Ultrahigh-strength Ti15Zr5Cu alloy and preparation method and application thereof

Abstract

The invention provides an ultrahigh-strength Ti15Zr5Cu alloy as well as a preparation method and application thereof, belongs to the technical field of additive manufacturing of medical titanium alloy materials, and solves the technical problems that an existing Ti-Zr-Cu alloy is relatively poor in mechanical property and cannot meet the mechanical property requirements of high strength and the like of an oral medical implant material. The Ti15Zr5Cu alloy comprises the following chemical components in percentage by weight: 13 to 14.9 percent of Zr, 4 to 5 percent of Cu and the balance of Ti. The preparation method of the Ti15Zr5Cu alloy comprises the steps of raw material smelting, high-temperature forging, atomization powder preparation, powder screening, airflow classification, heat preservation drying and 3D printing. The tensile strength of the Ti15Zr5Cu alloy reaches 1618-1672 MPa, and the ductility of the Ti15Zr5Cu alloy is reduced to 6%, namely about 7%; the material can be widely applied to oral medical implant materials.

Description

Technical Field

[0001] The present invention relates to the field of additive manufacturing of titanium alloy materials for medical use, and in particular to an ultra-high strength Ti 15 Zr5Cu alloy and its preparation method and application. Background Art

[0002] As people pay more and more attention to oral health, the demand for implant dentures in the treatment of tooth defects has shown a rapid growth trend. In the research history of dental implant materials, researchers have found that adding Zr elements to Cp-Ti not only makes the implant have excellent biocompatibility, but also increases the axial ratio of the α phase and activates the non-cylindrical slip of the α phase, thereby improving the alloy's strain hardening ability and uniform plastic deformation ability. Therefore, the addition of Zr elements is regarded as an effective way to improve the comprehensive performance of Cp-Ti. With the expansion of the application of titanium-zirconium alloys, higher requirements are placed on the antibacterial activity of titanium-zirconium alloys. To this end, researchers have proposed a research idea to incorporate the metal antibacterial element Cu into the implant surface and matrix to improve the alloy.

[0003] The invention with publication number CN112322932A discloses a nanocrystalline Ti-Zr-Cu alloy and a laser selective melting additive manufacturing method thereof. The chemical composition of the alloy is as follows (weight %): Cu: 1-10; Zr: 15-20; the balance is Ti; the preparation method of the nanocrystalline Ti-Zr-Cu alloy is: using the selective melting additive manufacturing technology, the laser power is 350-450W, the scanning speed is 1200-2500mm·S -1 , interlayer deflection angle 45~100°, energy density 50~120J·mm -3 The tensile strength of the nanocrystalline Ti-Zr-Cu alloy reaches 1200-1500 MPa, and the elongation is ≥12%.

[0004] According to the use requirements of human oral teeth, the central incisor is the tooth with the highest frequency of biting food. Compared with other teeth, the mechanical properties of incisor screws made of implant alloy materials are required to be higher. The above-mentioned Ti-Zr-Cu alloy has low tensile strength and high elongation, and undergoes large deformation when subjected to low external force. Therefore, it cannot meet the mechanical properties requirements such as high strength of oral medical implant incisor screws. The reasons are mainly manifested in two aspects: on the one hand, during the additive manufacturing process, pre-alloyed powder is prone to solid-state cracking and delayed cracking caused by residual stress; on the other hand, the mixed powder is sensitive to temperature during processing, resulting in uneven tissue during forming. Summary of the invention

[0005] The purpose of the present invention is to solve the shortcomings of the above-mentioned technology and provide an ultra-high strength Ti 15Zr5Cu alloy and its preparation method and application can improve tensile strength and reduce elongation to meet the high strength and other mechanical property requirements of oral medical implant materials.

[0006] To this end, the present invention provides an ultra-high strength Ti 15 Zr5Cu alloy, in terms of weight percentage, the chemical composition of the titanium alloy is: Zr: 13-14.9%; Cu: 4-5%; the balance is Ti. The content of impurity elements in the alloy should comply with the corresponding requirements of the national standard "Titanium and Titanium Alloy Grades and Chemical Composition Table".

[0007] An ultra-high strength Ti 15 The preparation method of Zr5Cu alloy comprises the following steps:

[0008] Raw material smelting: The alloy material containing titanium, zirconium and copper elements is smelted according to the ultra-high strength Ti 15 The weight percentage of each element in the Zr5Cu alloy is fully melted to obtain a titanium zirconium copper ingot;

[0009] High temperature forging: The smelted titanium-zirconium-copper ingot is fully forged at a certain temperature to obtain a titanium-zirconium-copper alloy rod;

[0010] Atomization powder making: atomizing and powdering the forged titanium-zirconium-copper alloy rod to obtain titanium-zirconium-copper alloy powder;

[0011] Powder screening and airflow classification: The titanium-zirconium-copper alloy powder after atomization is screened and then subjected to airflow classification to obtain a titanium-zirconium-copper alloy powder with a particle size range of 11 to 72 μm;

[0012] Heat preservation and drying: the titanium-zirconium-copper alloy powder after airflow classification is fully heat-insulated and dried to obtain titanium-zirconium-copper alloy powder for 3D printing;

[0013] The titanium-zirconium-copper alloy powder for 3D printing was heat-dried and manufactured by laser selective melting to obtain ultra-high strength Ti 15 Zr5Cu alloy.

[0014] Preferably, in the raw material smelting step, the smelting temperature is controlled at 1000-1100°C.

[0015] Preferably, in the high temperature forging step, the forging temperature is controlled at 900-1000°C.

[0016] Preferably, in the atomization powder making step, the titanium-zirconium-copper alloy rod is atomized into droplets by an inert gas flow, and the droplets are solidified to form alloy powder to obtain titanium-zirconium-copper alloy powder; wherein the inert gas pressure is controlled at 35 to 45 bar, and the vacuum degree is ≤5 Pa; the inert gas can be argon.

[0017] Preferably, in the powder screening and airflow classification steps, the titanium-zirconium-copper alloy powder after atomization is subjected to ultrasonic vibration screening and grading treatment under an inert gas protective atmosphere to complete powder screening; wherein the pressure of the inert gas is controlled at 38 to 40 bar; the inert gas can be argon.

[0018] Preferably, in the powder screening and airflow classification steps, the titanium-zirconium-copper alloy powder after powder screening is effectively separated by an airflow screening machine to obtain a titanium-zirconium-copper alloy powder with a particle size range of 11 to 72 μm; wherein the frequency of the classifying wheel of the airflow separator is controlled at 30 to 35 Hz.

[0019] Preferably, in the heat preservation and drying step, the drying temperature is controlled at 100-110°C.

[0020] Preferably, the parameter conditions of laser selective melting additive manufacturing include:

[0021] Preheat the substrate before 3D printing at a temperature of 50-150°C to reduce the solidification temperature gradient and the tendency of thermal cracking;

[0022] High-purity argon gas is passed through the printing chamber. High-purity argon gas (usually 99.999%) is passed through the printing chamber to replace oxygen. The argon pressure is 0.4-0.8MPa, and the oxygen concentration is controlled below 400ppm.

[0023] Laser power 120-180W, scanning speed 1100-1200mm / s, scanning spacing 0.09-0.12mm; interlayer thickness 0.03mm; scanning strategy with a rotation angle of 67° between adjacent layers; powder spreading rate set at 100-200%; energy density 37-55.6J·mm -3 .

[0024] A kind of ultra-high strength Ti 15 Application of Zr5Cu alloy in oral medical implant materials.

[0025] An ultra-high strength Ti prepared by the method described above 15 Application of Zr5Cu alloy in oral medical implant materials.

[0026] The design concept of the present invention is:

[0027] The present invention obtains nanoscale structure by designing powder preparation process to control alloy powder structure and 3D printing parameters, and mainly consists of equiaxed α grains with an average grain size of 6.7 μm, further improving alloy strength. βThe microstructure obtained by forging deformation at -30℃ is equiaxed α structure. Coarse grains will gradually be broken into finer grains. The dislocation density inside the grains increases, reducing the internal stress concentration points to ensure that the internal microstructure holes and cracks are avoided. The alloy rods are atomized and condensed into high-density spherical powders by aerosol method. With appropriate energy density, the microstructure is mainly equiaxed crystals. A large number of fine lath-shaped α′ martensite with high aspect ratio is observed inside the columnar grains. Most of the α′ martensite nucleates at the β grain boundary and grows in the β phase grains where it is located. A few α′ martensite extends into adjacent β grains. Needle-shaped and lath-shaped α′ martensite of different widths intersect with each other. Nanoscale α′ martensite seems to nucleate and grow in the early stage of heating, and then further grows in subsequent thermal cycles to form a nanoscale HCP structure alpha' phase, which greatly improves Ti 15 Strength of Zr5Cu alloy.

[0028] The present invention provides an ultra-high strength Ti 15 Zr5Cu alloy and its preparation method and application have the following beneficial effects:

[0029] (1) The present invention reasonably designs the matching value between the laser power and the scanning rate of the 3D technology, and uses the ImageJ image software to count the metallographic defects of the alloys prepared with different process parameters, thereby obtaining a Ti alloy without cracks and with a density of 99.99%. 15 Zr5Cu alloy, compared with the prior art, the present invention Ti 15 The tensile strength of Zr5Cu alloy is 1618-1672MPa, and its elongation after fracture is about 6% and 7%, which meets the mechanical property requirements of oral medical implants such as incisor screws, such as high strength.

[0030] (2) The 3D technology used in the present invention is fast and simple to prepare high-strength Ti15Zr5Cu alloy products. After 3D printing, it can directly reach more than 1600MPa. There is no need to perform solid solution heat treatment below the phase transition point of the alloy as in the prior art, and high-strength mechanical properties can be achieved with few internal defects and low cost.

[0031] (3) The microstructure of the present invention is mainly equiaxed crystals, and a large amount of fine lath-shaped α′ martensite with a high aspect ratio is observed inside the columnar grains, which greatly improves the strength of the alloy. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application.

[0033] Figure 1The Ti for 3D printing prepared in step 5 of Example 1 of the present invention 15 Zr5Cu alloy powder morphology photo;

[0034] Figure 2 The Ti for 3D printing prepared in step 5 of Example 1 of the present invention 15 Particle size distribution of Zr5Cu alloy powder;

[0035] Figure 3 S1, S2, and S3 are Ti obtained in Examples 1 to 3 of the present invention respectively. 15 Cross-sectional metallographic photograph of Zr5Cu alloy;

[0036] Figure 4 a) is Ti obtained in Example 1 of the present invention 15 Cross-sectional micromorphology of Zr5Cu alloy; Figure 4 b) is Figure 4 a) Schematic diagram of statistical defects after processing by Image J software;

[0037] Figure 5 a) is the Ti treated with the etching solution obtained in Example 1 of the present invention. 15 Microstructure photo of Zr5Cu alloy; Figure 5 b) is the Ti treated with the etching solution obtained in Example 1 of the present invention. 15 SEM image of Zr5Cu alloy;

[0038] Figure 6 The 3D printed Ti obtained in Example 1 of the present invention 15 Actual photo of tensile specimen of Zr5Cu alloy;

[0039] Figure 7 The stress-strain curves of the tensile specimens of the titanium-zirconium-copper alloys prepared in Examples 1 to 3 and Comparative Examples 1 to 3 are shown. DETAILED DESCRIPTION

[0040] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0041] Unless otherwise specified, the methods used in the present invention are all conventional methods; the raw materials and devices used are all conventional commercially available products unless otherwise specified.

[0042] Example 1

[0043] The present invention provides an ultra-high strength Ti 15The preparation method of Zr5Cu alloy comprises the following steps:

[0044] Step 1, raw material smelting: The raw material composition is in the weight percentage ratio: Zr: 14.9%, Cu: 5%, and the balance is Ti. The alloy raw material is placed in an arc furnace with a water-cooled copper crucible under an argon atmosphere for smelting, the smelting temperature is controlled at 1000-1100°C, and remelted 4 times to obtain a titanium zirconium copper ingot;

[0045] Step 2, high temperature forging: the titanium-zirconium-copper ingot obtained in step 1 is subjected to a first-time forging at a forging temperature of 900° C. to obtain a titanium-zirconium-copper alloy rod;

[0046] Step 3, atomization powder making: the titanium-zirconium-copper alloy ingot rod obtained in step 2 is clamped in an atomization barrel, and is atomized into fine droplets when it meets a high-speed argon gas flow, and the atomized droplets are rapidly solidified into alloy powder in a closed atomization barrel, that is, the titanium-zirconium-copper alloy rod is atomized into droplets by an inert gas flow, and the droplets are solidified to form alloy powder, thereby obtaining titanium-zirconium-copper alloy powder; wherein the atomization gas pressure is controlled at 35-45 bar, and the vacuum degree is ≤5 Pa;

[0047] Step 4: Powder screening and airflow classification: The titanium-zirconium-copper alloy powder obtained in step 3 is subjected to ultrasonic vibration screening and classification treatment under an argon protective atmosphere, and the pressure of the argon is controlled at 38-40 bar.

[0048] Then, the titanium-zirconium-copper alloy powders of different particle sizes after powder screening are effectively separated by an airflow screening machine, and the frequency of the classification wheel of the airflow separator is controlled at 30 to 35 Hz to obtain titanium-zirconium-copper alloy powders with a particle size range of 11 to 72 μm;

[0049] Step 5: Heat preservation and drying: the powder obtained after screening in step 4 is placed in a drying oven for drying, the drying temperature is controlled at 100-110°C, the drying time is 12 hours, and titanium-zirconium-copper alloy powder for 3D printing is obtained.

[0050] Step 6: The titanium-zirconium-copper alloy powder for 3D printing obtained in step 5 is subjected to laser selective melting additive manufacturing to prepare the ultra-high strength Ti 15 Zr5Cu alloy.

[0051] Among them, the parameter conditions of the laser selective melting additive manufacturing include:

[0052] The 3D printing substrate uses a TC4 titanium alloy substrate, which is preheated before 3D printing at a preheating temperature of 150°C;

[0053] High-purity argon is passed through the printing chamber to replace oxygen. The argon pressure is 0.8MPa, and the oxygen concentration is controlled below 400ppm.

[0054] The laser power is 120W, the scanning speed is 1100mm / s, the scanning interval is 0.09mm, the interlayer thickness is 0.03mm, the scanning strategy is a rotation angle of 67° between adjacent layers, the powder spreading rate is set to 100%, and the energy density is 37J·mm -3 .

[0055] Example 2

[0056] The present invention provides an ultra-high strength Ti 15 The preparation method of Zr5Cu alloy comprises the following steps:

[0057] Step 1, raw material smelting: The difference from step 1 of the above embodiment 1 is that the raw material composition is in the following weight percentage ratio: Zr: 14%, Cu: 4.5%, and the balance is Ti; the other contents are the same and will not be repeated; titanium zirconium copper ingot is obtained;

[0058] Step 2, high temperature forging: The difference from step 1 of the above embodiment 1 is that the forging temperature is 950° C. The other contents are the same and will not be repeated; a titanium-zirconium-copper alloy rod is obtained;

[0059] Step 3, argon gas atomization powder preparation: the contents are the same as those of step 3 in the above embodiment 1, and will not be repeated here; titanium zirconium copper alloy powder is obtained;

[0060] Step 4: powder screening and airflow classification: the contents are the same as those of step 4 in the above embodiment 1 and will not be repeated here; titanium-zirconium-copper alloy powder with a particle size range of 11 to 72 μm is obtained;

[0061] Step 5: heat preservation and drying: the contents are the same as those of step 5 in the above-mentioned embodiment 1 and will not be described again; titanium-zirconium-copper alloy powder for 3D printing is obtained.

[0062] Step 6: The titanium-zirconium-copper alloy powder for 3D printing obtained in step 5 is subjected to laser selective melting additive manufacturing to prepare the ultra-high strength Ti 15 Zr5Cu alloy.

[0063] Among them, the parameter conditions of the laser selective melting additive manufacturing include:

[0064] The 3D printing substrate uses a TC4 titanium alloy substrate, which is preheated before 3D printing at a temperature of 100°C;

[0065] High-purity argon is passed through the printing chamber to replace oxygen. The argon pressure is 0.6MPa, and the oxygen concentration is controlled below 400ppm.

[0066] The laser power is 150W, the scanning speed is 1150mm / s, the scanning interval is 0.10mm, the interlayer thickness is 0.03mm, the scanning strategy is a rotation angle of 67° between adjacent layers, the powder spreading rate is set to 150%, and the energy density is 46.3J·mm -3 .

[0067] Example 3

[0068] The present invention provides an ultra-high strength Ti 15 The preparation method of Zr5Cu alloy comprises the following steps:

[0069] Step 1, raw material smelting: the difference from step 1 of the above embodiment 1 is that the raw material composition is in the following weight percentage ratio: Zr: 13%, Cu: 4%, and the balance is Ti; the other contents are the same and will not be repeated; titanium zirconium copper ingot is obtained;

[0070] Step 2, high temperature forging: The difference from step 1 of the above embodiment 1 is that the forging temperature is 1000° C., and the other contents are the same and will not be repeated; a titanium-zirconium-copper alloy rod is obtained;

[0071] Step 3, argon gas atomization powder preparation: the contents are the same as those of step 3 in the above embodiment 1, and will not be repeated here; titanium zirconium copper alloy powder is obtained;

[0072] Step 4: powder screening and airflow classification: the contents are the same as those of step 4 in the above embodiment 1 and will not be repeated here; titanium-zirconium-copper alloy powder with a particle size range of 11 to 72 μm is obtained;

[0073] Step 5: heat preservation and drying: the contents are the same as those of step 5 in the above-mentioned embodiment 1 and will not be described again; titanium-zirconium-copper alloy powder for 3D printing is obtained.

[0074] Step 6: The titanium-zirconium-copper alloy powder for 3D printing obtained in step 5 is subjected to laser selective melting additive manufacturing to prepare the ultra-high strength Ti 15 Zr5Cu alloy.

[0075] Among them, the parameter conditions of the laser selective melting additive manufacturing include:

[0076] The 3D printing substrate uses a TC4 titanium alloy substrate, which is preheated before 3D printing at a temperature of 50°C;

[0077] High-purity argon is passed through the printing chamber to replace oxygen. The argon pressure is 0.4MPa, and the oxygen concentration is controlled below 400ppm.

[0078] The laser power is 180W, the scanning speed is 1200mm / s, the scanning interval is 0.12mm, the interlayer thickness is 0.03mm, the scanning strategy is a rotation angle of 67° between adjacent layers, the powder spreading rate is set to 200%, and the energy density is 55.6J·mm -3 .

[0079] Now, the above-mentioned embodiments 1 to 3 are 15 The chemical composition of Zr5Cu alloy and the main parameter conditions of laser selective melting additive manufacturing are summarized in Table 1.

[0080] Table 1 Examples 1-3Ti 15 Summary of chemical composition of Zr5Cu alloy and main parameters of laser selective melting additive manufacturing

[0081]

[0082] Comparative Example

[0083] Comparative Example 1

[0084] Comparative Example 1 provides a method for preparing a titanium-zirconium-copper alloy, which is similar to the ultra-high strength Ti 15 The preparation method of Zr5Cu alloy is different in that the raw material composition is Zr: 16%, Cu: 6%, and the balance is Ti according to the weight percentage, and some parameter conditions of laser selective melting additive manufacturing (see Table 2 below). The other contents are the same and will not be repeated.

[0085] Comparative Example 2

[0086] Comparative Example 1 provides a method for preparing a titanium-zirconium-copper alloy, which is similar to the ultra-high strength Ti 15 The preparation method of Zr5Cu alloy is different in that the raw material composition is Zr: 17%, Cu: 6.5%, and the balance is Ti according to the weight percentage, and some parameter conditions of laser selective melting additive manufacturing (see Table 2 below). The other contents are the same and will not be repeated.

[0087] Comparative Example 3 Comparative Example 1 provides a method for preparing a titanium-zirconium-copper alloy, which is different from the ultra-high strength Ti 15 The preparation method of Zr5Cu alloy is different in that the raw material composition is Zr: 15.5%, Cu: 8%, and the balance is Ti according to the weight percentage, and some parameter conditions of laser selective melting additive manufacturing (see Table 2 below). The other contents are the same and will not be repeated.

[0088] The chemical compositions of the titanium-zirconium-copper alloys of the above comparative examples 1 to 3 and the main parameter conditions of laser selective melting additive manufacturing are summarized in Table 2 below.

[0089] As shown in Table 2, the chemical compositions of Cu and Zr in Comparative Examples 1 to 3 are respectively higher than the maximum value of the weight percentage of the chemical compositions of Cu and Zr in the present invention; the laser powers of Comparative Examples 1 and 2 are lower than the minimum value of the laser powers of Examples 1 to 3 of the present invention; the laser power of Comparative Example 3 is higher than the maximum value of the laser powers of Examples 1 to 3 of the present invention; and the scanning speeds of Comparative Examples 1 to 3 are lower than the minimum value of the scanning speeds of Examples 1 to 3 of the present invention.

[0090] Table 2 Summary of chemical composition of titanium-zirconium-copper alloy and main parameters of laser selective melting additive manufacturing for comparative examples 1-3

[0091]

[0092] Experimental testing

[0093] 1. Figure 1 The Ti for 3D printing prepared in step 5 of Example 1 of the present invention 15 Zr5Cu alloy powder morphology photo; Figure 1 As shown, the prepared Ti 15 The Zr5Cu alloy powder has good sphericity.

[0094] Ti for 3D printing prepared in step 5 of Example 1 of the present invention 15 The particle size distribution of Zr5Cu alloy powder is Figure 2 As shown, the powder particle size D 10 =17.32μm, D 50 =33.58μm, D 90 =52.70μm.

[0095] 2. The ultra-high strength Ti prepared by the methods described in Examples 1 to 3 15 The Zr5Cu alloy was ground and polished. The polished alloys were marked as S1, S2, and S3 respectively. The cross-sectional optical microscopy photos of the polished alloys are shown in Figure 1. Figure 3 As shown, it can be seen that there are no cracks in the sample and few defects.

[0096] 3. Figure 4 a) is Ti obtained in Example 1 of the present invention 15 Cross-sectional micromorphology of Zr5Cu alloy; Figure 4 b) Figure 4 a) Schematic diagram of statistical defects after processing by Image J image processing software. On the one hand, the statistical defects after processing by Image J image processing software Figure 4a) shows all the grain sizes and numbers, and the average grain size is 6.7 μm. On the other hand, the threshold processing in Image J can be used to convert it into defect boundaries, and then the analyze particles operation in Image J can be used to determine the total defect ratio in the plane, and the density is 99.99%.

[0097] 4. Ultra-high strength Ti prepared by the method described in Example 1 15 The Zr5Cu alloy was wire cut to obtain a disc sample, which was hot-mounted. The sample was polished step by step using sandpaper of 400 mesh, 1000 mesh, and 2000 mesh to make the sample surface smooth and traceless. Next, the sample was corroded in a metallographic corrosive agent, which was composed of three solutions of HF, HNO3, and H2O in a volume ratio of 5:20:75, and the corrosion time was 30s. Finally, the alloy structure was observed by metallographic microscope and scanning electron microscope.

[0098] The ultra-high strength Ti prepared by the method described in Example 1 and treated with the etching solution 15 The microstructure of Zr5Cu alloy is shown in the figure Figure 5 a), and scanning electron microscope photos such as Figure 5 As shown in b), the microstructure is mainly equiaxed crystals, and a large number of fine lath-shaped α′ martensite with high aspect ratio is observed inside the columnar grains. Most of the α′ martensite nucleates at the β grain boundary and grows in the β phase grains where it is located, and a few α′ martensite extends into the adjacent β grains. Needle-shaped and lath-shaped α′ martensite of different widths intersect with each other. The nanoscale α′ martensite seems to nucleate and grow in the early stage of heating, and then further grows in the subsequent thermal cycle to form the nanoscale HCP structure alpha' phase, which greatly improves Ti 15 Strength of Zr5Cu alloy.

[0099] 5. The titanium-zirconium-copper alloy prepared by the methods described in Examples 1 to 3 and Comparative Examples 1 to 3 was processed into standard tensile specimens using a lathe. The dimensions of the standard tensile specimens were 6 mm in thread diameter, 3 mm in gauge diameter, and 4.5 mm in length. Two parallel samples were taken for each standard tensile specimen of each Example and Comparative Example. Figure 6 shown.

[0100] The standard tensile test specimens of Examples 1 to 3 and Comparative Examples 1 to 3 were tested for tensile mechanical properties at room temperature using a metal tensile testing machine, with a tensile rate of 0.1 mm / min. The test results are shown in Table 3 and Figure 7 shown.

[0101] Table 3 Summary of mechanical properties test results of Examples 1-3 and Comparative Examples 1-3

[0102]

[0103]

[0104] From Table 3, Figure 7 As shown, the strain rate of the tensile test machine is 1×10 -3 / s, the tensile strengths of Examples 1 to 3 are all greater than 1600 MPa, and the tensile strength of Example 1 is close to 1700 MPa, and the yield strength Rp 0.2 is 1483-1536MPa, while the tensile strength and yield strength Rp of Comparative Examples 1-3 are higher than those of Examples 1-3. 0.2 and elongation were significantly reduced.

[0105] Compared with the prior art Ti-Zr-Cu alloy, the Ti 15 The tensile strength of Zr5Cu alloy is increased by 50-200MPa. Among them, different stretching conditions have little effect on the stretching results. The reason is that for those skilled in the art, when the diameter of the tensile specimen is small, the strain rate will be set smaller, and vice versa, the strain rate will be set larger.

[0106] In addition, in the laser selective melting additive manufacturing process of the present invention, the energy density is 37 to 55.6 J·mm -3 , much lower than the existing technology 50 ~ 120J mm -3 , the manufacturing process reduces energy consumption and reduces production costs.

[0107] It can be seen that the 3D printing Ti of the present invention 15 Zr5Cu alloy powder, after laser 3D printing, has high density and no cracks in the sample. 15 The Zr5Cu alloy specimens can obtain high-strength mechanical properties without any heat treatment, meeting the requirements for the use of oral medical implant materials.

[0108] Preferably, the implant alloy material of the present invention can be used to prepare central incisor screws, meeting the requirements of mechanical properties such as high strength.

[0109] It should be noted that:

[0110] (1) The present invention is used to blow away the splashes generated during the printing process during the laser selective melting additive manufacturing process. It should be noted that the wind speed should not be too small (failure to blow away the splashes) or too large (titanium zirconium copper alloy powder is relatively light, and excessive wind speed will blow the powder away). This wind speed control is a routine operation.

[0111] (2) The number of times of raw material melting and remelting, the number of high-temperature forging, the heat preservation and drying time, and the 3D printing substrate material in the present invention can be adjusted according to actual conditions.

[0112] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application, for example, the implant alloy material of the present invention can be used not only as a medical implant for human oral cavity, but also for other medical implants for human body, as well as medical implants for animals such as rabbits, dogs and pigs, etc., according to actual conditions, shall be included in the protection scope of the present application.

Claims

1. An ultra-high strength Ti 15 Zr5Cu alloy, characterized in that Calculated by weight percentage, the chemical composition of the titanium alloy is: Zr: 13-14.9%; Cu: 4-5%; and the balance is Ti.

2. An ultra-high strength Ti 15 The preparation method of Zr5Cu alloy is characterized in that: The steps include: Raw material smelting: The alloy material containing titanium, zirconium and copper elements is smelted according to the ultra-high strength Ti 15 The weight percentage of each element in the Zr5Cu alloy is fully melted to obtain a titanium zirconium copper ingot; High temperature forging: The smelted titanium-zirconium-copper ingot is fully forged at a certain temperature to obtain a titanium-zirconium-copper alloy rod; Atomization powder making: atomizing and powdering the forged titanium-zirconium-copper alloy rod to obtain titanium-zirconium-copper alloy powder; Powder screening and airflow classification: The titanium-zirconium-copper alloy powder after atomization is screened and then subjected to airflow classification to obtain a titanium-zirconium-copper alloy powder with a particle size range of 11 to 72 μm; Heat preservation and drying: the titanium-zirconium-copper alloy powder after airflow classification is fully heat-insulated and dried to obtain titanium-zirconium-copper alloy powder for 3D printing; The titanium-zirconium-copper alloy powder for 3D printing after heat preservation and drying is manufactured by laser selective melting to obtain the ultra-high strength Ti 15 Zr5Cu alloy.

3. The ultra-high strength Ti according to claim 2 15 The preparation method of Zr5Cu alloy is characterized in that: In the raw material smelting step, the smelting temperature is controlled at 1000-1100°C.

4. The ultra-high strength Ti according to claim 2 15 Zr5Cu alloy and its preparation method and application, characterized in that: In the high temperature forging step, the forging temperature is controlled at 900-1000°C.

5. The ultra-high strength Ti according to claim 2 15 The preparation method of Zr5Cu alloy is characterized in that: In the atomization powder making step, the titanium-zirconium-copper alloy rod is atomized into droplets by an inert gas flow, and the droplets are solidified to form alloy powder to obtain the titanium-zirconium-copper alloy powder; wherein the inert gas pressure is controlled at 35 to 45 bar, and the vacuum degree is ≤5 Pa.

6. The ultra-high strength Ti according to claim 2 15 The preparation method of Zr5Cu alloy is characterized in that: In the powder screening and airflow classification step, the titanium-zirconium-copper alloy powder after atomization is subjected to ultrasonic vibration screening and classification treatment under an inert gas protective atmosphere to complete the powder screening; wherein the pressure of the inert gas is 38 to 40 bar.

7. The ultra-high strength Ti according to claim 2 15 The preparation method of Zr5Cu alloy is characterized in that: In the powder screening and airflow classification steps, the titanium-zirconium-copper alloy powder after powder screening is effectively separated by an airflow screening machine to obtain a titanium-zirconium-copper alloy powder with a particle size range of 11 to 72 μm; wherein the frequency of the classification wheel of the airflow separator is 30 to 35 Hz.

8. The ultra-high strength Ti according to claim 2 15 The preparation method of Zr5Cu alloy is characterized in that: In the heat preservation and drying step, the drying temperature is controlled at 100-110°C.

9. The ultra-high strength Ti according to claim 2 15 The preparation method of Zr5Cu alloy is characterized in that: The parameter conditions of the laser selective melting additive manufacturing include: Preheat the substrate before 3D printing at a temperature of 50-150°C; High-purity argon is passed through the printing chamber to replace oxygen. The argon pressure is 0.4-0.8MPa, and the oxygen concentration is controlled below 400ppm. Laser power 120-180W, scanning speed 1100-1200mm / s, scanning spacing 0.09-0.12mm; interlayer thickness 0.03mm; scanning strategy with a rotation angle of 67° between adjacent layers; powder spreading rate set at 100-200%; energy density 37-55.6J·mm -3 .

10. The ultra-high strength Ti according to claim 1 15 Application of Zr5Cu alloy or the ultra-high strength Ti15Zr5Cu alloy prepared by the method according to any one of claims 2-9 in oral medical implant materials.

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