CN115948676A - Self-adaptive implant for bone insufficiency, titanium-zirconium-iron alloy and preparation method thereof - Google Patents
Self-adaptive implant for bone insufficiency, titanium-zirconium-iron alloy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of biomedical titanium alloy materials, and relates to a self-adaptive implant for insufficient bone mass, a titanium-zirconium-iron alloy and a preparation method thereof. According to the titanium-zirconium-iron alloy, a proper amount of Zr element is added into the titanium alloy, so that the solid solution strengthening effect is achieved, and the mechanical property is improved; fe element has the function of stabilizing beta phase, and a proper amount of Fe element is added into the titanium alloy, so that the structure can be refined, and the processing performance is improved. Meanwhile, zr element and Fe element have non-toxic property, so that excellent biocompatibility of the titanium-zirconium-iron alloy is ensured. According to the preparation method, high-temperature forging is carried out, alpha + beta two-phase region solution treatment and low-temperature aging treatment are combined, then alpha + beta phase region hot rolling and beta phase region hot drawing are carried out, and finally recrystallization annealing treatment is carried out, so that the finally obtained titanium alloy wire is fine and uniform in crystal grains, and good matching of strength and plasticity is guaranteed while low elastic modulus is achieved.
Description
Technical Field
The invention belongs to the technical field of biomedical titanium alloy materials, relates to a titanium-zirconium-iron alloy special for an implant, and particularly relates to a self-adaptive implant for insufficient bone mass, a titanium-zirconium-iron alloy and a preparation method thereof.
Background
The Ti-Zr-Fe alloy has the characteristics of low elastic modulus, high specific strength, excellent corrosion resistance, good biocompatibility and the like, and Zr is considered as a neutral element in the Ti solid-phase solution because the Zr does not influence the beta phase transformation temperature. Zr element is added into the titanium alloy to refine crystal grains and improve mechanical property. The cold-rolled titanium-zirconium-iron alloy is easy to crack, and the implant processed by the cold-rolled titanium-zirconium-iron alloy is even cracked in the use process. Fe element has the function of stabilizing beta phase in the titanium alloy, has strengthening effect on the matrix, and can refine crystal grains by regulating and controlling a thermal deformation process and a thermal treatment system, so as to obtain fine and uniform tissues, thereby obtaining good matching of strong plasticity.
When alveolar bone loses much bone or the bone quantity is insufficient, the direct implantation of the implant can cause perforation of mucosa of maxillary sinus and damage lower alveolar nerve and blood vessels. The requirements of planting are met by increasing the bone mass or changing the planting position in clinic, but the application is greatly limited due to the problems of poor clinical effect, high price, long recovery time and the like. The implant implanted by inclination is often used in combination with an angle abutment, most of the stress of the implant is concentrated on the neck of the implant, and improper stress is generated by the angle abutment, and researches show that the stress concentration at the joint of the implant abutment is the largest.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a self-adaptive implant for insufficient bone mass, a titanium-zirconium-iron alloy and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
in a first aspect, the invention provides a titanium-zirconium-iron alloy for an adaptive implant with insufficient bone mass, which comprises the following chemical components in percentage by weight: 19 to 30 percent of Zr, 0.1 to 2 percent of Fe, 0.1 to 0.3 percent of O and the balance of Ti.
Preferably, the Zr content is 22 to 27 percent, the Fe content is 0.5 to 1.5 percent and the balance is Ti according to weight percentage.
Furthermore, the titanium alloy structure is a fine equiaxial alpha phase, a partially elongated alpha phase and an intercrystalline beta phase, the tensile strength of the titanium-zirconium-iron alloy is 1120-1250 MPa, the yield strength is more than 1000MPa, the elongation after fracture is 25-30%, and the elastic modulus is 72-80 GPa.
In a second aspect, the invention further provides a preparation method of the self-adaptive implant titanium-zirconium-iron alloy, which comprises the following steps:
step 1, selecting high-purity titanium blocks, zirconium blocks and iron particles according to weight percentage, polishing to remove surface oxide layers of the titanium blocks and the zirconium blocks, and performing vacuum melting for three times by using a vacuum arc furnace to obtain titanium alloy ingots with uniform components; wherein the diameter of the electrode is 150-320 mm, the inner diameter of the crucible is 220-406 mm, the crucible ratio is 0.75-0.85, the smelting voltage is 32-45V, and the smelting current is 18-27 KA;
step 2, polishing the titanium alloy ingot obtained in the step 1, and performing cogging forging and precision forging to form a large-size bar;
step 3, carrying out alpha + beta two-phase region solution treatment on the large-size bar obtained in the step 2 under the vacuum condition and the protection of inert gas, and carrying out low-temperature aging treatment;
step 4, carrying out alpha + beta phase zone hot rolling on the titanium alloy bar subjected to solid solution and low-temperature aging treatment, wherein the accumulated deformation is not less than 70%, and the single deformation is 5-10%;
and 6, carrying out recrystallization annealing treatment on the titanium alloy wire subjected to hot drawing to obtain the titanium zirconium iron alloy wire with fine and uniform tissue and excellent comprehensive performance.
Further, in the step 1, the purity of the titanium block and the purity of the zirconium block are both higher than 99.9%, and the crucible ratio is 0.70-0.80; the primary smelting voltage is 32-35V, and the primary smelting current is 18-20 KA; the secondary smelting voltage is 36-39V, and the secondary smelting current is 21-23 KA; the third smelting voltage is 42-45V, and the third smelting current is 25-27 KA.
Further, the temperature of blank opening forging in the step 2 is 900-950 ℃, and the forging ratio is 4-5; the temperature of the precision forging is 850-900 ℃, and the forging ratio is 5-7.
Further, in the step 3, the temperature of the solution treatment is 750-800 ℃, the solution time is 0.5-2.5 h, and the water cooling is carried out rapidly; the aging treatment temperature is 380-460 ℃, the aging time is 6-10 h, and the air cooling is carried out.
Further, the hot rolling in the step 4 adopts multi-pass rolling, the steel is heated to 800-850 ℃ in a box type resistance furnace before rolling, and the final rolling temperature is not less than 750 ℃.
Furthermore, the drawing temperature in the step 5 is 850-880 ℃, the drawing speed is 20-50 mm/s, and the stress relief annealing treatment at 700-750 ℃ is performed twice in the middle of drawing.
Further, in the step 6, the recrystallization annealing temperature is 650-750 ℃, the heat preservation time is 1-5 h, and then air cooling is carried out.
In addition, the invention also provides a self-adaptive implant prepared from the titanium-zirconium-iron alloy prepared by the preparation method, wherein the self-adaptive implant is in a hole-shaped structure, the hole-shaped structure is distributed from 2mm above the root tip of the self-adaptive implant to 5mm below the neck of the self-adaptive implant, the hole-shaped structure can be prepared by adopting a mechanical processing method (such as drilling, turning) and the like, the hole diameter is 0.2-0.8 mm, the hole edge is 2-5 mm, and the hole-shaped structure comprises a trapezoid body, a cylinder body, a cuboid body, a cube and the like.
Further, the self-adaptive implant can form a hydrophilic surface layer through special surface treatment, and the specific surface treatment is as follows: sand blasting and acid etching are firstly carried out, then heat treatment is carried out for 1-2 days in water with the temperature of 40-60 ℃, and finally the mixture is soaked in potassium phosphate solution with the pH value of 7.3-7.6 for storage and standby.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
on one hand, the invention provides a self-adaptive implant titanium-zirconium-iron alloy for insufficient bone mass, which has the solid solution strengthening effect by adding a proper amount of Zr element in the titanium alloy, so that the mechanical property is improved; fe element has the function of stabilizing beta phase, and a proper amount of Fe element is added into the titanium alloy, so that the structure can be refined, and the processing performance is improved. Meanwhile, zr element and Fe element have non-toxic property, so that the titanium-zirconium-iron alloy has excellent biocompatibility.
On the other hand, the invention provides a preparation method of the self-adaptive implant titanium-zirconium-iron alloy for insufficient bone mass, which comprises the steps of forging at high temperature, combining solid solution water cooling treatment and low temperature aging treatment in a two-phase region (alpha + beta phase region), carrying out hot rolling in the alpha + beta phase region and hot drawing in the beta phase region, and finally carrying out recrystallization annealing treatment, so that the finally obtained titanium alloy wire material has fine and uniform crystal grains, and ensures that the strength and the plasticity are well matched while the lower elastic modulus is realized.
In addition, the invention also provides a self-adaptive structure implant prepared by the titanium-zirconium-iron alloy and aiming at patients with insufficient bone mass, which has the characteristics of low elastic modulus and small stress shielding effect, and a hydrophilic surface layer is formed by special surface treatment and can be quickly dissolved when contacting with water, body fluid or saliva and other liquids, the surface of the implant has higher surface energy, the implant-bone combination strength is high, the implantation stability is high, and the purpose of firm implantation can be realized.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
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 for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a flow chart of a method for preparing an adaptive implant Ti-Zr-Fe alloy for osteopenia provided by the invention;
FIG. 2 (a) is a transverse high magnification structural diagram of a Ti-Zr-Fe alloy prepared in example 1 of the present invention;
FIG. 2 (b) is a longitudinal high magnification structural diagram of the Ti-Zr-Fe alloy prepared in example 1 of the present invention;
FIG. 3 (a) is a transverse high magnification structural diagram of a Ti-Zr-Fe alloy prepared in example 2 of the present invention;
FIG. 3 (b) is a longitudinal high magnification structural diagram of the Ti-Zr-Fe alloy prepared in example 2 of the present invention;
FIG. 4 (a) is a transverse high magnification structural diagram of a Ti-Zr-Fe alloy prepared in example 3 of the present invention;
FIG. 4 (b) is a longitudinal high magnification structural view of a Ti-Zr-Fe alloy prepared in example 3 of the present invention;
FIG. 5 is a graph showing room temperature tensile properties of Ti-Zr-Fe alloys prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2;
fig. 6 is a structural view of an adaptive implant for bone insufficiency prepared according to the present invention.
Detailed Description
The exemplary embodiments will be described herein in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of products, methods consistent with certain aspects of the invention, as detailed in the appended claims.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings and examples.
Example 1
The embodiment provides a medical titanium-zirconium-iron alloy for an adaptive implant with insufficient bone mass, which comprises the following components in percentage by mass, namely 19% of Zr, 0.2% of Fe, 0.1% of O and the balance of Ti.
In addition, the embodiment also provides a preparation method of the medical titanium-zirconium-iron alloy for the self-adaptive implant with insufficient bone mass, which is shown in fig. 1 and specifically comprises the following steps:
step 1, selecting high-purity titanium blocks, zirconium blocks and iron particles according to weight percentage, polishing to remove oxide layers on the surfaces of the titanium blocks and the zirconium blocks, and carrying out vacuum melting for three times by using a vacuum arc furnace to obtain alloy ingots with uniform components;
wherein the diameter of the electrode is 160mm, the inner diameter of the crucible is 220mm, the primary smelting voltage is 32V, the primary smelting current is 18KA, the secondary smelting voltage is 36V, the secondary smelting current is 21KA, the tertiary smelting voltage is 42V, and the tertiary smelting current is 25KA;
2, grinding the titanium alloy ingot obtained in the step 1, cogging and forging at 900 ℃, precisely forging at 850 ℃ with the forging ratio of 4, and forging to form a large-size bar;
step 3, carrying out alpha + beta two-phase region solution treatment on the large-size bar obtained in the step 2 under the vacuum condition and under the protection of inert gas, wherein the heating temperature is 800 ℃, the heat preservation time is 0.5h, and the cooling mode is air cooling; then carrying out low-temperature aging treatment, wherein the heating temperature is 380 ℃, the heat preservation time is 10h, and air cooling;
step 4, heating the titanium alloy bar subjected to solid solution and low-temperature aging treatment to 800 ℃ in a box-type resistance furnace for multi-pass hot rolling, wherein the final rolling temperature is not less than 750 ℃, the accumulated deformation is 90%, and the single deformation is 10%;
and 6, carrying out recrystallization annealing treatment on the drawn titanium alloy wire, wherein the heating temperature is 750 ℃, the heat preservation time is 1h, and carrying out air cooling to obtain the titanium-zirconium-iron alloy wire (I) with fine and uniform tissue, wherein the transverse high-power tissue diagram of the titanium-zirconium-iron alloy wire (I) is shown in a figure 2 (a), the longitudinal high-power tissue diagram of the titanium-zirconium-iron alloy wire (I) is shown in a figure 2 (b), the tensile strength of the titanium-zirconium-iron alloy wire (I) reaches 1195MPa, the elongation is 26%, and the elastic modulus is 77GPa.
Example 2
The embodiment provides a medical titanium-zirconium-iron alloy for an adaptive implant with insufficient bone mass, which comprises the following components in percentage by mass, zr content is 25%, fe content is 1.3%, O content is 0.2%, and the balance is Ti.
In addition, the embodiment also provides a preparation method of the medical titanium-zirconium-iron alloy for the self-adaptive implant with insufficient bone mass, which comprises the following steps:
step 1, selecting high-purity titanium blocks, zirconium blocks and iron particles according to weight percentage, polishing to remove oxide layers on the surfaces of the titanium blocks and the zirconium blocks, and performing vacuum melting for three times by using a vacuum arc furnace to obtain alloy ingots with uniform components;
wherein the diameter of the electrode is 320mm, the inner diameter of the crucible is 406mm, the primary smelting voltage is 35V, the primary smelting current is 20KA, the secondary smelting voltage is 39V, the secondary smelting current is 23KA, the tertiary smelting voltage is 45V, and the tertiary smelting current is 27KA;
2, grinding the titanium alloy ingot obtained in the step 1, cogging and forging at 950 ℃, precisely forging at 900 ℃ with the forging ratio of 5 and 7, and forging to form a large-size bar;
step 3, carrying out alpha + beta two-phase region solution treatment on the large-size bar obtained in the step 2 under the vacuum condition and under the protection of inert gas, wherein the heating temperature is 750 ℃, the heat preservation time is 1h, and the cooling mode is air cooling; then carrying out low-temperature aging treatment, wherein the heating temperature is 460 ℃, the heat preservation time is 6h, and air cooling;
step 4, heating the titanium alloy bar subjected to solid solution and low-temperature aging treatment to 850 ℃ in a box-type resistance furnace for multi-pass hot rolling, wherein the final rolling temperature is not less than 750 ℃, the accumulated deformation is 70%, and the single deformation is 5%;
and 6, carrying out recrystallization annealing treatment on the drawn titanium alloy wire, wherein the heating temperature is 650 ℃, the heat preservation time is 5h, and carrying out air cooling to obtain a titanium-zirconium-iron alloy wire (II) with a fine and uniform structure, wherein the transverse high-power structural diagram of the titanium-zirconium-iron alloy wire (II) is shown in a figure 3 (a), the longitudinal high-power structural diagram of the titanium-zirconium-iron alloy wire (II) is shown in a figure 3 (b), the tensile strength of the titanium-zirconium-iron alloy wire (II) reaches 1241MPa, the elongation of the titanium-zirconium-iron alloy wire (II) is 25%, and the elastic modulus of the titanium-zirconium-iron alloy wire (II) is 80GPa.
Example 3
The embodiment provides a medical titanium-zirconium-iron alloy for an adaptive implant with insufficient bone mass, which comprises the following components in percentage by mass, namely Zr content of 30%, fe content of 1.9%, O content of 0.3%, and the balance of Ti.
In addition, the embodiment also provides a preparation method of the medical titanium-zirconium-iron alloy for the self-adaptive implant with insufficient bone mass, which comprises the following steps:
step 1, selecting high-purity titanium blocks, zirconium blocks and iron particles according to weight percentage, polishing to remove oxide layers on the surfaces of the titanium blocks and the zirconium blocks, and performing vacuum melting for three times by using a vacuum arc furnace to obtain alloy ingots with uniform components;
wherein the diameter of the electrode is 280mm, the inner diameter of the crucible is 380mm, the primary smelting voltage is 33V, the primary smelting current is 19KA, the secondary smelting voltage is 37V, the secondary smelting current is 22KA, the tertiary smelting voltage is 43V, and the tertiary smelting current is 26KA;
2, grinding the titanium alloy ingot obtained in the step 1, cogging and forging at 930 ℃, precisely forging at 870 ℃ at a forging ratio of 4.5 and 6, and forging to form a large-size bar;
step 3, carrying out alpha + beta two-phase region solution treatment on the large-size bar obtained in the step 2 under the vacuum condition and under the protection of inert gas, wherein the heating temperature is 770 ℃, the heat preservation time is 2.5h, and the cooling mode is air cooling; then carrying out low-temperature aging treatment, cooling in air, wherein the heating temperature is 420 ℃, and the heat preservation time is 8 h;
step 4, heating the titanium alloy bar subjected to solid solution and low-temperature aging treatment to 830 ℃ in a box-type resistance furnace for multi-pass hot rolling, wherein the final rolling temperature is not less than 750 ℃, the accumulated deformation is 80%, and the single deformation is 7%;
and 6, carrying out recrystallization annealing treatment on the drawn titanium alloy wire, wherein the heating temperature is 700 ℃, the heat preservation time is 3h, and carrying out air cooling to obtain a titanium-zirconium-iron alloy wire (III) with a fine and uniform structure, wherein the transverse high-power structural diagram of the titanium-zirconium-iron alloy wire (III) is shown in a figure 4 (a), the longitudinal high-power structural diagram of the titanium-zirconium-iron alloy wire (III) is shown in a figure 4 (b), the tensile strength of the titanium-zirconium-iron alloy wire (III) reaches 1136MPa, the elongation is 29%, and the elastic modulus is 72GPa.
From examples 1 to 3, it can be seen that in the preparation method provided by the present invention, the α + β two-phase region solution treatment and the low temperature aging treatment are combined with the α + β region rolling and the β phase region drawing processes to form a fine and uniform equiaxial α phase and a partially elongated α phase, and the texture improves the overall performance of the ti-zr-fe alloy, and the ti-zr-fe alloy has a tensile strength of 1120 to 1250MPa, a yield strength of greater than 1000MPa, an elongation after fracture of 25 to 30%, and an elastic modulus of 72 to 80GPa.
In addition, in the adaptive implant made of the medical titanium-zirconium-iron alloy prepared by the above preparation method, as shown in fig. 6, the adaptive implant has a porous structure, the porous structure is distributed from 2mm above the root tip of the adaptive implant to 5mm below the neck of the adaptive implant, and the porous structure can be prepared by mechanical processing (such as drilling and turning), the pore size is 0.2-0.8 mm, the pore edge size is 2-5 mm, and the porous structure comprises a trapezoid, a cylinder, a cuboid, a cube and the like.
The self-adaptive implant can form a hydrophilic surface layer through special surface treatment, and the specific surface treatment is as follows: carrying out sand blasting and acid etching, then carrying out heat treatment in water at 40-60 ℃ for 1-2 days to form nanoscale holes, and combining a macroscopic porous structure to form a hydrophilic surface of a multistage micro-nano hole composite structure. The surface can significantly improve the bonding performance of the bone-implant interface while reducing the stress concentration of the implant. And finally, the hydrophilic surface implant is soaked in a potassium phosphate solution with the pH value of 7.3-7.6 for storage, so that the hydrophilic surface activity of the implant can be effectively prolonged, and the osteogenic growth of an implant-bone interface can be promoted.
In order to further verify the effectiveness of the technical scheme provided by the invention, comparison is performed by combining a comparative example, and specific components and proportions are shown in table 1:
table 1 examples 1 to 3 and comparative examples 1 to 2 relate to chemical composition comparison (wt.%) of titanium alloy materials
| Material | Zr | Fe | O | Ti |
| Example 1 | 19 | 0.2 | 0.1 | Balance of |
| Example 2 | 25 | 1.3 | 0.2 | Balance of |
| Example 3 | 30 | 1.9 | 0.3 | Allowance of |
| Comparative example 1 | 15 | 2.0 | - | Balance of |
| Comparative example 2 | 6 | 5 | - | Balance of |
The differences between comparative examples 1 to 2 and the examples of the present application are described below with reference to Table 1: comparative example 1 is a medical TiZr alloy containing a small amount of Fe element, and comparative example 2 is a medical titanium alloy containing a low Zr element content and a high Fe element content. Wherein, the preparation process of the comparative example 1 does not relate to the correlation among the processing technologies, and the preparation process of the comparative example 2 only relates to the heating temperature, the holding time and the cooling mode parameters of the solution treatment and the aging treatment, and does not relate to the thermal deformation technological parameters. The samples of examples 1 to 3 and comparative examples 1 to 2 were subjected to room temperature tensile property tests, and the mechanical property indexes obtained by the tests included tensile strength R m Yield strength R p0.2 The elongation after fracture A, the reduction of area Z and the elastic modulus E are shown in Table 2.
TABLE 2 results of measuring room-temperature tensile properties of titanium alloy materials of examples 1 to 3 and comparative examples 1 to 2
| Case(s) | R m (MPa) | R p0.2 (MPa) | A(％) | Z(％) | E(GPa) |
| Example 1 | 1241 | 1197 | 25 | 56 | 80 |
| Example 2 | 1195 | 1083 | 26 | 54 | 77 |
| Example 3 | 1136 | 1007 | 29 | 57 | 72 |
| Comparative example 1 | 1288 | 1254 | 15 | 42 | 90 |
| Comparative example 2 | 1362 | 1237 | 11 | 38 | 92 |
As shown in Table 2, the tensile strengths of comparative examples 1-2 exceed 1280MPa and the elongation after fracture is less than 16%, while the tensile strength of the present invention is between 1120MPa and 1250MPa, the elongation after fracture can reach 25-30%, and the elastic modulus is 75-80 GPa. Therefore, the strength of the titanium-zirconium-iron alloy provided by the invention is superior to that of the conventional pure titanium and TC4 alloy, and the stress shielding effect caused by overlarge elastic modulus can be avoided; in addition, the plasticity of the titanium zirconium iron alloy wire materials shown in examples 1-3 has obvious advantages compared with comparative examples 1 and 2, and because the tensile strength of the comparative examples 1 and 2 is too high, namely the hardness is too high, the implanted jaw bone is easy to abrade, and metal element ions are separated out, so that diseases such as periodontitis and the like are caused.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. The titanium-zirconium-iron alloy for the self-adaptive implant with insufficient bone mass is characterized by comprising the following chemical components in percentage by weight: 19 to 30 percent of Zr, 0.1 to 2 percent of Fe, 0.1 to 0.3 percent of O and the balance of Ti.
2. The titanium-zirconium-iron alloy for the adaptive implant of osteopenia according to claim 1, wherein the titanium-zirconium-iron alloy has a tensile strength of 1120 to 1250MPa, a yield strength of more than 1000MPa, an elongation after fracture of 25 to 30% and an elastic modulus of 72 to 80GPa.
3. A method for preparing an adaptive implant titanium zirconium iron alloy for osteopenia according to claim 1 or 2, comprising the steps of:
step 1, selecting high-purity titanium blocks, zirconium blocks and iron particles according to weight percentage, removing oxide layers on the surfaces of the titanium blocks and the zirconium blocks, and carrying out vacuum melting for three times by using a vacuum arc furnace to obtain titanium alloy ingots with uniform components; wherein the diameter of the electrode is 150-320 mm, the inner diameter of the crucible is 220-406 mm, the crucible ratio is 0.75-0.85, the smelting voltage is 32-45V, and the smelting current is 18-27 KA;
step 2, grinding the titanium alloy ingot obtained in the step 1, and forming a large-size bar through cogging forging and precision forging;
step 3, carrying out alpha + beta two-phase region solution treatment and low-temperature aging treatment on the large-size bar obtained in the step 2 under the vacuum condition and the protection of inert gas;
step 4, carrying out hot rolling on the titanium alloy bar subjected to the solid solution and low-temperature aging treatment, wherein the accumulated deformation is not less than 70%, and the single deformation is 5-10%;
step 5, carrying out hot drawing treatment on the titanium alloy bar subjected to hot rolling, wherein the accumulated deformation is not less than 70%, and the single deformation is 5-10%, so as to obtain a titanium alloy wire;
and 6, carrying out recrystallization annealing treatment on the titanium alloy wire subjected to hot drawing to obtain the target titanium-zirconium-iron alloy wire.
4. The method for preparing the self-adaptive implant titanium-zirconium-iron alloy for insufficient bone mass according to claim 3, wherein the specific parameters of the three times of vacuum melting in the step 1 are as follows: the primary smelting voltage is 32-35V, and the primary smelting current is 18-20 KA; the secondary smelting voltage is 36-39V, and the secondary smelting current is 21-23 KA; the third smelting voltage is 42-45V, and the third smelting current is 25-27 KA.
5. The method for preparing the titanium-zirconium-iron alloy for the adaptive implant with insufficient bone mass according to claim 3, wherein the temperature of the cogging forging in the step 2 is 900 to 950 ℃, and the forging ratio is 4 to 5; the temperature of the precision forging is 850-900 ℃, and the forging ratio is 5-7.
6. The method for preparing the titanium-zirconium-iron alloy for the adaptive implant with insufficient bone mass according to the claim 3, wherein the temperature of the solution treatment in the step 3 is 750-800 ℃, the time of the solution treatment is 0.5-2.5 h, and the water cooling is performed rapidly; the aging treatment temperature is 380-460 ℃, the aging time is 6-10 h, and the air cooling is carried out.
7. The method for preparing the titanium-zirconium-iron alloy for the self-adaptive implant with insufficient bone mass according to the claim 3, wherein the hot rolling in the step 4 is specifically as follows: heating to 800-850 ℃ in a box type resistance furnace before rolling, wherein the finishing temperature is not less than 750 ℃.
8. The method for preparing the titanium-zirconium-iron alloy for the adaptive implant with insufficient bone mass according to claim 3, wherein the drawing temperature in the step 5 is 850-880 ℃, the drawing speed is 20-50 mm/s, and the stress relief annealing treatment at 700-750 ℃ is performed twice in the middle of drawing.
9. The method for preparing the titanium zirconium iron alloy for the self-adaptive implant with insufficient bone mass according to claim 3, wherein the recrystallization annealing temperature in the step 6 is 650 to 750 ℃, the holding time is 1 to 5 hours, and then air cooling is carried out.
10. An adaptive implant for osteopenia, which is manufactured using the titanium zirconium iron alloy manufactured by the method according to any one of claims 3 to 9, and has a porous structure with a pore size of 0.2 to 0.8mm and a pore edge size of 2 to 5mm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1305879A (en) * | 1970-07-13 | 1973-02-07 | ||
| JPS60224727A (en) * | 1984-04-24 | 1985-11-09 | Haruyuki Kawahara | Ti-zr sintered alloy |
| JPH051342A (en) * | 1991-06-24 | 1993-01-08 | Sumitomo Heavy Ind Ltd | Production of titanium alloy and sintered titanium alloy |
| JP2001003126A (en) * | 1999-04-23 | 2001-01-09 | Terumo Corp | MEDICAL APPLIANCE COMPOSED OF Ti-Zr ALLOY |
| CN109487121A (en) * | 2018-12-11 | 2019-03-19 | 南京航空航天大学 | A kind of gear division titanium alloy and preparation method thereof |
| US20190111482A1 (en) * | 2016-02-08 | 2019-04-18 | Abdelmadjid Djemai | Process for producing a beta-alloy Titanium Niobium Zirconium (TNZ) with a very low modulus of elasticity for biomedical applications and its embodiment by additive manufacturing. |
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1305879A (en) * | 1970-07-13 | 1973-02-07 | ||
| JPS60224727A (en) * | 1984-04-24 | 1985-11-09 | Haruyuki Kawahara | Ti-zr sintered alloy |
| JPH051342A (en) * | 1991-06-24 | 1993-01-08 | Sumitomo Heavy Ind Ltd | Production of titanium alloy and sintered titanium alloy |
| JP2001003126A (en) * | 1999-04-23 | 2001-01-09 | Terumo Corp | MEDICAL APPLIANCE COMPOSED OF Ti-Zr ALLOY |
| US20190111482A1 (en) * | 2016-02-08 | 2019-04-18 | Abdelmadjid Djemai | Process for producing a beta-alloy Titanium Niobium Zirconium (TNZ) with a very low modulus of elasticity for biomedical applications and its embodiment by additive manufacturing. |
| CN109487121A (en) * | 2018-12-11 | 2019-03-19 | 南京航空航天大学 | A kind of gear division titanium alloy and preparation method thereof |
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