Preparation process and application of Zu-Cu alloy based on regulation and control of deformation

Abstract

The invention relates to a Zu-Cu alloy preparation process and application based on deformation regulation and control, and relates to the field of biomedical materials, in particular to the field of zinc alloys.The Zu-Cu alloy preparation process comprises the steps that a Zn-Cu ingot blank and calcium carbonate are smelted at the temperature of 450-500 DEG C to obtain a melt, casting is conducted through a semi-continuous casting process, and a Zn-Cu alloy ingot is obtained; and after the Zn-Cu alloy ingot is subjected to homogenization treatment, the Zn-Cu alloy ingot is subjected to rotary swaging, the total deformation of rotary swaging ranges from 64% to 98%, and the Zn-Cu alloy is obtained. According to the method, the yield strength, tensile strength and elongation at break of the alloy are remarkably improved through 64%-98% of the total deformation of rotary swaging and the grain refinement effect caused by large deformation, meanwhile, the corrosion uniformity of the zinc-copper alloy is improved, and precise adaptation of the mechanical property and the degradation rate of the zinc alloy is achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of biomedical materials, particularly relates to the field of zinc alloy, and specifically relates to a preparation process and application of Zu-Cu alloy based on deformation control. BACKGROUND

[0002] In the field of degradable orthopedic implant materials, Zn-Cu series alloys are concerned due to their good biocompatibility and degradation characteristics, but their poor room temperature plasticity processing ability seriously restricts their practical application. The conventional room temperature pressure processing method is difficult to effectively prepare the alloy, mainly because of its easy brittle fracture, which cannot obtain ideal forming effect and mechanical property matching through traditional processes such as rolling and extrusion. Although the rotary forging process provides a feasible path to solve the problem of low zinc alloy plasticity at room temperature, the existing process parameters and deformation mechanism still have significant limitations in regulating the mechanical properties and degradation performance of the alloy, which is difficult to meet the stringent requirements of implant materials.

[0003] From the perspective of mechanical properties, the existing rotary forging process easily leads to insufficient deformation uniformity of zinc alloy. The mismatch between pass deformation and axial feed speed can cause metal flow disorder, resulting in local brittle fracture of the workpiece. The strong texture formed by rotary forging can inhibit grain boundary sliding, although it can improve strength by refining grains, but it often sacrifices plasticity, making it difficult to achieve the coordinated optimization of strength and plasticity, especially for Zn-Cu series alloys, the second phase (such as CuZn5) is easy to form coarse or continuous network structure during deformation, which further aggravates brittleness.

[0004] In terms of degradation performance, the existing rotary forging process has blindness in regulating the corrosion behavior of zinc alloy. The grain refinement and dislocation density increase caused by deformation can accelerate the initial corrosion, and the difference in microstructure between the core and the surface can easily cause local corrosion unevenness, leading to fluctuation of degradation rate. At the same time, the process parameters are insufficient to regulate the distribution of the second phase, if CuZn5 and other phases are unevenly dispersed, it will form a corrosion galvanic effect, causing intergranular corrosion or local accelerated degradation, which is difficult to match the dynamic needs of bone healing period.

[0005] In summary, the existing rotary forging process has obvious shortcomings in the matching of mechanical properties and degradation performance of zinc alloy, and it is urgent to develop a more suitable process system to meet the application requirements of degradable orthopedic implant materials. SUMMARY

[0006] The purpose of the present application is to provide a preparation process and application of Zu-Cu alloy based on deformation control, which is expected to solve the problem of mismatch between mechanical properties and degradation performance of zinc alloy in rotary forging process by controlling deformation.

[0007] The present application achieves the above-mentioned purpose through the following technical solutions:

[0008] A process for preparing Zu-Cu alloys based on controlled deformation includes the following steps:

[0009] (1) Zn-Cu ingot and calcium carbonate are melted at 450-500℃ to obtain a melt, and then cast using a semi-continuous casting process to obtain Zn-Cu alloy ingot.

[0010] (2) After homogenizing the Zn-Cu alloy ingot, the Zn-Cu alloy ingot is then subjected to rotary forging. The total deformation of the rotary forging is 64%-98%, and a Zn-Cu alloy is obtained.

[0011] As a further optimization of the above invention, in step (1), the Zn-Cu ingot is one of Zn-2Cu alloy, Zn-3Cu alloy, and Zn-4Cu alloy.

[0012] As a further optimization of the above invention, in step (1), the amount of calcium carbonate used is 2%-4% of the mass of the Zn-Cu ingot.

[0013] As a further optimization of the above invention, in step (2), the Zn-Cu alloy ingot is homogenized in a resistance furnace, and the homogenization process is 200-300℃ / 24h.

[0014] As a further optimization of the above invention, in step (2), after homogenization, the oxidation and dirt on the surface of the Zn-Cu alloy ingot are removed by sandpaper or grinding wheel, and then acidified, and hot-dip galvanized on the surface of the Zn-Cu alloy ingot.

[0015] As a further optimization of the above invention, the hot-dip galvanizing specifically involves immersing a Zn-Cu alloy ingot in a zinc plating solution at 220-330°C for 10-15 minutes.

[0016] As a further optimization of the above invention, the zinc plating solution is composed of ZnO, NaOH and water, with a pH of 8-10.

[0017] As a further optimization of the above invention, the process parameters of the rotary forging are: temperature 100-300℃, conical feed angle 10°-21.67°, friction coefficient 0.1-0.3, axial feed speed 3-20mm / s, deformation per pass 20%-40%, and 2-3 passes.

[0018] This invention also provides the application of the Zn-Cu alloy prepared by the above-described process in the preparation of bioactive implantable devices, including its application in the preparation of orthopedic implantable devices and bioactive membranes / patches.

[0019] The orthopedic implant body comprises at least one of a bone plate, a bone screw, a bone tissue repair bracket, an intramedullary needle, a bone setting sleeve or a spinal internal fixation instrument; and the bioactive membrane / patch comprises at least one of a guided bone regeneration membrane, a guided tissue regeneration membrane, a hernia patch, a fistula patch or an oral / dental barrier membrane.

[0020] The present application has the following beneficial effects:

[0021] (1) By 64%-98% of the total deformation amount of rotary forging, the grain refinement effect caused by large deformation (dynamic recrystallization and dislocation strengthening synergistic effect) is utilized to significantly improve the yield strength, tensile strength and elongation of the alloy, and the mechanical properties and degradation rate of the zinc alloy are precisely matched, meeting the dual requirements of mechanical bearing capacity and degradation period in different scenarios.

[0022] (2) The calcium carbonate added during the smelting process effectively improves the corrosion uniformity of the alloy, avoids local excessive corrosion or corrosion stagnation, and maintains a stable corrosion rate of the alloy during service or degradation, thereby improving the consistency and reliability of the material performance.

[0023] (3) The plating layer formed by hot-dip galvanizing endows the alloy surface with higher chemical stability, wear resistance and hardness, while strengthening the interface compatibility between the plating layer and the substrate, reducing the risk of interface peeling, prolonging the service life of the material and widening its application range in complex environments. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 Tensile engineering stress-strain curves of zinc-copper alloys (Zn-2Cu, Zn-3Cu, Zn-4Cu) with different deformation amounts at room temperature;

[0025] Figure 2 Fracture morphology of Zn-2Cu after room temperature tensile with different deformation amounts (a): 36%; (b): 64%; (c): 84%;

[0026] Figure 3 Fracture morphology of Zn-3Cu after room temperature tensile with different deformation amounts (a) 36%; (b) 64%; (c) 84%.

[0027] Figure 4 Potentiodynamic polarization curves of zinc-copper alloys with different deformation amounts in a simulated body fluid;

[0028] Figure 5 Microstructure of Zn-2Cu samples after 3-day immersion: (a) 36%; (b) 64%; (c) 84%.

[0029] Figure 6Microstructure of Zn-Cu alloy samples with different additive components after immersion for 3 days: (a) Zn-2Cu (CaCO3); (b) Zn-2Cu (CaO); (c) Zn-2Cu-0.2Ca > Zn-2Cu; (d) Zn-2Cu. DETAILED DESCRIPTION

[0030] It is necessary to point out here that the following detailed description is only used to further illustrate the application and cannot be understood as limiting the scope of the application. Those skilled in the art can make some non-essential improvements and adjustments to the application according to the above application content.

[0031] I. Description

[0032] (1) The Zn-Cu ingot includes Zn-2Cu alloy, Zn-3Cu alloy, Zn-4Cu alloy, and Zn-0.2Cu alloy.

[0033] The raw materials of the Zn-Cu ingot are industrial pure zinc and industrial pure copper, and the smelting is performed in a graphite crucible. During the stirring process, 5# covering agent is continuously sprayed to reduce the oxidation loss of the melt. Then, hydrogen is introduced for impurity removal refining. SF6+CO2 mixed gas is used for protection during the standing process. After the standing process is completed, semi-continuous casting process is used for casting, and a copper crystallizer is selected for the crystallizer. Finally, a Zn-Cu ingot (round ingot) with a diameter of 90 mm and a length of about 1500 mm is obtained.

[0034] (2) The application discloses a preparation process of a Zn-Cu alloy based on regulation of deformation amount, which comprises the following steps:

[0035] (1) Zn-Cu ingot and calcium carbonate are smelted at a temperature of 450-500 DEG C to obtain a melt, and semi-continuous casting process is used for casting to obtain a Zn-Cu alloy ingot;

[0036] (2) After the Zn-Cu alloy ingot is subjected to homogenization treatment, the Zn-Cu alloy ingot is subjected to rotary swaging, and the total deformation amount of rotary swaging is 64%-98% to obtain a Zn-Cu alloy.

[0037] In step (1), the Zn-Cu ingot is one of Zn-2Cu alloy, Zn-3Cu alloy, Zn-4Cu alloy and Zn-0.2Cu alloy.

[0038] In step (1), the amount of calcium carbonate is 2%-4% of the mass of the Zn-Cu ingot.

[0039] In step (2), the Zn-Cu alloy ingot is subjected to homogenization treatment in a resistance furnace, and the homogenization treatment process is 200-300 DEG C / 24h.

[0040] In step (2), after homogenization, the surface of the Zn-Cu alloy ingot is removed by sanding with sandpaper or a grinding wheel to remove oxidation and dirt, followed by acidification, and then hot-dip galvanizing. Specifically, the Zn-Cu alloy ingot is immersed in a zinc plating solution at 220-330℃ for 10-15 minutes. The zinc plating solution consists of ZnO, NaOH, and water, with a pH of 8-10.

[0041] In step (3), the process parameters for rotary forging are: temperature 100-300℃, cone feed angle 10°-21.67°, friction coefficient 0.1-0.3, axial feed speed 3-20mm / s, deformation per pass 20%-40%, and 2-3 passes.

[0042] (3) Performance Testing

[0043] The tensile test was performed according to the standard ASTM E8-2015a on an electronic universal testing machine, model 1NSTRON 5982.

[0044] The tensile fracture morphology of zinc-copper alloy bars was analyzed using a JSM-6700 scanning electron microscope.

[0045] The testing instrument was a ZENNIUM™ 6 electrochemical workstation. The simulated body fluid used in the electrochemical experiment was SBF solution with the pH adjusted to 7.4 to simulate the normal human body fluid environment.

[0046] The corrosion immersion test was conducted in strict accordance with the standard ASTM-G31-2004, and the static corrosion rate was measured using static weight loss test in accordance with the standard ASTM G31-72.

[0047] Unless otherwise specified, all methods used in this invention are conventional methods known to those skilled in the art, and all reagents and materials used are commercially available products, and all instruments used are conventional instruments known to those skilled in the art.

[0048] II. Methods

[0049] 2.1 Effect of Deformation Amount on Zn-Cu Alloy in Rotary Forging Process

[0050] Zn-Cu ingot (Zn-2Cu alloy, Zn-3Cu alloy, Zn-4Cu alloy) and 2% calcium carbonate were melted at a temperature of 500°C to obtain a melt, and a semi-continuous casting process was used for casting to obtain a Zn-Cu alloy ingot. The Zn-Cu alloy ingot was cut into about 500mm in length by a sawing machine, and the Zn-Cu alloy ingot was subjected to homogenization treatment in an electric resistance furnace to eliminate composition segregation and casting stress in the as-cast alloy. The homogenization treatment process was 300°C / 24h. The homogenized Zn-Cu alloy ingot was cut into an alloy ingot with a diameter of 20mm and a length of 10mm by machining. Three dies were used to rotate around the Zn-Cu alloy ingot at high speed while applying radial high-frequency short-stroke forging to the Zn-Cu alloy ingot. The rotary forging temperature was 300°C, the conical feeding angle was 10.5°, the friction coefficient was 0.1, the axial feeding speed was 3mm / s, the pass deformation was 20%-40%, and the pass was 3 times.

[0051] 2.1.1 The total deformation and the corresponding mechanical property statistics are shown in Table 1, and the stress-strain curve is shown in Figure 1

[0052] Table 1 Tensile mechanical properties of zinc-copper alloy rods with different deformations at room temperature

[0053]

[0054] It can be seen that the yield strength, tensile strength and fracture elongation of the zinc-copper alloy with a deformation of 0 are all low. With the increase of the deformation to 84%, the yield strength, tensile strength and fracture elongation are significantly improved. When the deformation increases to 98%, the yield strength and tensile strength decrease, while the fracture elongation increases. In summary, with the increase of the deformation, the yield strength and tensile strength of the zinc-copper alloy first increase and then decrease, while the fracture elongation always increases. When the deformation is in the range of 64%-98%, the yield strength, tensile strength and fracture elongation are significantly improved, and the optimal strength is achieved when the total deformation is 84%. Moreover, through zinc-copper alloys with different Cu contents, when the Zn-2Cu alloy is used as the original ingot, the yield strength, tensile strength and fracture elongation are all in an optimal range when the total deformation is 84%.

[0055] 2.1.2 In order to study the effect of different deformations and copper contents on the tensile fracture mode of zinc-copper alloy, the tensile fracture obtained after room temperature tensile test was observed under a scanning electron microscope using a secondary electron mode. The fracture morphology of Zn-2Cu alloy rods with deformations of 36%, 64% and 84% is shown in Figure 2 ; the fracture morphology of Zn-4Cu rods with deformations of 36%, 64% and 84% is shown in Figure 3 . From Figures 2-3 ​It can be seen that with the increase of deformation, the fracture morphology is more and more fine. With the increase of deformation, due to grain refinement, brittle fracture of cleavage fracture is transformed into ductile fracture. When the deformation is more than 64%, the rod obviously appears the characteristics of ductile fracture such as dimple, indicating that the alloy begins to have good plastic deformation ability.

[0056] 2.1.3 To evaluate the corrosion resistance of Zn-2Cu alloy with different deformation, the rod with 36%, 64%, 84% deformation prepared by rotary forging of Zn-2Cu alloy was subjected to electrochemical experiment in simulated body fluid (SBF solution, pH = 7.4) to study the corrosion law.

[0057] Figure 4 The potentiodynamic polarization curves of pure zinc and zinc-copper alloy with different deformation prepared by rotary forging in simulated body fluid are shown in the figure. As can be seen from the figure, the potential of Zn-2Cu alloy with different deformation changes obviously. When the deformation is 36%, the potential of Zn-2Cu alloy is slightly shifted to the positive direction compared with pure zinc. When the deformation is 64%, the potential of Zn-2Cu alloy is basically the same as pure zinc. When the deformation is 84%, the potential of Zn-2Cu alloy is shifted to the negative direction compared with pure zinc.

[0058] Table 2 is the fitting results of polarization curves of zinc-copper alloy with different deformation in simulated body fluid. As can be seen from table 2, the corrosion rates of Zn-2Cu alloy with deformation of 84% and 64% are 24.63 μm / year, 52.27 μm / year and 54.95 μm / year respectively. The worst corrosion resistance is Zn-2Cu alloy with deformation of 36%.

[0059] Table 2 corrosion data of zinc-copper alloy with different deformation in simulated body fluid

[0060]

[0061] The conclusions are as follows: the corrosion rate of Zn-2Cu alloy is faster than that of pure Zn. The corrosion potential of the three metals in simulated body fluid is between-1.184 and-1.153, with little difference; with the increase of deformation, the corrosion current density of zinc-copper alloy decreases, the corrosion rate decreases, and when the deformation reaches 64%, the corrosion rate of Zn-2Cu alloy decreases obviously.

[0062] 2.1.4 The surface morphology of Zn-2Cu alloy sample after immersion for 3 days was analyzed by scanning, and the corrosion morphology is shown in Figure 5 .

[0063] It can be seen that after 3 days of immersion in SBF, the surface of the Zn-2Cu alloy sample with different deformation amounts has been corroded to varying degrees, and the uniformity of corrosion is improved as the deformation amount increases. When the deformation amount reaches 64%, the uniformity of corrosion is significantly improved. At the same time, the corrosion resistance of the sample is reduced after adding Cu element.

[0064] 2.2 Influence of other factors on Zn-Cu alloy

[0065] 2.2.1 Influence of Zn-Cu alloy ingot preparation on Zn-Cu alloy

[0066] The Zn-2Cu ingot blank and 2% calcium oxide were melted at a temperature of 500°C to obtain a melt, and a semi-continuous casting process was used for casting to obtain a Zn-2Cu(CaO) alloy ingot. The Zn-2Cu(CaO) alloy ingot, Zn-2Cu ingot blank, and Zn-2Cu-0.2Ca alloy ingot were cut into lengths of about 500 mm on a sawing bed, and the three metals were subjected to homogenization treatment in an electric resistance furnace at a process of 300°C / 24h. The three metals after homogenization treatment were machined to obtain alloy ingots with a diameter of 20 mm and a length of 10 mm. Three dies were used to rotate at high speed while applying radial high-frequency short-stroke forging to the three metals, with a rotary forging temperature of 300°C, a conical feeding angle of 10.5°, a friction coefficient of 0.1, an axial feeding speed of 3mm / s, a pass deformation of 20%-40%, 3 passes, and a total deformation of 84%. The detected compositions of the four metals are shown in Table 3, and the corresponding mechanical property statistics are shown in Table 4.

[0067] Table 3 Detected composition of metals

[0068]

[0069] Table 4 Tensile mechanical properties of zinc-copper alloy rods with different added components at room temperature

[0070]

[0071] As can be seen from Tables 3-4, with the addition of Ca element, the tensile properties of zinc-copper alloy decrease significantly, and the yield strength, tensile strength and elongation of zinc-copper alloy decrease with the increase of Ca content.

[0072] The above four zinc-copper alloy rods were subjected to electrochemical experiments in a simulated body fluid (SBF solution) to study the corrosion law. Table 5 shows the fitting results of the polarization curves of the above zinc-copper alloys in the simulated body fluid, and it can be seen that Cu and Ca both accelerate the corrosion degradation of zinc alloy.

[0073] Table 5 Corrosion data of zinc-copper alloy rods with different added components in simulated body fluid

[0074]

[0075]

[0076] The surface morphology of four zinc-copper alloy samples after immersion for 3 days was scanned and analyzed. The corrosion morphology images are shown below. Figure 6 As shown, the corrosion uniformity is: Zn-2Cu(CaCO3) > Zn-2Cu-0.2Ca > Zn-2Cu > Zn-2Cu(CaO). Different degrees of corrosion occurred on the surfaces of the alloy samples in each state, with more pronounced corrosion at grain boundaries and phase boundaries. The corrosion uniformity of the Zn-2Cu alloy with added CaCO3 was better than that with added CaO. This is presumably because CaCO3 has high stability and is less prone to decomposition or agglomeration during alloy preparation (such as smelting and casting), making it more likely to be distributed as fine, uniform particles in the matrix. Its interfacial bonding with the matrix is ​​more stable, resulting in a weaker "local triggering" effect on corrosion. In contrast, CaO, due to its high reactivity, may agglomerate or segregate during alloy preparation or service due to localized high temperatures or moisture, or form unstable interfacial phases (such as calcium oxides / salts) with zinc and copper in the matrix. This makes the interface a weak point where corrosion preferentially occurs, further compromising corrosion uniformity.

[0077] 2.2.2 Effect of Pretreatment on Zn-Cu Alloy

[0078] Zn-2Cu alloy ingots and 2% calcium carbonate were melted at 500℃ to obtain a melt, which was then cast using a semi-continuous casting process to obtain Zn-Cu alloy ingots. The Zn-2Cu alloy ingots were cut into approximately 500mm lengths using a saw, and then homogenized in an electric resistance furnace at 300℃ for 24 hours. After homogenization, the Zn-2Cu alloy ingots were polished with sandpaper or a grinding wheel to remove oxidation and dirt from the surface, followed by acidification (10wt% HCl). The surface of the Zn-Cu alloy ingots was then hot-dip galvanized (the galvanizing solution consisted of ZnO, NaOH, and water, with a mass ratio of ZnO:NaOH = 1:1, pH = 10, 270℃, and a time of 10 minutes). After cleaning, the ingots were machined to produce alloy ingots with a diameter of 20mm and a length of 10mm. Three dies are used to simultaneously apply radial high-frequency short-stroke forging to the coated alloy ingot at high speed. The forging temperature is 300℃, the conical feed angle is 10.5°, the friction coefficient is 0.1, the axial feed speed is 3mm / s, the deformation per pass is 20%-40%, 3 passes are used, and the total deformation is 0%-84%. The coating detection and analysis are as follows:

[0079] Table 6. Analysis of Coating Detection on Zinc-Copper Alloy Rods

[0080]

[0081] Table 7 Tensile mechanical properties of plated zinc-copper alloy rods at room temperature

[0082]

[0083]

[0084] As can be seen from Table 7, the yield strength, tensile strength and elongation at break of the plated zinc-copper alloy are all improved, and the variation law is basically the same as that of the zinc alloy in 2.1.1. With the increase of the deformation amount, the yield strength and tensile strength of the zinc-copper alloy first increase and then decrease, while the elongation at break always increases, and when the deformation amount is in the range of 64%-98%, the yield strength, tensile strength and elongation at break are all significantly improved. Further, the plating layer can cover the small defects (such as casting lines, scratches) on the surface of the Zn-2Cu matrix, so that the grain size is more uniformized during the spinning process. At the same time, due to its chemical stability, it is not easy to turn black, and can make the zinc-copper alloy maintain a flat and uniform appearance for a long time.

[0085] The plated zinc-copper alloy rod was subjected to electrochemical experiment in simulated body fluid (SBF solution, pH = 7.4), and the fitting results of the polarization curve in the simulated body fluid are shown in Table 8. It can be seen that the plated layer slows down the corrosion degradation of the zinc alloy, but it can effectively prevent the phenomena of alloy pitting and crevice corrosion, and when the deformation amount reaches 64%, the corrosion rate of the alloy is significantly reduced, and when it reaches 84%, the corrosion rate reaches the minimum.

[0086] Table 8 Corrosion data of plated zinc-copper alloy rods in simulated body fluid

[0087]

[0088] Further, the plated zinc-copper alloy rod after corrosion treatment, the zinc-copper alloy rod after corrosion treatment in 2.1.3 and pure Zn-2Cu (deformation amounts are 36%, 64% and 84% respectively) were subjected to polishing treatment, and microhardness test was carried out under the type and specification Nanbei HVS-30T Vickers hardness tester, the test force was set to 10 kgf, the measurement was started, the pressure was maintained for 15 s, the Vickers hardness values of 6 points of each sample were measured, and the average value was taken. The hardness is shown in Table 9, which shows that the zinc oxide component in the plating layer has high microhardness and dense structure, and can significantly improve the wear resistance of the alloy surface.

[0089] Table 9 Hardness of different zinc-copper alloy rods

[0090]

[0091] In summary, the preparation process of the Zn-Cu alloy prepared by the application has good application prospects in the preparation of bioactive implant devices. In combination with the above mechanical properties, electrochemical properties and corrosion properties, the above Zn-Cu alloy has good application prospects in the preparation of bioactive implant devices and bioactive membranes / patches. In particular, the Zn-2Cu(CaCO3+plating layer)-84% zinc alloy, the orthopedic implant device body includes but is not limited to a bone plate, a bone screw, a bone tissue repair stent, an intramedullary needle, a bone setting sleeve or a spinal internal fixation device; the bioactive membrane / patch includes but is not limited to a guided bone regeneration membrane, a guided tissue regeneration membrane, a hernia patch, a fistula patch or an oral / dental barrier membrane.

[0092] The above-described embodiments only express several embodiments of the application, which are described in detail and specifically, but should not be understood as a limitation on the scope of the patent of the application. It should be noted that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the application, which are within the protection scope of the application.

Claims

1. A process for preparing Zu-Cu alloys based on controlled deformation, characterized in that, Includes the following steps: (1) Zn-Cu ingot and calcium carbonate are melted at 450-500℃ to obtain a melt, and then cast using a semi-continuous casting process to obtain Zn-Cu alloy ingot. (2) After homogenizing the Zn-Cu alloy ingot, the Zn-Cu alloy ingot is then forged by rotary forging. The total deformation of the rotary forging is 64%-98%, and a Zn-Cu alloy is obtained.

2. The process for preparing Zu-Cu alloys based on controlled deformation according to claim 1, characterized in that, In step (1), the Zn-Cu ingot is one of Zn-2Cu alloy, Zn-3Cu alloy, and Zn-4Cu alloy.

3. The process for preparing a Zu-Cu alloy based on controlled deformation according to claim 1, characterized in that, In step (1), the amount of calcium carbonate used is 2%-4% of the mass of the Zn-Cu ingot.

4. The process for preparing a Zu-Cu alloy based on controlled deformation as described in claim 1, characterized in that, In step (2), the Zn-Cu alloy ingot is homogenized in a resistance furnace for 200-300℃ / 24h.

5. The process for preparing a Zu-Cu alloy based on controlled deformation according to claim 1, characterized in that, In step (2), after homogenization, the oxidation and dirt on the surface of the Zn-Cu alloy ingot are removed by sanding with sandpaper or grinding wheel, followed by acidification, and then hot-dip galvanizing is performed on the surface of the Zn-Cu alloy ingot.

6. The process for preparing a Zu-Cu alloy based on controlled deformation according to claim 5, characterized in that, The hot-dip galvanizing process specifically involves immersing a Zn-Cu alloy ingot in a zinc plating solution at 220-330°C for 10-15 minutes.

7. The process for preparing a Zu-Cu alloy based on controlled deformation according to claim 6, characterized in that, The zinc plating solution is composed of ZnO, NaOH and water, with a pH of 8-10.

8. The process for preparing a Zu-Cu alloy based on controlled deformation according to claim 1, characterized in that, In step (3), the process parameters for rotary forging are: temperature 100-300℃, conical feed angle 10°-21.67°, friction coefficient 0.1-0.3, axial feed speed 3-20mm / s, deformation per pass 20-40%, and 2-3 passes.

9. The application of the alloy prepared by the Zu-Cu alloy preparation process based on the controlled deformation method according to any one of claims 1-8 in the preparation of bioactive implantable devices, including its application in the preparation of orthopedic implantable devices and bioactive membranes / patches.

10. The application according to claim 9, characterized in that, The orthopedic implant body includes at least one of bone plates, bone screws, bone tissue repair scaffolds, intramedullary nails, bone sheaths, or spinal fixation devices; the bioactive membrane / patch includes at least one of guiding bone regeneration membranes, guiding tissue regeneration membranes, hernia patches, fistula patches, or oral / dental barrier membranes.

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