Alloy material capable of improving barrier absorption

Abstract

The invention relates to the technical field of metal alloy materials, and discloses an alloy material capable of improving barrier absorption, which is prepared by the following steps: uniformly mixing modified titanium powder, zinc powder and copper powder, smelting to obtain a basic melt, adding magnesium powder and silver powder into the basic melt, and stirring at 970-1050 DEG C for 20-40 minutes to obtain an alloy melt; placing the alloy melt in a prefabricated mold, performing casting molding, cooling to room temperature, and demolding to obtain an alloy cast ingot; the alloy ingot is subjected to annealing treatment and cold rolling, then soaked in a surface treating agent, stirred, taken out and dried, and an alloy material is obtained; the alloy material is prepared by optimizing the proportion of the modified titanium powder, the zinc powder, the copper powder, the magnesium powder and the silver powder and the preparation technology, a gel layer is formed on the surface of the alloy material, and the alloy material has good barrier absorption performance and can improve the skin state.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of metal alloy materials, in particular to an alloy material with improved barrier absorption. BACKGROUND

[0002] In the field of biological tissue repair and skin care, the core requirements are to improve the self-healing ability of human skin, improve the brightness of human skin, and anti-wrinkle, etc. The materials used in the prior art for the above requirements are mainly biological extracts and chemical synthetic substances, which have the following disadvantages: single function, poor stability, limited biocompatibility, and limited wide application.

[0003] The existing alloy materials mainly focus on mechanical strength and corrosion resistance, and few are designed for "improving barrier absorption of the biological body" and "improving skin state". There is a lack of technical solutions for the synergistic combination of zinc, copper, titanium, magnesium and silver to realize the above composite functions. Therefore, it has become a problem to be solved in the field to develop an alloy material with stable performance, excellent biocompatibility, and the ability to simultaneously improve barrier absorption and skin state.

[0004] By optimizing the ratio and preparation process of titanium powder, zinc powder, copper powder, magnesium powder and silver powder, an alloy material with good mechanical properties and barrier absorption properties is prepared. However, the titanium powder, zinc powder, copper powder, magnesium powder and silver powder metal alloy material has the problems of strong phase particle agglomeration and insufficient dispersion of structural components during preparation. In addition, the melting points of titanium powder, zinc powder, copper powder, magnesium powder and silver powder are quite different, resulting in poor uniformity of the prepared alloy material, affecting the mechanical properties and barrier absorption properties of the alloy material. In addition, the surface of the alloy material has high inertness and poor compatibility, which affects the barrier absorption of the alloy material. SUMMARY

[0005] The application provides an alloy material with improved barrier absorption, which solves the problem of poor uniformity of the prepared alloy material due to the large difference in melting points of titanium powder, zinc powder, copper powder, magnesium powder and silver powder, affecting the mechanical properties and barrier absorption properties of the alloy material.

[0006] The technical scheme of the application is as follows:

[0007] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0008] S1. uniformly mix modified titanium powder, zinc powder and copper powder, melt at 1000-1100 DEG C for 30-60 min to obtain a base melt, add magnesium powder and silver powder to the base melt, and stir at 970-1050 DEG C for 20-40 min to obtain an alloy melt;

[0009] S2. The alloy melt is placed in a prefabricated mold, cast into shape, cooled to room temperature, demolded, and an alloy ingot is obtained;

[0010] S3. After annealing and cold rolling, the alloy ingot is immersed in a surface treatment agent, stirred at 40-50℃ for 20-30min, taken out, dried, and an alloy material is obtained;

[0011] The modified titanium powder is obtained by synthesizing a porous carbon layer on the surface of titanium powder, and then mixed with calcium hydroxide and phosphoric acid for reaction.

[0012] The surface treatment agent is obtained by mixing composite hydrogel and deionized water at a mass ratio of (5-10):90.

[0013] The composite hydrogel is obtained by mixing hyaluronic acid surface modified bioactive glass, polyvinyl alcohol, and carboxymethyl cellulose.

[0014] Further, in step S1, the mass ratio of modified titanium powder, zinc powder, copper powder, magnesium powder, and silver powder is (1-1.5):(4.5-6):(1.5-2.5):(0.5-1.2):(0.1-0.5).

[0015] Further, in step S2, the casting pressure is 20-30MPa.

[0016] Further, in step S3, the annealing temperature is 300-400℃, and the annealing time is 2-4h.

[0017] Further, in step S3, the cold rolling pressure is 300-350MPa.

[0018] Further, the modified titanium powder is prepared by the following steps:

[0019] A1. Titanium powder and tannic acid are added to ethanol, stirred until uniform, glucose is added, stirred until uniform, filtered, washed, dried, placed in a tube furnace, potassium hydroxide solution is added, nitrogen is introduced, carbonized, cooled to room temperature, taken out, washed, and dried to obtain titanium powder loaded with a porous carbon layer;

[0020] A2. Calcium hydroxide is added to deionized water, stirred until completely dissolved, titanium powder loaded with a porous carbon layer is added, stirred until uniform, phosphoric acid is added, continued stirring, hydrothermal reaction, cooled to room temperature, filtered, washed, and dried to obtain modified titanium powder.

[0021] Further, in the above A1 reaction process, tannic acid as a connecting agent makes the glucose coated on the surface of titanium powder through citric acid, and through high-temperature carbonization, the glucose is decomposed by heat to form a dense carbon layer. Potassium hydroxide solution as an activator can form pores on the surface of the dense carbon layer, so as to synthesize a porous carbon layer on the surface of titanium powder, and obtain titanium powder loaded with a porous carbon layer.

[0022] Further, in the above A2 reaction process, the surface of titanium powder loaded with a porous carbon layer contains a large number of porous structures and has good adsorption performance, so as to adsorb calcium ions in calcium hydroxide to the surface of titanium powder loaded with a porous carbon layer. Calcium ions combine with phosphate ions to form calcium phosphate complex. After hydrothermal treatment, the calcium phosphate complex is crystallized to form hydroxyapatite, so as to synthesize hydroxyapatite with a size of 60 nm in the pores of the porous carbon layer on the surface of titanium powder, and obtain modified titanium powder.

[0023] Further, in step A1, the mass ratio of titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is (2-3):(0.5-1):(100-120):(2-2.5):(2-3).

[0024] Further, in step A2, the mass ratio of calcium hydroxide, deionized water, titanium powder loaded with a porous carbon layer and phosphoric acid is (1.5-2):(100-110):(2.5-3):(1-1.2).

[0025] Further, the composite hydrogel is prepared by the following steps:

[0026] B1. Add hyaluronic acid to deionized water and stir until it becomes viscous. Add bioactive glass and stir until uniform. Filter, wash and dry to obtain hyaluronic acid modified bioactive glass.

[0027] B2. Add carboxymethyl cellulose and polyvinyl alcohol to ethanol and ultrasonic treat. Add epoxy chloropropane and hyaluronic acid modified bioactive glass and stir to form a gel. Filter and wash to obtain a composite hydrogel.

[0028] Further, in the above B1 reaction process, hyaluronic acid modifies bioactive glass. The carboxyl groups in hyaluronic acid can combine with the cations in bioactive glass, so that hyaluronic acid is coated on the surface of bioactive glass to obtain hyaluronic acid modified bioactive glass.

[0029] Further, in the B2 reaction process, the hyaluronic acid modified bioactive glass is further mixed with polyvinyl alcohol and carboxymethyl cellulose, and the polyvinyl alcohol and carboxymethyl cellulose are combined by hydrogen bond, and under the action of crosslinking agent epichlorohydrin, a cellulose gel is formed, and in the process of forming the gel, the carboxyl contained in the hyaluronic acid modified bioactive glass can also participate in the gel reaction, so that the hyaluronic acid modified bioactive glass is embedded into the cellulose gel to form a composite hydrogel.

[0030] Further, in the B1 step, the mass ratio of hyaluronic acid, deionized water and bioactive glass is (2-3):(40-50):(3-3.5).

[0031] Further, in the B2 step, the mass ratio of carboxymethyl cellulose, polyvinyl alcohol, ethanol, epichlorohydrin and hyaluronic acid modified bioactive glass is (0.8-1.2):(0.5-1):(90-100):(1-1.2):(1.5-2).

[0032] The present application has the following beneficial effects:

[0033] (1) In the technical scheme of the present application, a porous carbon layer is synthesized on the surface of titanium powder. On the one hand, the porous carbon layer has excellent adsorption performance and porous structure due to its rich porosity, which is beneficial to the formation of hydroxyapatite on the surface of titanium powder, and the titanium powder can improve the biocompatibility of the alloy material and further improve the barrier absorption performance of the alloy material, thereby improving the skin condition. On the other hand, the synthesized porous carbon layer provides a large amount of carbon elements, which can form carbide reinforced phase with zinc powder, copper powder, magnesium powder and silver powder dispersed in the alloy material matrix, forming a dense alloy material and improving the mechanical strength of the alloy material. In addition, the addition of the porous carbon layer and the formation of the carbide reinforced phase with the metal can avoid the difference in melting point of zinc, copper, magnesium and silver metal powder, which leads to poor performance of the formed alloy material and affects the barrier absorption performance of the alloy material.

[0034] (2) In the technical scheme of the present application, nano-hydroxyapatite is synthesized in the pores of the porous carbon layer on the surface of titanium powder. On the one hand, the synthesized hydroxyapatite has good biocompatibility, which can improve the compatibility of the alloy material, so that the alloy material can be better absorbed by the skin, improve the skin condition, and the released calcium ions can promote skin repair, increase the density and elasticity of the dermis layer, and improve the skin barrier and moisturizing. On the other hand, the synthesis of nano-hydroxyapatite in the pores of the porous carbon layer on the surface of titanium powder improves the dispersibility of nano-hydroxyapatite in the alloy material, avoids the agglomeration of nano-hydroxyapatite, and affects the barrier absorption performance of the alloy material. Moreover, the addition of nano-hydroxyapatite to the alloy material can improve the mechanical properties of the alloy material.

[0035] (3) In the technical scheme of the present application, hyaluronic acid is coated on the surface of bioactive glass. On the one hand, bioactive glass releases silicon, calcium, and phosphorus elements after degradation in the body, which can stimulate skin fibroblasts to produce more collagen, has the effect of anti-wrinkle and promoting skin repair, and hyaluronic acid itself has the characteristics of moisturizing, anti-inflammatory, and promoting repair. Cooperating with bioactive glass coated on the surface of the alloy material, a good alloy material with moisturizing, anti-wrinkle, and repair effect is formed, which has good barrier absorption performance. On the other hand, the coating of hyaluronic acid on the surface of bioactive glass endows it with active functional groups, which is beneficial to the embedding of hyaluronic acid and bioactive glass into the cellulose gel, avoiding the agglomeration of bioactive glass on the surface of the alloy material and affecting the barrier absorption performance of the alloy material.

[0036] (4) In the technical scheme of the present application, polyvinyl alcohol and carboxymethyl cellulose are combined by hydrogen bonds, and under the action of crosslinking agent epichlorohydrin, a cellulose gel is formed. The hyaluronic acid modified bioactive glass is embedded in the cellulose gel to form a composite hydrogel. The gel formed by polyvinyl alcohol and carboxymethyl cellulose as the matrix contains a large number of oxygen-containing functional groups, which has good bonding force with the alloy material, realizes the formation of a gel layer on the surface of the alloy material, improves the surface bonding force of the alloy material, and enhances the barrier absorption performance of the alloy material.

[0037] (5) In the technical scheme of the present application, the ratio of modified titanium powder, zinc powder, copper powder, magnesium powder, and silver powder and the preparation process are optimized to prepare an alloy material, and a gel layer is formed on the surface of the alloy material, which has good barrier absorption performance and can improve the skin condition. Among them, zinc and copper cooperate to promote zinc finger proteinase and copper blue proteinase to repair biological tissue, promote epidermal cell regeneration, mucosal barrier repair, and wound healing. Silver ions have antibacterial effect, which can reduce the risk of infection after barrier damage. Titanium and magnesium improve the biocompatibility of the alloy, which has good barrier absorption performance.

[0038] Zinc and copper components promote skin cell metabolism, reduce melanin deposition, and enhance skin brightness. Titanium and magnesium synergistically enhance skin collagen synthesis, inhibit elastase activity, and reduce wrinkle formation. The alloy material has excellent stability and good compatibility with the skin keratin layer, and has no adverse reactions such as redness and stinging, thereby significantly improving the skin condition. DETAILED DESCRIPTION

[0039] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0040] The raw materials used in the embodiments of the present application are shown below, and all the reagents used are analytical grade.

[0041] The titanium powder has a particle size of 2.5 μm and a purity of 99.95%, the zinc powder has a particle size of 3.5 μm and a purity of 99.9%, the copper powder has a particle size of 3 μm and a purity of 99.9%, the magnesium powder has a particle size of 2.5 μm and a purity of 99.95%, and the silver powder has a particle size of 5 μm and a purity of 99.99%.

[0042] The bioactive glass has a purity of 99% and is purchased from Wuhan Kemik Biomedical Technology Co., Ltd.

[0043] The carboxymethyl cellulose has a product number of C804618 and is purchased from Shanghai Macklin Biochemical Technology Co., Ltd.

[0044] Embodiment 1

[0045] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0046] S1. Mix the modified titanium powder, zinc powder and copper powder uniformly, put them into a smelting furnace, smelt at 1000℃ for 30 min to obtain a base melt, add magnesium powder and silver powder to the base melt, stir at 970℃ for 20 min to obtain an alloy melt; the mass ratio of the modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder is 1:4.5:1.5:0.5:0.1;

[0047] S2. Put the alloy melt into a preformed mold, cast and form, cool to room temperature, demold, and obtain an alloy ingot; the casting and forming pressure is 20 MPa;

[0048] S3. The alloy ingot is annealed, cold-rolled, immersed in a surface treatment agent, stirred at 40℃ for 20min, taken out, and dried at 80℃ for 20min to obtain an alloy material; the annealing temperature is 300℃, and the annealing time is 2h; the cold-rolling pressure is 300MPa.

[0049] The modified titanium powder is prepared by the following steps:

[0050] A1. The titanium powder and tannic acid are added to ethanol, stirred uniformly, and glucose is added, stirred at 70℃ for 30min, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10min, placed in a tube furnace, added with a 30% mass fraction potassium hydroxide solution, introduced with nitrogen, carbonized at 800℃ for 4h, cooled to room temperature, taken out, washed with deionized water for 3 times, dried in a 70℃ oven for 10min to obtain titanium powder loaded with porous carbon layer; the mass ratio of titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is 2:0.5:100:2:2;

[0051] A2. The calcium hydroxide is added to deionized water, stirred until completely dissolved, and the titanium powder loaded with porous carbon layer is added, stirred at 30℃ for 30min, and phosphoric acid is added, continued to be stirred at 400r / min for 30min, and then hydrothermal reaction is carried out at 60℃ for 2h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in a 65℃ oven for 10min to obtain modified titanium powder; the mass ratio of calcium hydroxide, deionized water, titanium powder loaded with porous carbon layer and phosphoric acid is 1.5:100:2.5:1;

[0052] The composite hydrogel is prepared by the following steps:

[0053] B1. The hyaluronic acid is added to deionized water, stirred until viscous, and the bioactive glass is added, stirred at 60℃ for 30min, filtered, washed with deionized water for 3 times, and dried in a 70℃ oven for 10min to obtain hyaluronic acid modified bioactive glass; the mass ratio of hyaluronic acid, deionized water and bioactive glass is 2:40:3;

[0054] B2. The carboxymethyl cellulose and polyvinyl alcohol are added to ethanol, ultrasonically treated at 30℃ and 40kHz for 5min, and the epoxy chloropropane and hyaluronic acid modified bioactive glass are added, stirred to form a gel, filtered, and washed with deionized water to obtain a composite hydrogel; the mass ratio of carboxymethyl cellulose, polyvinyl alcohol, ethanol, epoxy chloropropane and hyaluronic acid modified bioactive glass is 0.8:0.5:90:1:1.5.

[0055] Example 2

[0056] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0057] S1. The modified titanium powder, zinc powder and copper powder are uniformly mixed and put into a smelting furnace, smelted at 1050°C for 45 min to obtain a base melt, and then magnesium powder and silver powder are added to the base melt and stirred at 1010°C for 30 min to obtain an alloy melt; the mass ratio of the modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder is 1.3:5.2:2:1:0.4;

[0058] S2. The alloy melt is placed in a prefabricated mold, cast into shape, cooled to room temperature, demolded, and an alloy ingot is obtained; the casting forming pressure is 25 MPa;

[0059] S3. After the alloy ingot is annealed and cold-rolled, it is immersed in a surface treatment agent, stirred at 45°C for 25 min, taken out, and dried at 80°C for 20 min to obtain an alloy material; the annealing temperature is 350°C, and the annealing time is 3h; the cold rolling pressure is 330 MPa.

[0060] The modified titanium powder is prepared by the following steps:

[0061] A1. The titanium powder and tannic acid are added to ethanol, stirred uniformly, and then glucose is added, stirred at 70°C for 30 min, filtered, washed with deionized water for 3 times, dried in a 70°C oven for 10 min, placed in a tube furnace, added with a 30% potassium hydroxide solution, introduced with nitrogen, carbonized at 800°C for 4h, cooled to room temperature, taken out, washed with deionized water for 3 times, and dried in a 70°C oven for 10 min to obtain titanium powder loaded with a porous carbon layer; the mass ratio of the titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is 2.5:0.8:110:2.3:2.5;

[0062] A2. The calcium hydroxide is added to deionized water and stirred until completely dissolved, then the titanium powder loaded with a porous carbon layer is added, stirred at 30°C for 30 min, and then phosphoric acid is added, continued to stir at 400 r / min for 30 min, and then hydrothermal reaction is carried out at 60°C for 2h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in a 65°C oven for 10 min to obtain the modified titanium powder; the mass ratio of the calcium hydroxide, deionized water, titanium powder loaded with a porous carbon layer and phosphoric acid is 1.8:105:2.8:1;

[0063] The composite hydrogel is prepared by the following steps:

[0064] B1. The hyaluronic acid is added to deionized water and stirred until viscous, then the bioactive glass is added, stirred at 60°C for 30 min, filtered, washed with deionized water for 3 times, and dried in a 70°C oven for 10 min to obtain the hyaluronic acid modified bioactive glass; the mass ratio of the hyaluronic acid, deionized water and bioactive glass is 2.5:45:3.3.

[0065] B2. Carboxymethyl cellulose and polyvinyl alcohol are added into ethanol, ultrasonic treatment is carried out at 30 DEG C and 40 kHz for 5 min, epichlorohydrin and hyaluronic acid modified bioactive glass are added, stirring is carried out to form a gel, filtration is carried out, and deionized water is washed to obtain a composite hydrogel; the mass ratio of carboxymethyl cellulose, polyvinyl alcohol, ethanol, epichlorohydrin and hyaluronic acid modified bioactive glass is 1:0.8:95:1.1:1.8.

[0066] Example 3

[0067] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0068] S1. Modified titanium powder, zinc powder and copper powder are uniformly mixed, and then put into a smelting furnace to smelt at 1100 DEG C for 60 min to obtain a base melt, and then magnesium powder and silver powder are added to the base melt, and stirring is carried out at 1050 DEG C for 40 min to obtain an alloy melt; the mass ratio of modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder is 1.5:6:2.5:1.2:0.5;

[0069] S2. The alloy melt is placed in a prefabricated mold, cast into shape, cooled to room temperature, demolded, and an alloy ingot is obtained; the casting forming pressure is 30 MPa;

[0070] S3. After the alloy ingot is subjected to annealing treatment and cold rolling, it is immersed into a surface treatment agent, stirred at 50 DEG C for 30 min, taken out, and dried at 80 DEG C for 20 min to obtain an alloy material; the annealing treatment temperature is 400 DEG C, and the annealing treatment time is 4 h; the cold rolling pressure is 350 MPa.

[0071] The modified titanium powder is prepared by the following steps:

[0072] A1. Titanium powder and tannic acid are added into ethanol, stirred uniformly, glucose is added, stirring is carried out at 70 DEG C for 30 min, filtration is carried out, deionized water is washed for 3 times, drying is carried out in a 70 DEG C oven for 10 min, the obtained product is placed in a tube furnace, a 30% potassium hydroxide solution is added, nitrogen is introduced, carbonization is carried out at 800 DEG C for 4 h, the obtained product is cooled to room temperature, taken out, washed with deionized water for 3 times, and dried in a 70 DEG C oven for 10 min to obtain titanium powder loaded with a porous carbon layer; the mass ratio of titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is 3:1:120:2.5:3;

[0073] A2. Calcium hydroxide was added into deionized water and stirred until completely dissolved, and then titanium powder loaded with porous carbon layer was added and stirred at 30℃ for 30 min. Phosphoric acid was added and stirred at 400 r / min for 30 min, and then hydrothermal reaction was carried out at 60℃ for 2 h. After cooling to room temperature, filtration was performed, and deionized water washing was performed for 3 times. Drying was performed in an oven at 65℃ for 10 min to obtain modified titanium powder. The mass ratio of calcium hydroxide, deionized water, titanium powder loaded with porous carbon layer and phosphoric acid was 2:110:3:1.2;

[0074] The composite hydrogel was prepared by the following steps:

[0075] B1. Hyaluronic acid was added into deionized water and stirred until thick, and then bioactive glass was added and stirred at 60℃ for 30 min. Filtration was performed, and deionized water washing was performed for 3 times. Drying was performed in an oven at 70℃ for 10 min to obtain hyaluronic acid modified bioactive glass. The mass ratio of hyaluronic acid, deionized water and bioactive glass was 3:50:3.5.

[0076] B2. Carboxymethyl cellulose and polyvinyl alcohol were added into ethanol and ultrasonic treatment was performed at 30℃ and 40 kHz for 5 min. Epichlorohydrin and hyaluronic acid modified bioactive glass were added and stirred to form a gel. Filtration was performed, and deionized water washing was performed to obtain a composite hydrogel. The mass ratio of carboxymethyl cellulose, polyvinyl alcohol, ethanol, epichlorohydrin and hyaluronic acid modified bioactive glass was 1.2:1:100:1.2:2.

[0077] Comparative Example 1

[0078] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0079] S1. Modified titanium powder, zinc powder and copper powder were uniformly mixed and placed in a smelting furnace. Smelting was performed at 1100℃ for 60 min to obtain a base melt. Magnesium powder and silver powder were added to the base melt and stirred at 1050℃ for 40 min to obtain an alloy melt. The mass ratio of modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder was 1.5:6:2.5:1.2:0.5.

[0080] S2. The alloy melt was placed in a preform mold and cast into shape. After cooling to room temperature, demolding was performed to obtain an alloy ingot. The casting forming pressure was 30 MPa.

[0081] S3. After annealing treatment and cold rolling of the alloy ingot, the alloy ingot was immersed in a surface treatment agent and stirred at 50℃ for 30 min. After taking out, drying was performed at 80℃ for 20 min to obtain an alloy material. The annealing treatment temperature was 400℃, and the annealing treatment time was 4 h. The cold rolling pressure was 350 MPa.

[0082] The modified titanium powder was prepared by the following steps:

[0083] Calcium hydroxide was added to deionized water, stirred until completely dissolved, titanium powder was added, stirred at 30℃ for 30min, phosphoric acid was added, continued to stir at 400r / min for 30min, then hydrothermal reaction was carried out at 60℃ for 2h, cooled to room temperature, filtered, washed with deionized water for 3 times, dried in an oven at 65℃ for 10min, to obtain modified titanium powder; the mass ratio of calcium hydroxide, deionized water, titanium powder and phosphoric acid was 2:110:3:1.2;

[0084] The composite hydrogel was prepared by the following steps:

[0085] B1. Hyaluronic acid was added to deionized water, stirred until thick, bioactive glass was added, stirred at 60℃ for 30min, filtered, washed with deionized water for 3 times, dried in an oven at 70℃ for 10min, to obtain hyaluronic acid modified bioactive glass; the mass ratio of hyaluronic acid, deionized water and bioactive glass was 3:50:3.5;

[0086] B2. Carboxymethyl cellulose and polyvinyl alcohol were added to ethanol, ultrasonic treatment was carried out at 30℃, 40kHz for 5min, epoxy chloropropane and hyaluronic acid modified bioactive glass were added, stirred to form a gel, filtered, washed with deionized water, to obtain a composite hydrogel; the mass ratio of carboxymethyl cellulose, polyvinyl alcohol, ethanol, epoxy chloropropane and hyaluronic acid modified bioactive glass was 1.2:1:100:1.2:2.

[0087] Comparative Example 2

[0088] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0089] S1. Titanium powder loaded with porous carbon layer, zinc powder, copper powder were mixed uniformly, put into a smelting furnace, smelted at 1100℃ for 60min to obtain a base melt, magnesium powder and silver powder were added to the base melt, stirred at 1050℃ for 40min to obtain an alloy melt; the mass ratio of titanium powder loaded with porous carbon layer, zinc powder, copper powder, magnesium powder and silver powder was 1.5:6:2.5:1.2:0.5;

[0090] S2. The alloy melt was placed in a prefabricated mold, cast into shape, cooled to room temperature, demolded to obtain an alloy ingot; the casting forming pressure was 30MPa;

[0091] S3. After annealing treatment and cold rolling of the alloy ingot, it was immersed into a surface treatment agent, stirred at 50℃ for 30min, taken out and dried at 80℃ for 20min to obtain an alloy material; the annealing treatment temperature was 400℃, the annealing treatment time was 4h; the cold rolling pressure was 350MPa.

[0092] The titanium powder loaded with porous carbon layer is prepared by the following steps:

[0093] The titanium powder and tannic acid are added into ethanol, stirred uniformly, glucose is added, stirred at 70 DEG C for 30 min, filtered, washed with deionized water for 3 times, dried in an oven at 70 DEG C for 10 min, placed in a tube furnace, 30% potassium hydroxide solution is added, nitrogen is introduced, carbonized at 800 DEG C for 4 h, cooled to room temperature, taken out, washed with deionized water for 3 times, dried in an oven at 70 DEG C for 10 min, to obtain the titanium powder loaded with porous carbon layer; the mass ratio of titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is 3:1:120:2.5:3;

[0094] The composite hydrogel is prepared by the following steps:

[0095] B1. The hyaluronic acid is added into deionized water, stirred to be viscous, the bioactive glass is added, stirred at 60 DEG C for 30 min, filtered, washed with deionized water for 3 times, dried in an oven at 70 DEG C for 10 min, to obtain the hyaluronic acid modified bioactive glass; the mass ratio of hyaluronic acid, deionized water and bioactive glass is 3:50:3.5;

[0096] B2. The carboxymethyl cellulose and polyvinyl alcohol are added into ethanol, ultrasonic treated at 30 DEG C, 40 kHz for 5 min, the epoxy chloropropane and the hyaluronic acid modified bioactive glass are added, stirred to form a gel, filtered, washed with deionized water, to obtain the composite hydrogel; the mass ratio of carboxymethyl cellulose, polyvinyl alcohol, ethanol, epoxy chloropropane and hyaluronic acid modified bioactive glass is 1.2:1:100:1.2:2.

[0097] Comparative example 3

[0098] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0099] S1. The modified titanium powder, zinc powder and copper powder are mixed uniformly, put into a smelting furnace, smelted at 1100 DEG C for 60 min to obtain a base melt, the magnesium powder and silver powder are added into the base melt, stirred at 1050 DEG C for 40 min to obtain an alloy melt; the mass ratio of modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder is 1.5:6:2.5:1.2:0.5;

[0100] S2. The alloy melt is placed in a prefabricated mold, cast into shape, cooled to room temperature, demolded to obtain an alloy ingot; the casting forming pressure is 30 MPa;

[0101] S3. The alloy ingot is annealed, cold-rolled, immersed in a surface treatment agent, stirred at 50℃ for 30 min, taken out, and dried at 80℃ for 20 min to obtain an alloy material; the annealing temperature is 400℃, and the annealing time is 4h; the cold-rolling pressure is 350MPa.

[0102] The modified titanium powder is prepared by the following steps:

[0103] A1. The titanium powder and tannic acid are added to ethanol, stirred uniformly, and glucose is added, stirred at 70℃ for 30 min, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10 min, placed in a tube furnace, added with a 30% mass fraction potassium hydroxide solution, introduced with nitrogen, carbonized at 800℃ for 4h, cooled to room temperature, taken out, washed with deionized water for 3 times, dried in a 70℃ oven for 10 min to obtain titanium powder loaded with a porous carbon layer; the mass ratio of titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is 3:1:120:2.5:3;

[0104] A2. The calcium hydroxide is added to deionized water, stirred until completely dissolved, and the titanium powder loaded with a porous carbon layer is added, stirred at 30℃ for 30 min, and phosphoric acid is added, continued to stir at 400r / min for 30 min, and then hydrothermal reaction is carried out at 60℃ for 2h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in a 65℃ oven for 10 min to obtain modified titanium powder; the mass ratio of calcium hydroxide, deionized water, titanium powder loaded with a porous carbon layer and phosphoric acid is 2:110:3:1.2;

[0105] The composite hydrogel is prepared by the following steps:

[0106] The carboxymethyl cellulose and polyvinyl alcohol are added to ethanol, ultrasonically treated at 30℃ and 40kHz for 5 min, and the epichlorohydrin and bioactive glass are added, stirred to form a gel, filtered, and washed with deionized water to obtain a composite hydrogel; the mass ratio of carboxymethyl cellulose, polyvinyl alcohol, ethanol, epichlorohydrin and bioactive glass is 1.2:1:100:1.2:2.

[0107] Comparative Example 4

[0108] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0109] S1. The modified titanium powder, zinc powder and copper powder are uniformly mixed, placed in a smelting furnace, smelted at 1100℃ for 60 min to obtain a base melt, and the magnesium powder and silver powder are added to the base melt, stirred at 1050℃ for 40 min to obtain an alloy melt; the mass ratio of modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder is 1.5:6:2.5:1.2:0.5;

[0110] S2. The alloy melt is placed in a prefabricated mold, cast into shape, cooled to room temperature, demolded, and an alloy ingot is obtained; the casting pressure is 30 MPa;

[0111] S3. After annealing and cold rolling of the alloy ingot, the alloy ingot is immersed in a surface treatment agent, stirred at 50℃ for 30 min, taken out, and dried at 80℃ for 20 min, and an alloy material is obtained; the annealing temperature is 400℃, and the annealing time is 4h; the cold rolling pressure is 350 MPa.

[0112] The modified titanium powder is prepared by the following steps:

[0113] A1. The titanium powder and tannic acid are added to ethanol, stirred uniformly, and glucose is added, stirred at 70℃ for 30 min, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10 min, placed in a tube furnace, added with a 30% mass fraction potassium hydroxide solution, introduced with nitrogen, carbonized at 800℃ for 4h, cooled to room temperature, taken out, washed with deionized water for 3 times, dried in a 70℃ oven for 10 min, and a titanium powder loaded with a porous carbon layer is obtained; the mass ratio of the titanium powder, tannic acid, ethanol, glucose, and potassium hydroxide solution is 3:1:120:2.5:3;

[0114] A2. The calcium hydroxide is added to deionized water, stirred until completely dissolved, and the titanium powder loaded with a porous carbon layer is added, stirred at 30℃ for 30 min, and phosphoric acid is added, continued to be stirred at 400r / min for 30 min, and then hydrothermal reaction is carried out at 60℃ for 2h, cooled to room temperature, filtered, washed with deionized water for 3 times, and dried in a 65℃ oven for 10 min, and a modified titanium powder is obtained; the mass ratio of the calcium hydroxide, deionized water, titanium powder loaded with a porous carbon layer, and phosphoric acid is 2:110:3:1.2;

[0115] The composite hydrogel is prepared by the following steps:

[0116] B1. The hyaluronic acid is added to deionized water, stirred until viscous, and the bioactive glass is added, stirred at 60℃ for 30 min, filtered, washed with deionized water for 3 times, and dried in a 70℃ oven for 10 min, and a hyaluronic acid modified bioactive glass is obtained; the mass ratio of the hyaluronic acid, deionized water, and bioactive glass is 3:50:3.5;

[0117] B2. The polyvinyl alcohol is added to ethanol, ultrasonically treated at 30℃ and 40kHz for 5 min, and the epoxy chloropropane and hyaluronic acid modified bioactive glass are added, stirred to form a gel, filtered, and washed with deionized water, and a composite hydrogel is obtained; the mass ratio of the polyvinyl alcohol, ethanol, epoxy chloropropane, and hyaluronic acid modified bioactive glass is 2.2:100:1.2:2.

[0118] Comparative Example 5

[0119] A preparation method of an alloy material with improved barrier absorption, comprising the following preparation steps:

[0120] S1. The modified titanium powder, zinc powder and copper powder are uniformly mixed, and then put into a smelting furnace and smelted at 1100°C for 60 min to obtain a base melt. Magnesium powder and silver powder are added to the base melt, and stirred at 1050°C for 40 min to obtain an alloy melt. The mass ratio of the modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder is 1.5:6:2.5:1.2:0.5.

[0121] S2. The alloy melt is placed in a prefabricated mold, cast into shape, cooled to room temperature, demolded, and an alloy ingot is obtained. The casting forming pressure is 30 MPa.

[0122] S3. After annealing treatment and cold rolling of the alloy ingot, it is immersed in a surface treatment agent, stirred at 50°C for 30 min, taken out, and dried at 80°C for 20 min to obtain an alloy material. The annealing treatment temperature is 400°C, and the annealing treatment time is 4 h. The cold rolling pressure is 350 MPa.

[0123] The modified titanium powder is prepared by the following steps:

[0124] A1. The titanium powder and tannic acid are added to ethanol, stirred uniformly, and glucose is added. Stirring is carried out at 70°C for 30 min, filtered, washed with deionized water for 3 times, dried in a 70°C oven for 10 min, placed in a tube furnace, added with a 30% mass fraction potassium hydroxide solution, introduced with nitrogen, carbonized at 800°C for 4 h, cooled to room temperature, taken out, washed with deionized water for 3 times, and dried in a 70°C oven for 10 min to obtain titanium powder loaded with a porous carbon layer. The mass ratio of the titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is 3:1:120:2.5:3.

[0125] A2. The calcium hydroxide is added to deionized water and stirred until completely dissolved. The titanium powder loaded with a porous carbon layer is added and stirred at 30°C for 30 min. Phosphoric acid is added and stirring is continued at 400 r / min for 30 min. Then, hydrothermal reaction is carried out at 60°C for 2 h. After cooling to room temperature, filtration is carried out, and washing with deionized water is carried out for 3 times. Drying is carried out in a 65°C oven for 10 min to obtain the modified titanium powder. The mass ratio of the calcium hydroxide, deionized water, titanium powder loaded with a porous carbon layer and phosphoric acid is 2:110:3:1.2.

[0126] The composite hydrogel is prepared by the following steps:

[0127] B1. hyaluronic acid was added to deionized water, stirred to viscous, added bioactive glass, stirred at 60°C for 30 min, filtered, washed with deionized water for 3 times, dried in an oven at 70°C for 10 min to obtain hyaluronic acid modified bioactive glass; the mass ratio of hyaluronic acid, deionized water and bioactive glass was 3:50:3.5;

[0128] B2. carboxymethyl cellulose was added to ethanol, ultrasonic treated at 30°C, 40 kHz for 5 min, added epoxy chloropropane, hyaluronic acid modified bioactive glass, stirred to form a gel, filtered, washed with deionized water to obtain a composite hydrogel; the mass ratio of carboxymethyl cellulose, ethanol, epoxy chloropropane and hyaluronic acid modified bioactive glass was 2.2:100:1.2:2.

[0129] The alloy materials prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to performance detection.

[0130] Thirty-three healthy women aged 30-50 years old with healthy skin and facial oily sensitive skin were selected by using lactic acid sting method to screen skin sensitive population, and the healthy female subjects with lactic acid sting score > 3 were continuously used for 28 days. Instrument detection was used to observe the changes before and after the use of the test sample, so as to comprehensively evaluate the long-acting effect of the test sample used for 28 days.

[0131] Experimental method: the above prepared alloy material was installed at the water inlet of the faucet, and water was discharged for 5 minutes before each use. Volunteers washed their faces every day, and the water contacted the skin 6-8 times each day, once in the morning and once in the evening.

[0132] Elasticity and firmness efficacy detection: skin firmness and skin elasticity were detected by multi-probe skin test system CK-Cutometer MPA 580;

[0133] Skin glossiness efficacy detection: skin brightness L value and skin color ITA° were detected by multi-probe skin test system CK-Skin clororimeter CL400;

[0134] Moisturizing efficacy detection: skin keratin layer water content was detected by multi-probe skin test system CK-Corneometer CM825; trans-epidermal water loss rate TEWL was detected by multi-probe skin test system CK-Tewameter TM Hex;

[0135] Anti-wrinkle efficacy detection: wrinkle parameters SEw, corner wrinkle depth, corner wrinkle length, corner wrinkle area, corner wrinkle volume, frown wrinkle depth, frown wrinkle length, frown wrinkle area, frown wrinkle volume were detected by three-dimensional rapid imaging system PRIMOS-CR;

[0136] Sebumeter SM815 to detect the facial skin oil content;

[0137] Mexameter MX18 to detect the hematin content EI;

[0138] The results of the above tests were recorded to show the increase or decrease rate compared with the base value without using the test product.

[0139] Mechanical strength test: The tensile strength and yield strength of the alloy material prepared above were determined according to the standard GB / T 228.1-2010 "Metallic materials-tensile testing at ambient temperature".

[0140] The test results are shown in Tables 1, 2, 3 and 4 below.

[0141] Table 1: Performance test of alloy materials prepared in Examples 1-3 and Comparative Examples 1-5

[0142] Item Decrease rate of skin firmness / % Increase rate of skin elasticity / % Increase rate of skin brightness L value / % Increase rate of skin color ITA° / % Increase rate of skin horny layer moisture content / % Decrease rate of transdermal water loss / % Example 1 13.77 9.32 2.07 6.71 13.92 8.67 Example 2 13.79 9.33 2.09 6.73 13.94 8.69 Example 3 13.75 9.31 2.05 6.70 13.91 8.66 Comparative Example 1 10.32 7.32 1.55 4.21 10.45 6.21 Comparative Example 2 11.71 7.56 1.59 4.44 11.27 6.85 Comparative Example 3 5.56 3.27 0.58 2.11 5.37 3.01 Comparative Example 4 6.11 4.11 1.02 2.32 6.52 4.21 Comparative Example 5 5.95 3.75 0.67 2.27 5.68 3.88

[0143] Table 2: Performance test of alloy materials prepared in Examples 1-3 and Comparative Examples 1-5

[0144] Item Decrease rate of wrinkle parameter SEw / % Decrease rate of wrinkle depth at the corner of the eye / % Decrease rate of wrinkle length at the corner of the eye / % Decrease rate of wrinkle area at the corner of the eye / % Decrease rate of wrinkle volume at the corner of the eye / % Decrease rate of wrinkle depth at the order of the eye / % Decrease rate of wrinkle length at the order of the eye / % Decrease rate of wrinkle area at the order of the eye / % Decrease rate of wrinkle volume at the order of the eye / % Example 1 9.86 3.28 9.07 6.92 7.74 6.06 6.98 7.36 8.81 Example 2 9.88 3.30 9.09 6.93 7.76 6.08 7.00 7.38 8.83 Example 3 9.85 3.27 9.06 6.91 7.73 6.05 6.97 7.35 8.80 Comparative Example 1 7.21 2.11 7.27 4.56 5.65 4.33 4.55 5.12 6.32 Comparative Example 2 7.55 2.57 7.38 4.67 5.95 4.51 4.69 5.59 6.66 Comparative Example 3 4.11 1.06 3.44 1.01 2.11 2.41 1.55 2.06 2.45 Comparative Example 4 4.21 1.13 4.32 1.22 3.12 3.01 1.95 2.31 3.76 Comparative Example 5 4.16 1.10 3.98 1.18 2.92 2.67 1.67 2.22 2.65

[0145] Table 3: Performance test of alloy materials prepared in Examples 1-3 and Comparative Examples 1-5

[0146] Item Decrease rate of facial skin oil content / % Increase rate of hematin content EI / % Example 1 13.82 5.57 Example 2 13.88 5.59 Example 3 13.78 5.52 Comparative Example 1 10.33 3.21 Comparative Example 2 11.27 3.54 Comparative Example 3 5.74 1.02 Comparative Example 4 6.31 1.11 Comparative Example 5 5.91 1.08

[0147] Table 4: Performance test of alloy materials prepared in Examples 1-3 and Comparative Examples 1-5

[0148] Item Tensile strength / MPa Yield strength / MPa Example 1 642 441 Example 2 643 442 Example 3 641 440 Comparative Example 1 321 185 Comparative Example 2 398 201 Comparative Example 3 638 438 Comparative Example 4 635 433 Comparative Example 5 636 435

[0149] As can be seen from the data in Tables 1, 2, 3 and 4, the alloy materials prepared in Examples 1-3 have high mechanical strength and good barrier absorption performance.

[0150] The modified titanium powder prepared by replacing the porous carbon layer loaded titanium powder with titanium powder in the alloy material has decreased mechanical strength and barrier absorption performance, which proves that the porous carbon layer on the surface of the titanium powder is beneficial to the formation of hydroxyapatite on the surface of the titanium powder, improves the biocompatibility of the alloy material, and further improves the barrier absorption performance of the alloy material. In addition, the synthesized porous carbon layer provides a large amount of carbon elements, which can form carbide reinforced phase dispersed in the alloy material matrix with zinc powder, copper powder, magnesium powder and silver powder, form a dense structure alloy material, and improve the mechanical strength of the alloy material. In addition, it can slowly release zinc, copper, magnesium, silver and other metal elements to improve the skin condition.

[0151] The modified titanium powder prepared by replacing the porous carbon layer loaded titanium powder with titanium powder in the alloy material has decreased mechanical strength and barrier absorption performance, which proves that the porous carbon layer on the surface of the titanium powder is beneficial to the formation of hydroxyapatite on the surface of the titanium powder, improves the biocompatibility of the alloy material, and further improves the barrier absorption performance of the alloy material. In addition, the synthesized porous carbon layer provides a large amount of carbon elements, which can form carbide reinforced phase dispersed in the alloy material matrix with zinc powder, copper powder, magnesium powder and silver powder, form a dense structure alloy material, and improve the mechanical strength of the alloy material. In addition, it can slowly release zinc, copper, magnesium, silver and other metal elements to improve the skin condition.

[0152] The composite hydrogel prepared by replacing the hyaluronic acid modified bioactive glass with bioactive glass in the comparative example 3 is coated on the surface of the alloy material, and the barrier absorption performance is decreased, which proves that the hyaluronic acid coated on the surface of the bioactive glass endows the active functional group, which is beneficial to the embedding of the hyaluronic acid and the bioactive glass into the cellulose gel, avoids the aggregation of the bioactive glass on the surface of the alloy material, and affects the barrier absorption performance of the alloy material. In addition, the hyaluronic acid itself has the characteristics of moisturizing, anti-inflammatory and promoting repair, and cooperates with the bioactive glass coated on the surface of the alloy material to form an alloy material with good moisturizing, anti-wrinkle and repair effect, and has good barrier absorption performance.

[0153] The composite hydrogel prepared by replacing the carboxymethyl cellulose with polyvinyl alcohol in the comparative example 4 and replacing the polyvinyl alcohol with carboxymethyl cellulose in the comparative example 5 is coated on the surface of the alloy material, and the barrier absorption performance is decreased, which proves that the gel formed by taking polyvinyl alcohol and carboxymethyl cellulose as the matrix contains a large amount of oxygen-containing functional groups, and has good binding force with the alloy material. Form a gel layer on the surface of the alloy material, improve the surface binding force of the alloy material, and enhance the barrier absorption performance of the alloy material.

[0154] Long-term stability test:

[0155] The alloy material samples prepared in Examples 1-3 and Comparative Examples 1-5 were placed in a constant temperature and humidity chamber at 40℃ and 75% relative humidity to simulate the accelerated aging conditions of the daily use environment for 1 month and 3 months, respectively. At each time point, the samples were taken out and tested for the retention rate of tensile strength and stratum corneum moisture content increase rate to detect the long-term stability of the mechanical properties and functions of the samples. Among them, the performance detection method is as described above, the functional retention rate = (moisture content increase rate of the sample after aging / moisture content increase rate of the fresh sample) x 100%, and the specific test results are shown in Tables 5 and 6.

[0156] Table 5 Long-term stability test of mechanical properties of alloy materials prepared in Examples 1-3 and Comparative Examples 1-5

[0157] Item Initial tensile strength / MPa Tensile strength after 1 month / MPa Tensile strength after 3 months / MPa Example 1 642 640 640 Example 2 643 641 640 Example 3 641 639 639 Comparative Example 1 321 315 311 Comparative Example 2 398 390 388 Comparative Example 3 638 601 598 Comparative Example 4 635 625 622 Comparative Example 5 636 627 621

[0158] Table 6 Long-term stability test of function of alloy materials prepared in Examples 1-3 and Comparative Examples 1-5

[0159] Item Initial moisture increase rate (%) Function retention rate after 6 months (%) Example 1 13.92 98.5 Example 2 13.94 98.7 Example 3 13.91 98.3 Comparative Example 1 10.45 92.1 Comparative Example 2 11.27 94.3 Comparative Example 3 5.37 82.5 Comparative Example 4 6.52 88.8 Comparative Example 5 5.68 87.5

[0160] From the results in Tables 5 and 6, it can be seen that the samples in Examples 1-3 exhibit good long-term stability, with a small decrease in tensile strength and a high functional retention rate after accelerated aging simulation. Therefore, by constructing a porous carbon layer on the surface of titanium powder and in-situ synthesizing nano-hydroxyapatite, and by compounding a hyaluronic acid-modified bioactive glass / cellulose gel layer on its surface, the structural stability and functional durability of the material are fundamentally enhanced. The carbide reinforcing phase formed by the porous carbon layer and the matrix metal provides a stable mechanical skeleton; the uniformly dispersed nano-hydroxyapatite and the firmly combined composite hydrogel layer together form a stable and continuous functional element release and action interface, effectively resisting the performance degradation caused by humid heat aging.

[0161] The results in Comparative Examples 1 and 2 verify the indispensability of the porous carbon layer as a reinforcing phase and the nano-hydroxyapatite as a bioactive stabilizer for maintaining the long-term performance of the material. Without either of them, the structural integrity and stability of the bioactive interface of the material are weakened. From the results in Comparative Examples 3-5, it can be seen that the modification of hyaluronic acid is crucial for the stable immobilization of bioactive glass in the gel, which can prevent it from falling off or deactivating during the aging process. The interpenetrating network gel matrix composed of polyvinyl alcohol and carboxymethyl cellulose provides excellent adhesion and cohesive stability. Without any of the ingredients, the structural integrity of the gel layer, the bonding force with the alloy matrix, and the protection of active ingredients will all decrease, leading to premature loss or deactivation of functional elements, thereby significantly reducing the long-term efficacy.

[0162] In the description, references to "one embodiment," "an example," "certain examples" etc. mean that the particular feature, structure, material, or characteristic being described is included in at least one embodiment or example of the application. The appearances of an item in various examples or embodiments is not necessarily indicative of a frequency of occurrence in the various examples or embodiments. Moreover, descriptions of well-known methods associated are omitted so as not to obscure the disclosure.

[0163] The foregoing merely illustrates the principles of the application. Various modifications and adaptations will occur to those skilled in the art after consideration of the preceding description. All such modifications and adaptations employing the principles of the application are intended to be within the scope of the claims.

Claims

1. A method of making an alloy material having enhanced barrier absorption, characterized by, The preparation method comprises the following steps: S1. The modified titanium powder, zinc powder and copper powder are uniformly mixed and put into a smelting furnace, and then smelted at 1000-1100 DEG C for 30-60 min to obtain a base melt; the magnesium powder and silver powder are added into the base melt, and stirred at 970-1050 DEG C for 20-40 min to obtain an alloy melt; S2. The alloy melt is put into a prefabricated mold, cast into shape, cooled to room temperature, demolded, and an alloy ingot is obtained; S3. The alloy ingot is subjected to annealing treatment and cold rolling, then immersed into a surface treatment agent, stirred at 40-50 DEG C for 20-30 min, taken out, dried, and an alloy material is obtained; The modified titanium powder is obtained by synthesizing a porous carbon layer on the surface of titanium powder, and then mixed with calcium hydroxide and phosphoric acid for reaction; The surface treatment agent is obtained by mixing the composite hydrogel and deionized water according to a mass ratio of (5-10):90; The composite gel is obtained by mixing the hyaluronic acid surface modified bioactive glass, polyvinyl alcohol and carboxymethyl cellulose.

2. The method of claim 1, wherein the alloy material has improved barrier absorption. The modified titanium powder is specifically prepared by the following steps: A1. The titanium powder and tannic acid are added into ethanol, stirred uniformly, and then glucose is added and stirred uniformly; after filtration, washing and drying, the titanium powder loaded with the porous carbon layer is obtained by adding potassium hydroxide solution into a tube furnace, passing nitrogen, carbonizing, and then cooling to room temperature, washing and drying; A2. The calcium hydroxide is added into deionized water and stirred until completely dissolved; the titanium powder loaded with the porous carbon layer is added and stirred uniformly; and then the phosphoric acid is added and stirred; after hydrothermal reaction, cooling to room temperature, filtration, washing and drying, the modified titanium powder is obtained.

3. The method of claim 2, wherein the alloy material has improved barrier absorption. In step A1, the mass ratio of the titanium powder, tannic acid, ethanol, glucose and potassium hydroxide solution is (2-3):(0.5-1):(100-120):(2-2.5):(2-3).

4. The method of claim 2, wherein the alloy material has improved barrier absorption. In step A2, the mass ratio of the calcium hydroxide, deionized water, titanium powder loaded with the porous carbon layer and phosphoric acid is (1.5-2):(100-110):(2.5-3):(1-1.2).

5. The method of claim 1, wherein the alloy material has improved barrier absorption. The composite gel is specifically prepared by the following steps: B1. The hyaluronic acid is added into deionized water and stirred until viscous; and then the bioactive glass is added and stirred uniformly; after filtration, washing and drying, the hyaluronic acid modified bioactive glass is obtained; B2. The carboxymethyl cellulose and polyvinyl alcohol are added into ethanol and subjected to ultrasonic treatment; then the epichlorohydrin and the hyaluronic acid modified bioactive glass are added and stirred to form a gel; after filtration and washing, the composite gel is obtained.

6. The method of claim 5, wherein the alloy material has improved barrier absorption. In step B1, the mass ratio of the hyaluronic acid, deionized water and bioactive glass is (2-3):(40-50):(3-3.5).

7. The method of claim 5, wherein the alloy material has improved barrier absorption. In step B2, the mass ratio of the carboxymethyl cellulose, polyvinyl alcohol, ethanol, epichlorohydrin and hyaluronic acid modified bioactive glass is (0.8-1.2):(0.5-1):(90-100):(1-1.2):(1.5-2).

8. The method of claim 1, wherein the alloy material has improved barrier absorption. The mass ratio of the modified titanium powder, zinc powder, copper powder, magnesium powder and silver powder in step S1 is (1-1.5):(4.5-6):(1.5-2.5):(0.5-1.2):(0.1-0.5).

9. The method of claim 1, wherein the alloy material has improved barrier absorption. In step S2, the pressure for the casting forming is 20-30 MPa.

10. The method of claim 1, wherein the alloy material has improved barrier absorption. In step S3, the annealing treatment temperature is 300-400℃, the annealing treatment time is 2-4h, and the cold rolling pressure is 300-350 MPa.