailed Description
Example 1
The embodiment comprises the following steps:
smelting for 2 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, grinding the titanium alloy cast ingot obtained in the step one into a cylindrical ingot after riser and defect removal, then annealing for 1h at 780 ℃, carrying out isothermal forging on the annealed cylindrical ingot by adopting 1250 thermoforming equipment, wherein the forging speed is 0.2mm/s, the forging temperature is 650 ℃, the forging deformation is 50%, and obtaining a grain refining plate blank;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 1 mm; the temperature of the low-temperature annealing treatment is 400 ℃, and the heat preservation time is 60min; the pass deformation of warm rolling is 15%;
step four, wrapping the plates obtained in the step three, and then accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.1 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: mo 10%, ag 0.2%, impurity O0.06%, and the balance Ti; the material adopted by the sheath is a 304L stainless steel plate with the thickness of 1mm, and the total deformation of the accumulated lap rolling is 90%.
Fig. 1 is a TEM microscopic morphology diagram of the medical high performance antibacterial titanium alloy sheet prepared in this example, and as can be seen from fig. 1, the medical high performance antibacterial titanium alloy sheet has a uniform and consistent ultrafine grain structure, the average grain size is about 200nm, and the phase structure is a beta phase.
Example 2
The embodiment comprises the following steps:
smelting for 2 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, removing a riser and defects of the titanium alloy cast ingot obtained in the step one, grinding the cast ingot into a cylindrical ingot, then annealing the cylindrical ingot at 780 ℃ for 1.5 hours, carrying out isothermal forging on the annealed cylindrical ingot by adopting 680 thermoforming equipment, wherein the forging speed is 0.2mm/s, the forging temperature is 700 ℃, and the forging deformation is 60%, so as to obtain a fine-crystallized slab;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 2 mm; the temperature of the low-temperature annealing treatment is 420 ℃, and the heat preservation time is 60min; the pass deformation of warm rolling is 20%;
step four, wrapping the plates obtained in the step three, and then accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.2 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: 15% of Mo, 1% of Ag, 0.09% of impurity O and the balance of Ti; the material adopted by the sheath is a 304L stainless steel plate with the thickness of 1.5mm, and the total deformation of the accumulated lap rolling is 90%.
Example 3
The embodiment comprises the following steps:
smelting for 2 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, removing a riser and defects of the titanium alloy cast ingot obtained in the step one, grinding the cast ingot into a cylindrical ingot, then annealing the cylindrical ingot at 800 ℃ for 1.5 hours, and carrying out isothermal forging on the annealed cylindrical ingot by adopting 630T superplastic forming equipment, wherein the forging speed is 0.2mm/s, the forging temperature is 700 ℃, and the forging deformation is 60%, so as to obtain a grain refining plate blank;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 3 mm; the temperature of the low-temperature annealing treatment is 450 ℃, and the heat preservation time is 50min; the pass deformation of warm rolling is 20%;
step four, wrapping the plates obtained in the step three, and then accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.4 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: 10% of Mo, 3% of Ag, 0.09% of impurity O and the balance of Ti; the material adopted by the sheath is a 304L stainless steel plate with the thickness of 1.5mm, and the total deformation of the accumulated lap rolling is 86.7%.
Example 4
The embodiment comprises the following steps:
smelting for 3 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, removing a riser and defects of the titanium alloy cast ingot obtained in the step one, grinding the cast ingot into a cylindrical ingot, then annealing the cylindrical ingot at the temperature of 820 ℃ for 1.5 hours, carrying out isothermal forging on the annealed cylindrical ingot by adopting 1250 thermoforming equipment, wherein the forging speed is 0.23mm/s, the forging temperature is 730 ℃, and the forging deformation is 65%, so as to obtain a grain refining plate blank;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 3.5 mm; the temperature of the low-temperature annealing treatment is 470 ℃, and the heat preservation time is 40min; the pass deformation of warm rolling is 22%;
step four, wrapping the plates obtained in the step three, and then accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.5 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: 10% of Mo, 3% of Ag, 0.1% of impurity O and the balance of Ti; the material adopted by the sheath is a 304L stainless steel plate with the thickness of 2mm, and the total deformation of the accumulated lap rolling is 85.7%.
Example 5
The embodiment comprises the following steps:
smelting for 3 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, removing a riser and defects of the titanium alloy cast ingot obtained in the step one, grinding the cast ingot into a cylindrical ingot, then annealing the cylindrical ingot at 850 ℃ for 1.5 hours, carrying out isothermal forging on the annealed cylindrical ingot by adopting 680 thermoforming equipment, wherein the forging speed is 0.25mm/s, the forging temperature is 750 ℃, and the forging deformation is 70%, so as to obtain a grain refining plate blank;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 4 mm; the temperature of the low-temperature annealing treatment is 480 ℃, and the heat preservation time is 40min; the pass deformation of warm rolling is 25%;
step four, wrapping the plates obtained in the step three, and then accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.8 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: 15% of Mo, 3.3% of Ag, 0.12% of impurity O and the balance of Ti; the material adopted by the sheath is a 304L stainless steel plate with the thickness of 2mm, and the total deformation of the accumulated lap rolling is 80%.
Example 6
The embodiment comprises the following steps:
smelting for 3 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, grinding the titanium alloy cast ingot obtained in the step one into a cylindrical ingot after riser and defect removal, then annealing for 2 hours at 850 ℃, and carrying out isothermal forging on the annealed cylindrical ingot by adopting 630T superplastic forming equipment, wherein the forging speed is 0.3mm/s, the forging temperature is 800 ℃, and the forging deformation is 80%, so as to obtain a grain refining plate blank;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 5 mm; the temperature of the low-temperature annealing treatment is 500 ℃, and the heat preservation time is 30min; the pass deformation of warm rolling is 20%;
step four, wrapping the plate obtained in the step three, and then accumulating and rolling to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 1 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: 25% of Mo, 5% of Ag, 0.15% of impurity O and the balance of Ti; the material adopted by the sheath is a 304L stainless steel plate with the thickness of 1.5mm, and the total deformation of the accumulated lap rolling is 80%.
The room temperature properties of the medical high performance antibacterial titanium alloy sheets prepared in examples 1 to 6 of the present invention were tested according to GB/T13810-2017 titanium and titanium alloy for surgical implant and GB/T228-2002 room temperature sheet tensile test specimen, and the results are shown in Table 1 and FIG. 2.
TABLE 1 Properties of medical high-performance antibacterial titanium alloy sheets prepared in examples 1 to 6 of the present invention
As can be seen from Table 1, the medical high-performance antibacterial titanium alloy plates prepared in examples 1 to 6 of the invention have average grain sizes of 0.2-0.8 μm, tensile strengths of 937-1308 MPa, yield strengths of 919-1242 MPa, elastic moduli of 72-76 GPa, elongation of 15.5-21%, microhardness HV of 360-430 and antibacterial rates of more than 94%, which indicates that the medical high-performance antibacterial titanium alloy plates prepared in the invention have low moduli, high strength, good antibacterial properties and osseointegration capability. Compared with the common medical Ti-15Mo plate with the same thickness, the medical high-performance antibacterial titanium alloy plate prepared in the embodiment 6 has smaller average grain size and the microstructure realizes superfine crystallization, so that the tensile strength, the yield strength, the elastic modulus, the elongation, the microhardness HV and the antibacterial rate of the medical high-performance antibacterial titanium alloy plate are all superior to those of the common medical Ti-15Mo plate.
Fig. 2 is a graph of room temperature tensile properties of the medical high-performance antibacterial titanium alloy plates prepared in examples 1 to 6, and as can be seen from fig. 2, the medical high-performance antibacterial titanium alloy plates prepared in the invention have tensile strength of more than 930MPa and elongation after break of more than 15.5% while maintaining low elastic modulus (72 GPa-76 GPa), which shows that the biological mechanical property adaptability of the medical high-performance antibacterial titanium alloy plates is higher, and the medical high-performance antibacterial titanium alloy plates are novel high-performance antibacterial beta-type titanium alloy very suitable for surgical implantation.
The medical high-performance antibacterial titanium alloy plates prepared in the examples 1-2, 4 and 6 of the invention and the comparative sample are subjected to cell culture and cell viability value detection, an osteoblast cell line (MC 3T 3-E1) is selected as a model for evaluating the cell biocompatibility, and a conventional method is selectedAs a comparative sample, the Ti-15Mo medical titanium alloy of (a) was analyzed for cell adhesion and proliferation by a commercial Live-read staining kit and alamarblue assay kit (Life Technologies), the specific procedure was: first, the samples of the comparative example and each example were sterilized with 75% ethanol for 2 hours and irradiated with Ultraviolet (UV) light for 30 minutes before cell culture, and then placed in 24-well culture plates, and cells were inoculated on the surfaces of each sample at a density of 4000 cells/cm 2 And after 1 day, 3 days, and 5 days of inoculation, respectively, an indicator of alamarBluet assay kit was added to each well and incubated for 4 hours, then 100 μl of medium in each well was added to a 96-well black plate, fluorescence intensity was recorded using a microplate reader (Spectramax i3, molecular Devices), and at least 3 samples were tested for each; finally, living cells and Dead cells were routinely stained by Live-read kit assay, and the adhesion state of the stained cells on the surface of each titanium alloy plate was observed by a forward fluorescent microscope (BX 53, olympus), and the cell viability value of each titanium alloy plate was calculated and a bar graph was drawn, and the results are shown in fig. 3.
FIG. 3 is a bar graph showing cell viability values of the medical high-performance antibacterial titanium alloy plates prepared in examples 1-2, example 4 and example 6 and the comparative sample after culturing for 1, 3 and 5 days, and as can be seen from FIG. 3, the cell proliferation capacities of the surfaces of the comparative sample and the medical high-performance antibacterial titanium alloy plate are obviously different under the same culturing time and condition, namely, compared with the conventional Ti-15Mo medical titanium alloy, the cell viability value of the medical high-performance antibacterial titanium alloy plate prepared in the invention is larger, and the medical high-performance antibacterial titanium alloy plate has better differentiation and proliferation capacities; meanwhile, along with the increase of the culture days, the cell proliferation rate is also obviously increased, and particularly, the average grain size of the equiaxed ultrafine crystals in the titanium alloy plate is closer to the nanoscale, the cell proliferation capacity is stronger, but when the average grain size is more than 200nm, the cell proliferation capacity is not obviously different.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (4)
1. The preparation method of the medical high-performance antibacterial titanium alloy plate is characterized by comprising the following steps of:
smelting for 2-3 times by adopting a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy cast ingot with uniform components;
step two, removing riser and defects of the titanium alloy ingot obtained in the step one, grinding the ingot into a cylindrical ingot, then annealing the cylindrical ingot at 780-850 ℃ for 1-2 h, and carrying out isothermal forging on the annealed cylindrical ingot by adopting superplastic forming equipment or thermoforming equipment, wherein the forging speed is 0.2-0.3 mm/s, the forging temperature is 650-800 ℃, and the forging deformation is 50-80%, so as to obtain a grain refining plate blank;
step three, carrying out low-temperature annealing treatment on the fine-grain plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid washing to obtain a plate with the thickness of 1-5 mm;
step four, wrapping the plates obtained in the step three, and then accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate with the thickness of 0.1-1 mm; the medical high-performance antibacterial titanium alloy plate comprises the following element components in mass content: 10 to 25 percent of Mo, 0.2 to 5 percent of Ag, less than or equal to 0.15 percent of impurity O and the balance of Ti.
2. The method for preparing the medical high-performance antibacterial titanium alloy plate according to claim 1, wherein the temperature of the low-temperature annealing treatment in the step three is 400-500 ℃ and the heat preservation time is 30-60 min; the pass deformation of warm rolling is 15% -25%.
3. The method for preparing the medical high-performance antibacterial titanium alloy plate, which is characterized in that in the fourth step, the sheath is made of a 304L stainless steel plate with the thickness of 1-2 mm, and the total deformation of the accumulated lap rolling is more than 80%.
4. The method for preparing the medical high-performance antibacterial titanium alloy plate according to claim 1, wherein in the fourth step, the medical high-performance antibacterial titanium alloy plate has the tensile strength of 937 MPa-1308 MPa, the yield strength of 919 MPa-1242 MPa, the elastic modulus of 72 GPa-76 GPa, the elongation of 15.5% -21% and the microhardness HV of 360-430.
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