CN114959364A

CN114959364A - Degradable Zn-xRE alloy and preparation method thereof

Info

Publication number: CN114959364A
Application number: CN202210775115.2A
Authority: CN
Inventors: 林继兴; 童先; 孙学成; 麻健丰; 黄盛斌; 朱莉
Original assignee: SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU MEDICAL UNIVERSITY
Current assignee: SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU MEDICAL UNIVERSITY
Priority date: 2022-07-01
Filing date: 2022-07-01
Publication date: 2022-08-30

Abstract

The invention belongs to the technical field of biodegradable medical zinc alloy, and particularly relates to a degradable Zn-xRE alloy, which comprises a main material element Zn and an alloy element RE, and is characterized in that: the alloy element RE also comprises dysprosium (Dy), holmium (Ho), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), neodymium (Nd), terbium (Tb) and erbium (Er), wherein x is 3.05-10.05 wt% and the balance is Zn in percentage by mass.

Description

Degradable Zn-xRE alloy and preparation method thereof

Technical Field

The invention belongs to the technical field of biodegradable medical zinc alloy, and particularly relates to a degradable Zn-xRE alloy and a preparation method thereof.

Background

In the degradable metal material, iron and its alloy can be degraded in physiological environment, but its degradation rate is too low and its degradation product is difficult to be completely degraded, so that it is the direct reason for limiting its application in orthopedics field, although magnesium and magnesium alloy has mechanical property and elastic modulus which are more close to human bone to avoid the generation of stress shielding effect and good osteogenesis promoting function, most of magnesium alloy has faster degradation rate, in the course of degradation, hydrogen bubble is produced and implantation position is alkalized to result in the early failure of implant, so that it can seriously affect the normal growth and development of bone tissue, zinc and zinc alloy have standard electrode potential of zinc between magnesium and iron, its degradation rate and chemical activity between magnesium and iron and its corrosion product can be completely degraded to obtain the degradable metal material which can be extensively studied in recent years, zinc as the necessary trace element for human body is mainly distributed in human bone, In skeletal muscle, skin, liver and brain, zinc is almost involved in the metabolism of all cells of human body and the synthesis of various enzymes, and is used as an accessory factor of specific enzymes of bone and cartilage to promote the skeletal development and tissue regeneration of human body, improve insulin efficacy and enhance the regeneration and healing capability of wound tissues, and is used as a nerve regulator to promote thinking agility, etc. However, zinc deficiency results in slow growth, delayed sexual maturation, altered taste and smell, and in addition, zinc deficiency in the mother leads to abnormal nucleic acid metabolism, thereby slowing down the synthesis speed and the cell division capability of DNA and protein, causing slow fetal growth and even development deformity, and the cast pure zinc and the zinc alloy have better biocompatibility and moderate degradation rate, but the mechanical property of most as-cast zinc alloy is difficult to meet the requirement of bone implant and the degradation rate of most zinc alloy is far less than the degradation rate requirement of 0.5mm/a of the bone implant, not matched with the bone healing period which needs stable support for 12-24 weeks, at present, the combination of alloying treatment by adding alloying elements and deformation process can obviously improve the mechanical property of the degradable zinc alloy biomaterial, and many alloying elements and deformation processes also contribute to the improvement of the corrosion resistance rate and biocompatibility of the alloy.

Since rare earth elements generally have high magnetic moments and short electron relaxation times, many rare earth ions are considered to be promising candidates for ultra-high field MRI contrast agents, including Dy ³⁺ And Gd ³⁺ Meanwhile, most of rare earth elements can replace calcium to form a more stable compound due to high charge in the blood coagulation process, the normal blood coagulation process is damaged to achieve the anticoagulation effect, the rare earth elements also have stronger affinity with cell phospholipid and have the activation or inhibition effect on various enzymes, and the obvious antibacterial and anti-inflammatory effects are achieved, at present, the research of rare earth zinc alloy is mainly developed around Zn-Al series alloy, the rare earth elements form rare earth-containing compounds with high thermal stability in ZA27 alloy, the rare earth elements are distributed in a network shape in crystal boundaries or dendrite spaces, tissues and secondary dendrite arms are refined, the deformation of a matrix and the movement of the crystal boundaries are effectively hindered, so the high-temperature performance of the alloy is obviously improved, meanwhile, the rare earth elements can refine the grain size of the ZA27 alloy and reduce the spacing of the secondary dendrite arms, and the segregation of lead, cadmium, tin and other impurity elements is reduced, at present, the research on the alloying treatment of the Al-free biological zinc alloy by the rare earth elements is less, most of the research mainly surrounds the rare earth microalloying treatment of the medical multi-element zinc alloy, mainly because the rare earth elements have higher melting point and lower solid solubility in Zn, the preparation difficulty of the medical Zn-RE binary alloy with high content of the rare earth elements is very high, patent CN111334688A discloses a Zn-RE series zinc alloy and a preparation method and application thereof, the mass percent of RE is 0-3%, the preferred range is 0-1.5%, the more preferred range is 0-0.6%, but 0% is not included, however, the addition amount of the RE elements in the patent is still less, and most of the alloys need to be added with the REAdding Zn-RE intermediate alloy for smelting, greatly increasing the preparation procedures, wherein the tensile strength range in the patent is 104-219 MPa, the maximum yield strength is 52-173 MPa, the elongation at break is 21.6-39.5%, the mechanical strength is still obviously lower than the tensile strength more than 300MPa and the yield strength more than 220MPa required by the degradable bone implant material, according to our investigation, only Shuai and the like (reference documents: Shuai C, Yang M, Deng F, et al]Journal of Zhenjiang University-SCIENCE A,2020,21(11):876-891.) and Yang et al (ref: yang Y, Yang M, He C, et al, Rare earth impedance structures and deep resistance of additive manufactured Zn implants [ J]Composites Part B: Engineering,2021,216:108882.) high rare earth content Zn-Nd and Zn-Ce binary alloys were prepared by additive manufacturing processes that would significantly increase the cost and difficulty of preparing Zn-RE alloys due to the need for expensive additive manufacturing equipment.

In conclusion, no research on the conventional smelting and deformation-treated Zn-xRE alloy with high RE addition and the preparation method thereof is reported, so that the application of the Zn-xRE alloy with high RE content as the degradable biomedical material in the next stage is proposed.

Disclosure of Invention

The invention aims to solve the technical problems, and provides a degradable Zn-xRE alloy and a preparation method thereof, so that the effects of high plasticity, degradation rate, wear resistance, cell compatibility and antibacterial property are achieved.

In view of the above, the invention provides a degradable Zn-xRE alloy, where the RE element in the Zn-xRE binary biomedical zinc alloy includes dysprosium (Dy), holmium (Ho), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), neodymium (Nd), terbium (Tb), and erbium (Er). According to the mass percent, x is 3.05-10.05 wt.%, the preferable range is 3.05-8.05%, and the balance is Zn.

The invention also discloses a preparation method of the degradable Zn-xRE alloy, which comprises the following steps: the main raw materials of the Zn-xRE binary alloy for smelting are as follows: zn ingot with the purity of 99.99 percent and pure RE block with the purity of 99.99 percent are weighed according to the mass ratio of two simple substances in the Zn-xRE binary alloy components. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature is 450-800 ℃, and the temperature is kept for 20-40 min, so that the raw materials are fully melted and the elements are uniformly distributed. And when the pouring temperature is reduced to 420-770 ℃, pouring the alloy melt into a steel casting mold preheated to 150-250 ℃ to obtain an alloy cast ingot. And (3) carrying out heat preservation on the cast ingot at 250-350 ℃ for 2-10 h for carrying out homogenization annealing, and cooling by adopting water cooling or air cooling. The steel wire is cut into square strips with the diameter of 70mm multiplied by 10mm by linear cutting, and the square strips are subjected to equal-diameter angular extrusion and hot rolling treatment. And (3) carrying out 2-20 times of continuous equal channel extrusion in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 250-350 ℃, the preheating time is 5-20 min, and the extrusion speed is 1-10 mm/s, so as to obtain the bar blocks with fine second phases. And finally, adopting a hot rolling process with the pass reduction of 2-10%, the inter-pass heating process of 230-330 ℃, the heat preservation time of 2-10 min and the rolling speed of 10-50 mm/s to the strip blocks, and finally obtaining the plate or foil with the total deformation of 50-99%.

In the technical scheme, compared with the prior art, the degradable Zn-xRE alloy has the characteristics of high plasticity, degradation rate, wear resistance, cell compatibility and antibacterial property.

In the above technical solution, further, in the fifth step, a hot rolling mill is used to perform the processing of isometric angle extrusion in cooperation with hot rolling.

In the above technical solution, further, the hot rolling mill further includes: the device comprises a rack, a material conveying channel and a material conveying device, wherein the rack is provided with the material conveying channel; the hot roller group comprises a pair of hot rollers, and the hot rollers are rotatably arranged on the frame; the conveying roller group comprises a pair of conveying rollers, and the conveying roller group is rotatably arranged on the rack; the constant-diameter angle rolling die is arranged on the discharge side of the hot roller group;

the hot roller group is positioned in the conveying channel, and the conveying roller group is positioned on the feeding side of the hot roller group.

In this technical scheme, the square billet of treating processing is carried to the hot roller set along defeated material passageway in the frame, and the conveying roller set can improve the transport stability of square billet, and the square billet carries out the cooperation hot rolling processing of constant diameter angle extrusion at the in-process through hot roller set and constant diameter angle rolling mould.

In the above technical solution, further, the hot roll further includes: the cavity is arranged in the hot roll, and a plurality of slots are formed in the inner wall of the cavity; the power roller is arranged in the cavity, and a plurality of telescopic insertion blocks are arranged on the power roller; the heating mechanism comprises a swinging shaft, a swinging rod and a heating coil; the first transmission mechanism is used for connecting the power roller with the swinging shaft in a transmission way;

the power roll can drive the swinging shaft to rotate in a reciprocating mode through the first transmission mechanism, and the plurality of telescopic insertion blocks and the plurality of insertion grooves are matched with each other to drive the hot roll to rotate.

In this technical scheme, mutually support through scalable inserted block and slot, make things convenient for power roll control hot roll to open and stop, when the hot roll stops, the cooperation is relieved simultaneously with the slot to the inserted block, make the power roll not take the hot roll to rotate when rotating, heating mechanism then continues to swing along with the rotation of power roll under a drive mechanism's effect, keep warm and make the heating effect even to the hot roll, the hot rolling treatment effect of square strip has been improved, make things convenient for the hot roll to start fast, and prevent that the hot roll is local overheated and the phenomenon that the damage appears, the service life of hot roll has been improved.

In the above technical solution, further, the method further includes: the dust hood is arranged on the feeding side of the conveying roller set; the air blowing mechanism is arranged in the rack; the gas supply pipeline comprises a main gas circuit and a branch gas circuit, and a one-way gas valve is arranged on the branch gas circuit;

wherein, the dust excluding hood is connected with the blowing mechanism through an air supply pipeline.

In this technical scheme, the square bar is its surface in transportation process adheres to impurity such as dust easily, dust and impurity can influence the hot rolling treatment effect of square bar, alloy finished product quality has been reduced, and the dust excluding hood is at square bar transportation process, air blowing mechanism carries the air current to the dust excluding hood through the air supply pipe, the dust excluding hood spouts the air current to the square bar surface, thereby get rid of square bar surface adhered to dust impurity, prevent that dust impurity from influencing square bar hot rolling treatment effect, the finished product quality of alloy has been improved.

In the above technical solution, further, the blowing mechanism further includes: the piston cavity is movably provided with a piston, and an air outlet is formed in the piston cavity; the piston rod is arranged at the lower end of the piston; the crankshaft is arranged at the lower end of the piston rod and is used for driving the piston rod to move in a reciprocating manner; the second transmission mechanism is in transmission connection with the first transmission mechanism and is used for driving the crankshaft to rotate;

wherein, the gas outlet is located the top of piston, the air feed pipeline is connected with the gas outlet.

In this technical scheme, along with the rotation of power roller, first drive mechanism transmits the drive power of power roller to second drive mechanism, second drive mechanism drives the bent axle and rotates, the piston rod drives the piston along with the rotation of bent axle and reciprocates to the air in the extrusion piston chamber produces the air current, the air current that produces in the piston chamber passes through the gas outlet and gets into the pipeline of supplying gas and flow to the dust excluding hood, at last through the dust excluding hood blowout, make air blowing mechanism need not extra power supply, energy resource consumption and manufacturing cost have been reduced.

In the above technical solution, further, the conveying roller further includes: the conveying roller conveying device comprises a plurality of limiting strips, wherein the limiting strips are uniformly distributed at intervals along the circumferential direction of the conveying roller, the length direction of each limiting strip is parallel to the axial direction of the conveying roller, the limiting strips are made of rubber, and fluid is filled in the limiting strips.

In this technical scheme, when the square billet skew appears in transportation process, the fluid in the spacing strip is received the extrusion and is flowed to one side in addition, leads to the volume increase of one side in addition to make the frictional force of one side in addition increase, the unbalanced messenger square billet of frictional force in both sides can return gradually just, thereby prevents that the phenomenon of skew from appearing in transportation process in the square billet, has improved the transport stability of square billet.

In the above technical scheme, further, the dust removing cover is provided with dust removing bristles, and the dust removing bristles are located on one side of the dust removing cover close to the conveying roller set.

In the technical scheme, the dust removal bristles can further remove dust impurities attached to the surfaces of the square bars before the square bars are subjected to hot rolling treatment.

The invention has the beneficial effects that:

1. the high-strength plasticity, degradation rate, wear resistance, cell compatibility and antibacterial property of the degradable Zn-xRE alloy are improved;

2. the hot roll and the heating mechanism are controlled by the power roll, so that the hot roll can be conveniently and quickly started, the phenomenon of damage caused by local overheating of the hot roll is prevented, the service life of the hot roll is prolonged, and the hot rolling treatment effect of square bars is improved;

3. the dust cover prevents dust and impurities from influencing the hot rolling treatment effect of the square bars, so that the finished product quality of the alloy is improved;

4. by the arrangement of the conveying assembly, the phenomenon of deviation of the square strips in the conveying process is prevented, and the conveying stability of the square strips is improved;

5. through the cooperation of the air blowing mechanism and the second transmission mechanism, the air blowing mechanism does not need an additional power source, and the energy consumption and the production cost are reduced.

Drawings

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 that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is an XRD pattern of as-cast and as-deformed Zn-5Dy alloy according to an embodiment of the present invention.

FIG. 2 is a metallographic structure diagram of an as-cast and as-deformed Zn-5Dy alloy according to the present invention; wherein, FIG. 2(a) is a metallographic structure diagram of an as-cast Zn-5Dy alloy, and FIG. 2(b) is a metallographic structure diagram of a deformed Zn-5Dy alloy.

FIG. 3 is SEM image and EDS analysis result of metallographic structure of as-cast and as-deformed Zn-5Dy alloy.

FIG. 4 is a polarization curve of the as-cast and as-deformed Zn-5Dy alloys of the present invention in Hanks' solution.

FIG. 5 is a graph showing the friction coefficients of the as-cast and as-deformed Zn-5Dy alloys of the present invention in Hanks' solution.

FIG. 6 is a graph showing the comparison of activities of deformed pure Zn and Zn-5Dy alloy leaching solutions of different concentrations on MC-3T3 cells.

FIG. 7 is a comparison of the antibacterial ring of the as-cast pure titanium and deformed Zn-5Dy alloy of the present invention against Staphylococcus aureus.

FIG. 8 is a schematic side view of the hot rolling mill of the present invention.

FIG. 9 is a schematic view of a main view of a hot rolling mill according to the present invention.

Fig. 10 is a partial sectional view of the frame according to the present invention.

FIG. 11 is a schematic view of the structure of the air supply pipe.

The labels in the figure are:

1-rack, 100-material conveying channel, 2-hot roll, 20-cavity, 21-slot, 22-power roll, 23-telescopic insert block, 24-oscillating shaft, 25-oscillating rod, 26-heating coil, 27-first transmission mechanism, 270-rack, 271-connecting rod, 272-first driving gear, 273-first driven gear, 3-conveying roll, 30-limit strip, 4-dust hood, 40-dust removal brush, 5-air blowing mechanism, 50-piston cavity, 51-piston, 52-piston rod, 53-crankshaft, 54-second transmission mechanism, 540-second driving gear, 541-second driven gear, 542-third driving gear, 6-main air channel, 7-branch air channel, 7-air channel, 8-one-way air valve.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.

In the description of the present application, it is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. For convenience of description, the dimensions of the various features shown in the drawings are not necessarily drawn to scale. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.

It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It will be appreciated that the data so used may be interchanged under appropriate circumstances such that embodiments of the application may be practiced in sequences other than those illustrated or described herein, and that the terms "first," "second," and the like are generally used herein in a generic sense and do not limit the number of terms, e.g., the first term can be one or more than one. In addition, "and/or" in the specification and claims means at least one of connected objects, a character "/" generally means that a preceding and succeeding related objects are in an "or" relationship.

It should be noted that in the description of the present application, the orientation or positional relationship indicated by the terms such as "front, back, up, down, left, right", "lateral, vertical, horizontal" and "top, bottom" and the like are generally based on the orientation or positional relationship shown in the drawings for convenience of description and simplicity of description only, and in the case of not making a reverse description, these orientation terms do not indicate and imply that the device or element being referred to must have a specific orientation or be constructed and operated in a specific orientation, and therefore, should not be construed as limiting the scope of the present application; the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.

It should be noted that, in the present application, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Further, it should be noted that the scope of the methods and apparatus of the embodiments of the present application is not limited to performing the functions in the order illustrated or discussed, but may include performing the functions in a substantially simultaneous manner or in a reverse order based on the functions involved, e.g., the methods described may be performed in an order different than that described, and various steps may be added, omitted, or combined. In addition, features described with reference to certain examples may be combined in other examples.

Example 1:

the embodiment of the application provides a degradable Zn-xRE alloy, which adopts a Zn ingot with the purity of 99.99 percent and a pure Dy block with the purity of 99.99 percent, and is weighed according to the mass ratio of two simple substances in the components of a Zn-5Dy binary alloy, metal raw materials are placed in a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace, the smelting temperature is 520 ℃, the temperature is kept for 20min so as to fully smelt the raw materials and ensure the elements to be uniformly distributed, the temperature to be casted is reduced to 500 ℃, alloy melt is poured into a steel casting mold preheated to 200 ℃ to prepare an alloy ingot, the ingot is kept at 340 ℃ for 10h for homogenization annealing, water cooling is adopted for cooling, linear cutting is used for preparing 70mm multiplied by 10mm square strips for carrying out isodiametric angle extrusion and hot rolling processing, 5-pass continuous isodiametric angle extrusion is carried out in an isodiametric angle mold with an isodiametric angle of 90 degrees, preheating temperature is 350 ℃, preheating time is 10min, extrusion speed is 5mm/s, bar blocks with fine second phases are obtained, finally, the bar blocks are subjected to hot rolling process with pass reduction of 5%, inter-pass heating process of 320 ℃, heat preservation time of 5min and rolling speed of 30mm/s, and finally, plates with total deformation of 85% are obtained.

In this embodiment:

1. the relative mass content of Dy element in the Zn-5Dy alloy measured by X-ray fluorescence spectroscopy (XRF) is 5.03%, and the balance is Zn.

2. As can be seen from XRD in FIG. 1, the close-packed hexagonal alpha-Zn phase and DyZn exist in the as-cast and the co-morphic Zn-5Dy alloy ₅ And (4) phase(s).

3. As can be seen from the metallographic structure of FIG. 2, a white α -Zn matrix exists in the as-cast Zn-5Dy alloy, and light gray DyZn is uniformly distributed in the matrix ₅ Phase size reached 8.8 μm. After the cooperative deformation treatment, DyZn in the specimen in the cooperative deformation state ₅ The phases are uniformly distributed on the alpha-Zn matrix along the horizontal rolling direction, and no obvious cracks appear. DyZn ₅ The phase was slightly refined relative to the as-cast sample and the phase size was reduced to 6.1 μm.

4. As can be seen from the SEM image of fig. 3, the irregular bulk phase had more cracks. EDS analysis of the Zn-5Dy alloy revealed that the Zn-5Dy alloy in the two states consisted mainly of Zn and Dy. The position 1 in the as-cast Zn-5Dy alloy contained 99.4% by relative atomic content of zinc and 0.6% by relative atomic content of Dy element. The coarse irregular granular phase at position No. 2 contained 13.6% Dy and 86.4% Zn elements. Combining the XRD and EDS results, it can be concluded that the positions No. 1 and No. 2 are alpha-Zn and DyZn, respectively ₅ And (4) phase(s).

5. As can be seen from the mechanical properties and hardness data of Table 1, the yield strength (Rp) of the as-cast Zn-5Dy alloy _0.2 ) 84.5MPa, tensile strength (Rm) 111.8MPa, elongation (A) 0.9%, and Vickers hardness 99.1 HV. Yield strength (Rp) of a synergistically morphed Zn-5Dy alloy _0.2 ) 207.5MPa, tensile strength (Rm) 286.6MPaThe elongation (A) was 43.8% and the Vickers hardness value was 97.3 HV. It can be seen that the mechanical property of the Zn-5Dy alloy is greatly improved and the hardness is slightly weakened after the synergistic deformation treatment.

TABLE 1

6. As can be seen from the polarization plot of FIG. 4 and the corrosion parameters fitted to the Tafel region of FIG. 4 (see Table 2), the corrosion potential, corrosion current density and corrosion rate of the as-cast Zn-5Dy alloy obtained by polarization testing in Hanks' solution were-0.930V, 24.5. mu.A/cm ² And 347 mu m/a, the corrosion potential, the corrosion current density and the corrosion rate of the Zn-5Dy alloy with the coordinated deformation are-0.925V and 29.6 mu A/cm ² And 419 μm/a. After the immersion test in Hanks' solution for 1 month, the degradation rate of the as-cast Zn-5Dy alloy is 33.9 μm/a, and the degradation rate of the synergetic morphic Zn-5Dy alloy is 47.2 μm/a.

TABLE 2

7. As can be seen from the friction coefficient diagram of the alloy shown in FIG. 5, the friction coefficient curves of the as-cast and the co-morphed Zn-5Dy alloys both show a large fluctuation in the early stage of wear and a tendency to gradually level off later. The overall fluctuation degree of the friction coefficient curve of the as-cast Zn-5Dy alloy is smaller than that of the cooperative deformation Zn-5Dy alloy, and particularly at the initial stage and the middle stage of wear, the time for the as-cast Zn-5Dy alloy to enter the wear stable stage is shorter. The as-cast Zn-5Dy alloy in Hanks' solution had a coefficient of friction of 0.588 and an amount of wear of 3.2mg, and the co-morphic Zn-5Dy alloy had a coefficient of friction of 0.623 and an amount of wear of 14.8 mg.

8. As can be seen from the cell activities of the alloy leaching liquor in FIG. 6, the cell activities of the synergistic morphotropic Zn-5Dy alloy leaching liquor with the concentrations of 25% and 12.5% in MC-3T3 cells are 71.8% and 99.5%, respectively, which is higher than that of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-5Dy alloy with the concentration of 12.5 percent is grade 1, which shows that the Zn-5Dy has good in-vitro cell compatibility and nontoxicity, and meets the requirement of clinical medical biomaterials on the cell compatibility.

9. As can be seen from the comparison of the antibacterial ring of the alloy in FIG. 7, the as-cast pure titanium has almost no antibacterial ring, and the synergetic metamorphic Zn-5Dy alloy has an obvious antibacterial ring with the size of 7.42mm, which indicates that the Zn-5Dy alloy has good antibacterial performance.

Example 2:

the embodiment provides a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and also has the following technical characteristics: zn ingot with the purity of 99.99 percent and pure Dy block with the purity of 99.99 percent are adopted and weighed according to the mass ratio of two simple substances in the components of the Zn-3.1Dy binary alloy. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature was 500 ℃ and was maintained at this temperature for 20min to fully melt the raw materials and ensure uniform distribution of the elements. And when the pouring temperature is reduced to 490 ℃, pouring the alloy melt into a steel casting mold preheated to 200 ℃ to obtain an alloy ingot. And (3) preserving the temperature of the cast ingot at 340 ℃ for 10 hours for homogenization annealing, and cooling by adopting water cooling. The steel is prepared into 70mm multiplied by 10mm square strips by linear cutting, and the equal channel angular extrusion and the hot rolling are cooperated. And (3) carrying out continuous equal channel extrusion for 5 times in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 350 ℃, the preheating time is 10min, and the extrusion speed is 5mm/s, so as to obtain a bar with a fine second phase. And finally, adopting a hot rolling process with the pass reduction of 5%, the inter-pass heating process of 320 ℃, the heat preservation time of 5min and the rolling speed of 30mm/s for the strip blocks to finally obtain the plate with the total deformation of 85%.

In this example, the relative content by mass of Dy element in the Zn-3.1Dy alloy was 3.13% and the balance was Zn as measured by X-ray fluorescence spectroscopy (XRF). Yield strength (Rp) of as-cast Zn-3.1Dy alloy _0.2 ) 128.6MPa, tensile strength (Rm) 143.3MPa, elongation (A) 1.6%, Vickers hardness 83.4 HV. Yield strength (Rp) of a synergistically morphed Zn-3.1Dy alloy _0.2 ) Is 225.3MPa tensile strength (Rm) of 277.9MPa, elongation (A) of 57.3%, Vickers hardness of 84.6 HV. The corrosion potential, corrosion current density and corrosion rate of the as-cast Zn-3.1Dy alloy obtained by polarization test in Hanks' solution are-0.921V and 22.4 mu A/cm ² 317 mu m/a, the corrosion potential, the corrosion current density and the corrosion rate of the Zn-3.1Dy alloy with the coordinated deformation are-0.923V and 26.3 mu A/cm ² And 372 μm/a. After the alloy is soaked in Hanks' solution for 1 month, the degradation rate of the as-cast Zn-3.1Dy alloy is 33.9 mu m/a, and the degradation rate of the synergic metamorphic Zn-3.1Dy alloy is 44.9 mu m/a. The as-cast Zn-3.1Dy alloy in Hanks' solution had a coefficient of friction of 0.519 and an amount of wear of 3.0mg, and the co-morphed Zn-3.1Dy alloy had a coefficient of friction of 0.573 and an amount of wear of 10.8 mg. The cell activities of the synergistic morphotropic Zn-3.1Dy alloy leaching liquor with the concentration of 25% and 12.5% in MC-3T3 cells are respectively 78.9% and 104.4%, and are higher than the cell activity of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-3.1Dy alloy with the concentration of 12.5 percent is 0 grade, which shows that the Zn-3.1Dy alloy has good in-vitro cell compatibility and nontoxicity, and meets the requirement of clinical medical biomaterials on the cell compatibility. The synergetic morphotropic Zn-3.1Dy alloy has an obvious antibacterial ring, and the size of the antibacterial ring is 5.99mm, which shows that the Zn-3.1Dy alloy has good antibacterial performance.

Example 3:

the embodiment provides a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and has the following technical characteristics: zn ingots with the purity of 99.99 percent and pure Ho blocks with the purity of 99.99 percent are adopted and weighed according to the mass ratio of two simple substances in the components of the Zn-7Ho binary alloy. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature was 480 ℃ and maintained at this temperature for 30min to fully melt the raw materials and ensure uniform distribution of the elements. And when the pouring temperature is reduced to 460 ℃, pouring the alloy melt into a steel casting mold preheated to 200 ℃ to obtain an alloy ingot. And (3) preserving the temperature of the cast ingot at 340 ℃ for 10 hours for homogenization annealing, and cooling by adopting water cooling. The steel wire is cut into square strips with the diameter of 70mm multiplied by 10mm by linear cutting, and the square strips are subjected to equal-diameter angular extrusion and hot rolling treatment. And (3) carrying out 2-pass continuous equal channel extrusion in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 300 ℃, the preheating time is 5min, and the extrusion speed is 5mm/s, so as to obtain a bar with a fine second phase. And finally, adopting a hot rolling process with the pass reduction of 5%, the inter-pass heating process of 280 ℃, the heat preservation time of 5min and the rolling speed of 25mm/s for the strip blocks, and finally obtaining the plate with the total deformation of 80%.

In this example, the relative content by mass of the Ho element in the Zn-7Ho alloy was 7.05% by X-ray fluorescence spectroscopy (XRF), and the remainder was Zn. Yield strength (Rp) of as-cast Zn-7Ho alloy _0.2 ) 111.9MPa, tensile strength (Rm) 133.5MPa, elongation (A) 1.4%, and Vickers hardness 92.9 HV. Yield strength (Rp) of a synergetic morphotropic Zn-7Ho alloy _0.2 ) 192.4MPa, a tensile strength (Rm) of 242.3MPa, an elongation (A) of 42.9% and a Vickers hardness of 89.4 HV. The corrosion potential, corrosion current density and corrosion rate of the as-cast Zn-7Ho alloy obtained by polarization test in Hanks' solution are-0.949V and 24.6 muA/cm ² And 348 mu m/a, the corrosion potential, the corrosion current density and the corrosion rate of the co-morphic Zn-7Ho alloy are-0.956V and 27.2 mu A/cm ² And 384 μm/a. After 1 month of soaking test in Hanks' solution, the degradation rate of the as-cast Zn-7Ho alloy is 36.4 mu m/a, and the degradation rate of the synergetic morphic Zn-7Ho alloy is 44.9 mu m/a. The as-cast Zn-7Ho alloy in Hanks' solution had a coefficient of friction of 0.519 and an amount of wear of 2.8mg, and the co-morphic Zn-7Ho alloy had a coefficient of friction of 0.672 and an amount of wear of 10.3 mg. The cell activity of the synergistic morphotropic Zn-7Ho alloy leaching liquor with the concentration of 25 percent and 12.5 percent in MC-3T3 cells is 76.3 percent and 98.7 percent respectively, and the cell activity is higher than that of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-7Ho alloy with the concentration of 12.5 percent is 1 grade, which shows that the Zn-7Ho alloy has good in vitro cell compatibility and nontoxicity, and meets the requirement of clinical medical biomaterials on the cell compatibility. The synergetic metamorphic Zn-7Ho alloy has an obvious antibacterial ring, and the size of the antibacterial ring is 7.09mm, which shows that the Zn-7Ho alloy has good antibacterial performance.

Example 4:

the embodiment provides a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and has the following technical characteristics: zn ingots with the purity of 99.99 percent and pure Y blocks with the purity of 99.99 percent are adopted and weighed according to the mass ratio of two simple substances in the components of the Zn-4Y binary alloy. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature was 550 c and maintained at this temperature for 30min to fully melt the raw materials and ensure uniform distribution of the elements. And when the pouring temperature is reduced to 500 ℃, pouring the alloy melt into a cast steel mold preheated to 230 ℃ to obtain the alloy ingot. And (3) preserving the temperature of the cast ingot at 300 ℃ for 10 hours for carrying out homogenization annealing, and cooling by air cooling. The steel wire is cut into square strips with the diameter of 70mm multiplied by 10mm by linear cutting, and the square strips are subjected to equal-diameter angular extrusion and hot rolling treatment. And (3) carrying out continuous equal channel extrusion for 3 times in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 300 ℃, the preheating time is 10min, and the extrusion speed is 3mm/s, so as to obtain a bar with a fine second phase. And finally, adopting a hot rolling process with the pass reduction of 10%, the inter-pass heating process of 270 ℃, the heat preservation time of 5min and the rolling speed of 10mm/s to obtain the plate or foil with the total deformation of 90%.

In this example, the relative mass content of the element Y in the Zn-4Y alloy measured by X-ray fluorescence spectroscopy (XRF) was 3.97%, and the remainder was Zn. Yield strength (Rp) of as-cast Zn-4Y alloy _0.2 ) 102.3MPa, a tensile strength (Rm) of 130.9MPa, an elongation (A) of 1.6% and a Vickers hardness of 88.6 HV. Yield strength (Rp) of a synergistically morphed Zn-4Y alloy _0.2 ) 204.7MPa, tensile strength (Rm) 246.5MPa, elongation (A) 46.7%, Vickers hardness 84.7 HV. The as-cast Zn-4Y alloy obtained by polarization test in Hanks' solution had a corrosion potential, a corrosion current density and a corrosion rate of-0.953V and 20.3. mu.A/cm ² And 287 mu m/a, corrosion potential of the co-morphic Zn-4Y alloy, corrosion current density and corrosion rate of-0.960V, 26.6 mu A/cm ² And 376 μm/a. After 1 month of soaking test in Hanks' solution, the degradation rate of the as-cast Zn-4Y alloy is 32.0 mu m/a, and the degradation rate of the synergetic metamorphic Zn-4Y alloy is 38.7 mu m/a. As-cast Zn-4Y alloy in Hanks' solution with a coefficient of friction of 0505 and a wear loss of 4.9mg, the coefficient of friction of the co-morphic Zn-4Y alloy being 0.607 and the wear loss being 12.3 mg. The cell activity of the synergistic morphotropic Zn-4Y alloy leaching liquor with the concentration of 25 percent and 12.5 percent in MC-3T3 cells is 72.4 percent and 95.3 percent respectively, and the cell activity is higher than that of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-4Y alloy with the concentration of 12.5 percent is grade 1, which shows that the Zn-4Y alloy has good in vitro cell compatibility and nontoxicity, and meets the requirement of clinical medical biomaterials on the cell compatibility. The synergetic metamorphic Zn-4Y alloy has an obvious antibacterial ring, and the size of the antibacterial ring is 6.50mm, which shows that the Zn-4Y alloy has good antibacterial performance.

Example 5:

the embodiment provides a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and has the following technical characteristics: zn ingots with the purity of 99.99 percent and pure Er blocks with the purity of 99.99 percent are adopted and weighed according to the mass ratio of two simple substances in the components of the Zn-8Er binary alloy. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature was 650 deg.c and maintained at this temperature for 20min to fully melt the raw materials and ensure uniform distribution of the elements. And when the pouring temperature is reduced to 620 ℃, pouring the alloy melt into a steel casting mold preheated to 250 ℃ to obtain the alloy ingot. And (3) preserving the temperature of the cast ingot at 340 ℃ for 10 hours for homogenization annealing, and cooling by adopting water cooling. The steel wire is cut into square strips with the diameter of 70mm multiplied by 10mm by linear cutting, and the square strips are subjected to equal-diameter angular extrusion and hot rolling treatment. And (3) carrying out 10-pass continuous equal channel extrusion in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 320 ℃, the preheating time is 15min, and the extrusion speed is 5mm/s, so as to obtain the bar blocks. And finally, adopting a hot rolling process with the pass reduction of 10%, the inter-pass heating process of 280 ℃, the heat preservation time of 5min and the rolling speed of 30mm/s for the strip blocks, and finally obtaining the plate with the total deformation of 80%.

In this example, the relative content by mass of Er element in the Zn-8Er alloy was 8.03% by X-ray fluorescence spectroscopy (XRF), and the balance was Zn. Yield strength (Rp) of as-cast Zn-8Er alloy _0.2 ) 129.5MPa, tensile strength (Rm) 167.3MPa, and elongation (A)1.2% and a Vickers hardness value of 97.9 HV. Yield strength (Rp) of a synergistically morphed Zn-8Er alloy _0.2 ) 235.8MPa, a tensile strength (Rm) of 309.3MPa, an elongation (A) of 27.3% and a Vickers hardness of 93.6 HV. The corrosion potential, corrosion current density and corrosion rate of the as-cast Zn-8Er alloy obtained by polarization test in Hanks' solution are-0.989V and 30.5 mu A/cm ² And 431 mu m/a, the corrosion potential, the corrosion current density and the corrosion rate of the Zn-8Er alloy with the coordinated deformation are-0.997V and 33.9 mu A/cm ² And 480 μm/a. After the alloy is soaked in Hanks' solution for 1 month, the degradation rate of the as-cast Zn-8Er alloy is 38.9 mu m/a, and the degradation rate of the synergetic metamorphic Zn-8Er alloy is 47.3 mu m/a. The as-cast Zn-8Er alloy in Hanks' solution had a coefficient of friction of 0.577 and an amount of wear of 2.4mg, and the co-morphed Zn-8Er alloy had a coefficient of friction of 0.586 and an amount of wear of 8.9 mg. The cell activity of the synergistic morphotropic Zn-8Er alloy leaching liquor with the concentration of 25 percent and 12.5 percent in MC-3T3 cells is respectively 70.3 percent and 97.6 percent, and is higher than that of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-8Er alloy with the concentration of 12.5 percent is grade 1, which shows that the Zn-8Er alloy has good in vitro cell compatibility and nontoxicity and meets the requirements of clinical medical biomaterials on cell compatibility. The synergetic metamorphic Zn-8Er alloy has an obvious antibacterial ring, and the size of the antibacterial ring is 7.77mm, which shows that the Zn-8Er alloy has good antibacterial performance.

Example 6:

the embodiment provides a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and has the following technical characteristics: zn ingots with the purity of 99.99 percent and pure Sc blocks with the purity of 99.99 percent are adopted and weighed according to the mass ratio of two simple substances in the components of the Zn-10Sc binary alloy. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature was 750 ℃ and was maintained at this temperature for 20min to fully melt the raw materials and ensure uniform distribution of the elements. And when the pouring temperature is reduced to 720 ℃, pouring the alloy melt into a steel casting mold preheated to 250 ℃ to obtain the alloy ingot. And (3) keeping the temperature of the cast ingot at 350 ℃ for 10 hours for carrying out homogenization annealing, and cooling by air cooling. The steel wire is cut into square strips with the diameter of 70mm multiplied by 10mm by linear cutting, and the square strips are subjected to equal-diameter angular extrusion and hot rolling treatment. And (3) carrying out continuous equal channel extrusion for 8 times in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 330 ℃, the preheating time is 5min, and the extrusion speed is 10mm/s, so as to obtain the bar blocks. And finally, adopting a hot rolling process with the pass reduction of 10%, the inter-pass heating process of 300 ℃, the heat preservation time of 3min and the rolling speed of 30mm/s to obtain the plate or foil with the total deformation of 80%.

In this example, the relative mass content of Sc element in the Zn-10Sc alloy was 9.95% by X-ray fluorescence spectroscopy (XRF), with the remainder being Zn. Yield strength (Rp) of as-cast Zn-10Sc alloy _0.2 ) 167.5MPa, a tensile strength (Rm) of 200.6MPa, an elongation (A) of 0.8% and a Vickers hardness of 105.9 HV. Yield strength (Rp) of a synergistically morphed Zn-10Sc alloy _0.2 ) 227.3MPa, tensile strength (Rm) 283.4MPa, elongation (A) 16.5% and Vickers hardness value 100.8 HV. The as-cast Zn-10Sc alloy obtained by polarization test in Hanks' solution has a corrosion potential, a corrosion current density and a corrosion rate of-0.997V and 32.7 muA/cm ² And 463 mu m/a, corrosion potential, corrosion current density and corrosion rate of the Zn-10Sc alloy with the coordinated deformation are-1.004V and 38.6 mu A/cm ² And 546 μm/a. The degradation rate of the as-cast Zn-10Sc alloy after 1 month of the soaking test in Hanks' solution is 43.9 μm/a, and the degradation rate of the co-morphic Zn-10Sc alloy is 50.2 μm/a. The as-cast Zn-10Sc alloy in Hanks' solution had a coefficient of friction of 0.603 and a wear loss of 1.8mg, and the co-morphed Zn-10Sc alloy had a coefficient of friction of 0.597 and a wear loss of 6.4 mg. The cell activity of the synergistic morphotropic Zn-10Sc alloy leaching solution with the concentration of 25 percent and 12.5 percent in MC-3T3 cells is 72.5 percent and 94.7 percent respectively, and is higher than that of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-10Sc alloy with the concentration of 12.5 percent is 1 grade, which shows that the Zn-10Sc alloy has good in-vitro cell compatibility and nontoxicity, and meets the requirement of clinical medical biomaterials on the cell compatibility. The synergetic metamorphic Zn-10Sc alloy has an obvious antibacterial ring, and the size of the antibacterial ring is 7.93mm, which shows that the Zn-10Sc alloy has good antibacterial performance.

Example 7:

the embodiment provides a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and has the following technical characteristics: zn ingots with the purity of 99.99 percent and pure Er blocks with the purity of 99.99 percent are adopted and weighed according to the mass ratio of two simple substances in the components of the Zn-8Er binary alloy. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature was 650 deg.c and maintained at this temperature for 20min to fully melt the raw materials and ensure uniform distribution of the elements. And when the pouring temperature is reduced to 620 ℃, pouring the alloy melt into a steel casting mold preheated to 250 ℃ to obtain the alloy ingot. And (3) preserving the temperature of the cast ingot at 340 ℃ for 10 hours for homogenization annealing, and cooling by air cooling. Single equal channel angular extrusion was performed using wire-cut to prepare 70mm by 10mm square bars. And (3) carrying out 10-pass continuous equal channel extrusion in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 320 ℃, the preheating time is 15min, and the extrusion speed is 5mm/s, so as to obtain the bar blocks.

In this example, the yield strength (Rp) of a Zn-8Er alloy in a single constant channel angular extrusion state _0.2 ) 202.5MPa, tensile strength (Rm) 267.4MPa, elongation (A) 16.6%, and Vickers hardness value 90.2 HV. The corrosion potential, the corrosion current density and the corrosion rate of the single isodiametric angular extrusion Zn-8Er alloy obtained by a polarization test in Hanks' solution are-0.999V and 42.3 mu A/cm ² And 599 μm/a. The degradation rate of the single isodiametric angular extrusion Zn-8Er alloy after 1 month of soaking test in Hanks' solution is 49.6 mu m/a. The friction coefficient of the single isodiametric angle extrusion Zn-8Er alloy in Hanks' solution is 0.593 and the abrasion loss is 9.2 mg. The cell activity of the single isodiametric angle extrusion Zn-8Er alloy leaching liquor with the concentration of 25 percent and 12.5 percent in MC-3T3 cells is 66.7 percent and 94.6 percent respectively, and is higher than that of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-8Er alloy with the concentration of 12.5 percent is 1 grade, which shows that the Zn-8Er alloy has good in vitro cell compatibility and nontoxicity, and meets the requirement of clinical medical biomaterials on the cell compatibility. The single isodiametric angle extrusion Zn-8Er alloy has an obvious antibacterial ring, the size of the antibacterial ring is 7.83mm, and the indication shows that the Zn-8Er alloy has a remarkable antibacterial effectThe alloy has good antibacterial performance.

Example 8:

the embodiment provides a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and has the following technical characteristics: zn ingot with the purity of 99.99 percent and pure Dy block with the purity of 99.99 percent are adopted and weighed according to the mass ratio of two simple substances in the components of the Zn-3.1Dy binary alloy. Putting the metal raw material into a pure niobium crucible to be smelted in a vacuum induction suspension smelting furnace. The melting temperature was 500 deg.c and maintained at this temperature for 20min to fully melt the raw materials and ensure uniform distribution of the elements. And when the pouring temperature is reduced to 490 ℃, pouring the alloy melt into a steel casting mold preheated to 200 ℃ to obtain an alloy ingot. And (3) preserving the temperature of the cast ingot at 340 ℃ for 10 hours for homogenization annealing, and cooling by adopting water cooling. A single hot rolling treatment was carried out using a wire cut to prepare a 70mm by 10mm square bar. And (3) adopting a hot rolling process of rolling the square strip at the rolling speed of 30mm/s with the pass reduction of 5%, the inter-pass heating process of 320 ℃ and the heat preservation time of 5min to finally obtain the plate with the total deformation of 85%.

In this example, the yield strength (Rp) of a Zn-3.1Dy alloy in a Single Hot Rolling State _0.2 ) 214.8MPa, tensile strength (Rm) 270.5MPa, elongation (A) 55.1%, Vickers hardness 80.5 HV. The corrosion potential, corrosion current density and corrosion rate of the single hot-rolled Zn-3.1Dy alloy obtained by polarization test in Hanks' solution are-0.923V and 27.9 muA/cm ² And 393 μm/a. The degradation rate of the single hot rolled Zn-3.1Dy alloy after 1 month of the immersion test in Hanks' solution was 47.2 μm/a. The friction coefficient of a single hot rolled Zn-3.1Dy alloy in Hanks' solution was 0.580 and the amount of wear was 11.6 mg. The cell activity of the single hot rolling Zn-3.1Dy alloy leaching liquor with the concentration of 25 percent and 12.5 percent in MC-3T3 cells is 75.6 percent and 102.1 percent respectively, and is higher than that of pure zinc. According to the ISO 10993-5 standard, the cytotoxicity grade of the Zn-3.1Dy alloy with the concentration of 12.5 percent is 1 grade, which shows that the Zn-3.1Dy alloy has good in-vitro cell compatibility and nontoxicity, and meets the requirement of clinical medical biomaterials on the cell compatibility. The single hot rolling state Zn-3.1Dy alloy has remarkable antibacterial ring and is antibacterialThe size of the bacterium ring is 6.08mm, which shows that the Zn-3.1Dy alloy has good antibacterial performance.

Example 9:

the embodiment provides a preparation method of a degradable Zn-xRE alloy, which comprises the technical scheme of the embodiment and also has the following technical characteristics that in the fifth step, a hot rolling mill is adopted to perform equal-diameter-angle extrusion and hot rolling treatment.

The hot rolling mill further comprises: the device comprises a frame 1, wherein a material conveying channel 100 is arranged on the frame 1; the hot roll group comprises a pair of hot rolls 2, and the hot rolls 2 are rotatably arranged on the frame 1; the conveying roller group comprises a pair of conveying rollers 3, and the conveying roller group is rotatably arranged on the rack; the constant diameter angle rolling die is arranged on the discharge side of the hot roller group;

wherein the hot roll group is positioned in the material conveying channel 100, and the conveying roll group is positioned at the feeding side of the hot roll group.

In this embodiment, the square bar that waits to process is carried to the hot roll group along the defeated material passageway on the frame, and the conveying stability of square bar can be improved to the conveying roller group, and the square bar carries out the hot rolling processing in coordination of isodiametric angle extrusion at the in-process through hot roll group and isodiametric angle rolling mould.

Example 10:

the embodiment provides a preparation method of a degradable Zn-xRE alloy, which includes the technical scheme of the above embodiment, and further has the following technical features, and the hot roll 2 further includes: the cavity 20 is arranged in the hot roll 2, and a plurality of slots 21 are formed in the inner wall of the cavity 20; the power roller 22 is arranged in the cavity 20, and a plurality of telescopic insertion blocks 23 are arranged on the power roller 22; a heating mechanism including a swing shaft 24, a swing lever 25, and a heating coil 26; a first transmission mechanism 27, wherein the first transmission mechanism 27 is used for connecting the power roller 22 with the swinging shaft 24 in a transmission way;

wherein, the power roller 22 can drive the swing shaft 24 to rotate back and forth through the first transmission mechanism 27, and the plurality of telescopic insertion blocks 23 are matched with the plurality of slots 21 for driving the hot rolling roll 2 to rotate.

And a plurality of slots are distributed at equal intervals along the circumferential direction of the inner side of the cavity, a plurality of telescopic insertion blocks are distributed at equal intervals along the circumferential direction of the power roller, a plurality of movable grooves are arranged on the power roller, the telescopic insertion blocks are respectively and slidably arranged in the movable grooves, the movable grooves are distributed at equal intervals along the circumferential direction of the power roller, the outer ends of the movable grooves extend to the surface of the power roller to form openings, return springs are arranged in the movable grooves, the return springs are connected with the telescopic insertion blocks to drive the telescopic insertion blocks to retract into the movable grooves, compressed air grooves are arranged in the power roller and are communicated with the inner ends of the movable grooves, air sources are externally connected with the compressed air grooves, the telescopic insertion blocks can extend out of the movable grooves under the action of air pressure, the oscillating shaft is coaxial with the hot rolling roller, the oscillating shaft is positioned in the cavity and is rotatably connected with the hot rolling roller, the oscillating rods are symmetrically arranged at two sides of the oscillating shaft, heating coils are arranged at one side of the oscillating rod, which is far away from the oscillating shaft, the heating coil can heat the surface of the hot-rolled shaft, the first transmission mechanism comprises a rack 270, a connecting rod 271, a first driving gear 272 in transmission connection with the power roller and a first driven gear 273 in transmission connection with the oscillating shaft, two ends of the connecting rod are respectively in rotation connection with the rack and the first driving gear, and the rack, the connecting rod, the first driving gear and the first driven gear form an eccentric crank slider mechanism for driving the oscillating shaft to rotate in a reciprocating mode.

In the embodiment, an external air source supplies air to a compressed air tank, after the compressed air tank is inflated, a telescopic insert block extends out of a movable difference under the action of air pressure and is matched with an insertion slot, a power roller rotates and controls the start and stop of a hot rolling roller through the mutual matching of the telescopic insert block and the insertion slot, when the hot rolling roller stops, the air in the compressed air tank is pumped out, so that the insert block retracts into the movable slot under the action of a reset spring and is disengaged from the insertion slot, the power roller does not drive the hot rolling roller to rotate when rotating, at the moment, the power roller keeps rotating and drives a first driving gear to rotate, a rack moves in a reciprocating manner along with the rotation of the first driving gear under the driving of a connecting rod so as to drive a first driven gear to rotate in a reciprocating manner, so that a swinging shaft rotates in a reciprocating manner, the swinging shaft drives a swinging rod to enable a heating coil to move along with the swinging rod, the hot rolling roller is insulated and the heating effect is uniform, the hot rolling treatment effect of the square bars is improved, the hot rolling roll is convenient to start quickly, the phenomenon that the hot rolling roll is damaged due to local overheating is prevented, and the service life of the hot rolling roll is prolonged.

Example 11:

the embodiment provides a preparation method of a degradable Zn-xRE alloy, which comprises the following technical characteristics in addition to the technical scheme of the embodiment, and further comprises the following steps: the dust hood 4 is arranged on the feeding side of the conveying roller set; the air blowing mechanism 5 is arranged in the rack 1; the gas supply pipeline comprises a main gas circuit 6 and a branch gas circuit 7, and a one-way gas valve 8 is arranged on the branch gas circuit 7;

wherein, the dust hood 4 is connected with the blowing mechanism 5 through an air supply pipeline.

The air blowing mechanism 5 further includes: a piston cavity 50, wherein a piston 51 is movably arranged in the piston cavity 50, and an air outlet is formed in the piston cavity 50; a piston rod 52, the piston rod 52 being disposed at a lower end of the piston 51; the crankshaft 53 is arranged at the lower end of the piston rod 52 and used for driving the piston rod 52 to reciprocate; the second transmission mechanism 54 is in transmission connection with the first transmission mechanism 27 and is used for driving the crankshaft 53 to rotate;

wherein, the gas outlet is located the top of piston 51, and the air feed pipeline is connected with the gas outlet.

Dust removal brush hair 40 is arranged on the dust excluding hood 4, and the dust removal brush hair 40 is positioned on one side of the dust excluding hood 4 close to the conveying roller group.

Moreover, the crankshaft is rotatably arranged at the lower end of the piston cavity, two ends of the piston rod are respectively movably connected with the piston and the crankshaft, the branch gas circuit comprises two gas inlets and two gas outlets, the one-way gas valves are respectively used for gas inlet and gas outlet, the one-way gas valves are connected with the branch gas circuit in series, the ventilation directions of the two one-way gas valves on the two branch gas circuits are opposite, the two gas circuits are connected with the main gas circuit in parallel, the second transmission mechanism comprises a second driving gear 540, the second driven gear 541 and the third driving gear 542 are connected with the crankshaft in a transmission mode, the second driving gear is meshed with the first driving gear, the second driven gear is meshed with the third driving gear, one end of the main gas path is connected with a gas outlet in the piston cavity, the other end of the main gas path is connected with the dust hood, a gas branch path for gas inlet in the two gas branch paths is connected with a filtering device 80 for filtering dust and impurities in series, and the filtering device is located on the gas inlet side of a one-way gas valve on the gas branch path.

In the embodiment, impurities such as dust and the like are easily attached to the surface of a square bar in the conveying process, the dust and the impurities can affect the hot rolling treatment effect of the square bar, the alloy finished product quality is reduced, the dust hood is in the square bar conveying process, the air blowing mechanism conveys air flow to the dust hood through the air supply pipeline, the dust hood sprays the air flow to the surface of the square bar, the dust and the impurities attached to the surface of the square bar are removed, the dust and the impurities are prevented from affecting the hot rolling treatment effect of the square bar, the alloy finished product quality is improved, meanwhile, along with the rotation of the power roller, the second driving gear rotates along with the first driving gear and drives the second driven gear to rotate, the third driving gear rotates along with the second driven gear and drives the crankshaft to rotate, the driving force of the power roller is transmitted to the second transmission mechanism through the first transmission mechanism to drive the crankshaft to rotate, the piston rod drives the piston to move up and down along with the rotation of the crankshaft, thereby the air in the extrusion piston chamber produces the air current, and the air current that produces in the piston chamber passes through the gas outlet and gets into air feed pipeline and flow to the dust excluding hood, through the dust excluding hood blowout at last for the mechanism of blowing need not extra power supply, has reduced energy resource consumption and manufacturing cost.

Example 12:

the embodiment provides a preparation method of a degradable Zn-xRE alloy, which includes the technical scheme of the above embodiment, and further has the following technical features, and the conveying roller 3 further includes: the conveying roller device comprises a plurality of limiting strips 30, wherein the limiting strips 30 are evenly distributed at intervals along the circumferential direction of the conveying roller 3, the length direction of each limiting strip 30 is axially parallel to the axial direction of the conveying roller 3, the limiting strips 30 are made of rubber, and fluid is filled in the limiting strips 30.

And, spacing fixed mounting is on the conveying roller, and the fluid of filling in the spacing is water or air, occupies three quarters internal volume when filling water in the spacing, occupies one quarter internal volume when filling air in the spacing, and a plurality of spacing include eight at least.

In this embodiment, when the square billet skew appears in transportation process, the fluid in the spacing strip is received the extrusion flow direction and is led to the volume increase of one side in addition to make the frictional force of one side in addition increase, the unbalanced two sides frictional force can make the square billet return gradually, thereby prevents that the phenomenon of skew from appearing in transportation process in the square billet, has improved the transport stability of square billet.

While the embodiments of the present application have been described in connection with the drawings, the embodiments and features of the embodiments of the present application can be combined with each other without conflict, and the present application is not limited to the above-mentioned embodiments, which are only illustrative and not restrictive, and those skilled in the art can make many forms without departing from the spirit and scope of the present application and the claims.

Claims

1. A degradable Zn-xRE alloy comprises a main material element Zn and an alloy element RE, and is characterized in that: the alloy element RE also comprises dysprosium (Dy), holmium (Ho), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), neodymium (Nd), terbium (Tb) and erbium (Er), wherein x is 3.05-10.05 wt% in percentage by mass, and the balance is Zn.

2. The degradable Zn-xRE alloy according to claim 1, wherein: the x accounts for 3.05-8.05 wt.%, and the balance is Zn.

3. A method for preparing the degradable Zn-xRE alloy of claim 2, comprising the steps of:

the method comprises the following steps: the main raw materials of the Zn-xRE binary alloy used for smelting are as follows: zn ingot with the purity of 99.99 percent and pure RE block with the purity of 99.99 percent are weighed according to the mass ratio of two simple substances in the Zn-xRE binary alloy components;

step two: putting a metal raw material into a pure niobium crucible, smelting in a vacuum induction suspension smelting furnace at the melting temperature of 450-800 ℃, and keeping the temperature for 20-40 min so as to fully melt the raw material and ensure the uniform distribution of elements;

step three: when the pouring temperature is reduced to 420-770 ℃, pouring the alloy melt into a steel casting mold preheated to 150-250 ℃ to obtain an alloy ingot;

step four: carrying out heat preservation on the cast ingot at 250-350 ℃ for 2-10 h for carrying out homogenization annealing, and cooling by adopting water cooling or air cooling;

step five: preparing a square strip with the diameter of 70mm multiplied by 10mm by linear cutting, and carrying out equal-diameter angular extrusion and hot rolling treatment;

step six: carrying out 2-20 times of continuous equal channel extrusion in an equal channel angular die with an equal channel angular angle of 90 degrees, wherein the preheating temperature is 250-350 ℃, the preheating time is 5-20 min, and the extrusion speed is 1-10 mm/s, so as to obtain strips with fine second phases;

step seven: and (3) adopting a hot rolling process with the pass reduction of 2-10%, the inter-pass heating process of 230-330 ℃, the heat preservation time of 2-10 min and the rolling speed of 10-50 mm/s to obtain the plate or foil with the total deformation of 50-99%.

4. The method for preparing the degradable Zn-xRE alloy according to claim 3, wherein: and in the fifth step, a hot rolling mill is adopted for carrying out equal channel angular extrusion and hot rolling treatment.

5. The method for preparing the degradable Zn-xRE alloy according to claim 4, wherein the hot rolling mill further comprises:

the device comprises a rack (1), wherein a material conveying channel (100) is arranged on the rack (1);

the hot roll group comprises a pair of hot rolls (2), and the hot rolls (2) are rotatably arranged on the frame (1);

the conveying roller group comprises a pair of conveying rollers (3), and the conveying roller group is rotatably arranged on the rack;

the constant-diameter angle rolling die is arranged on the discharge side of the hot roller group;

the hot roll set is positioned in the conveying channel (100), and the conveying roll set is positioned on the feeding side of the hot roll set.

6. The method for preparing a degradable Zn-xRE alloy according to claim 5, wherein the hot roll (2) further comprises:

the cavity (20) is arranged in the hot roll (2), and a plurality of slots (21) are formed in the inner wall of the cavity (20);

the power roller (22), the power roller (22) is arranged in the cavity (20), and a plurality of telescopic insertion blocks (23) are arranged on the power roller (22);

a heating mechanism including a swing shaft (24), a swing lever (25), and a heating coil (26);

a first transmission mechanism (27), wherein the first transmission mechanism (27) is used for connecting the power roller (22) with the swinging shaft (24) in a transmission way;

the power roll (22) can drive the swinging shaft (24) to rotate in a reciprocating mode through the first transmission mechanism (27), and the plurality of telescopic inserting blocks (23) are matched with the plurality of inserting grooves (21) to be used for driving the hot roll (2) to rotate.

7. The method for preparing the degradable Zn-xRE alloy according to claim 6, further comprising:

the dust hood (4), the dust hood (4) is arranged on the feeding side of the conveying roller set;

the air blowing mechanism (5), the air blowing mechanism (5) is arranged in the rack (1);

the gas supply pipeline comprises a main gas circuit (6) and a branch gas circuit (7), and a one-way gas valve (8) is arranged on the branch gas circuit (7);

wherein, the dust hood (4) is connected with the blowing mechanism (5) through an air supply pipeline.

8. The method for preparing a degradable Zn-xRE alloy according to claim 7, wherein the blowing mechanism (5) further comprises:

the piston cavity (50), a piston (51) is movably arranged in the piston cavity (50), and an air outlet is formed in the piston cavity (50);

a piston rod (52), the piston rod (52) being disposed at a lower end of the piston (51);

the crankshaft (53) is arranged at the lower end of the piston rod (52) and used for driving the piston rod (52) to move in a reciprocating mode;

the second transmission mechanism (54) is in transmission connection with the first transmission mechanism (27) and is used for driving the crankshaft (53) to rotate;

wherein, the gas outlet is positioned above the piston (51), and the gas supply pipeline is connected with the gas outlet.

9. The method for preparing a degradable Zn-xRE alloy according to claim 5, wherein the conveyor roll (3) further comprises:

the conveying roller is characterized in that the conveying roller is provided with a plurality of limiting strips (30), the limiting strips (30) are evenly distributed at intervals along the circumferential direction of the conveying roller (3), the length direction of the limiting strips (30) is axially parallel to the conveying roller (3), the limiting strips (30) are made of rubber, and fluid is filled in the limiting strips (30).

10. The method for preparing the degradable Zn-xRE alloy according to claim 7, wherein: the dust removing brush (40) is arranged on the dust removing cover (4), and the dust removing brush (40) is located on one side, close to the conveying roller set, of the dust removing cover (4).