CN112111733B

CN112111733B - Surface modified metal material and preparation method and application thereof

Info

Publication number: CN112111733B
Application number: CN201910876648.8A
Authority: CN
Inventors: 王国成; 杨明刚
Original assignee: Shenzhen Institute of Advanced Technology of CAS
Current assignee: Shenzhen Institute of Advanced Technology of CAS
Priority date: 2019-09-17
Filing date: 2019-09-17
Publication date: 2023-04-11
Anticipated expiration: 2039-09-17
Also published as: CN112111733A

Abstract

The invention relates to a surface modified metal material, a preparation method and application thereof. The preparation method comprises the following steps: and mixing the metal material with an acid solution, and then carrying out hydrothermal reaction to form a metal oxide film with a nano topological structure on the surface of the metal material in situ. The formation of the oxide film can obviously improve the biocompatibility of the material, and the oxide film has good tissue growth induction capability and good antibacterial performance; the oxide film is formed in situ on the metal matrix, no obvious interface exists between the oxide film and the matrix material, the risk of falling off the oxide film from the matrix is greatly reduced, the bonding strength between the modification layer and the substrate material is ensured, and the application range of the oxide film is expanded.

Description

Surface modified metal material and preparation method and application thereof

Technical Field

The invention relates to the technical field of material surface modification, in particular to a surface-modified metal material and a preparation method and application thereof, and especially relates to a surface-modified titanium-based material and a preparation method and application thereof.

Background

Biomedical materials are used for diagnosing, treating, repairing or replacing tissues and organs which have pathological changes, and improving functions. Many metal or alloy materials, especially titanium and titanium alloy, have excellent biocompatibility, corrosion resistance, excellent comprehensive performance and technological properties, are widely applied to dental implants, artificial joints and bone wounds, and become the preferred materials for human hard tissue substitutes and restorations. In order to improve the bioactivity, wear resistance/corrosion resistance and blood compatibility of titanium and titanium alloys, surface modification of titanium and titanium alloys is required. At present, the commonly used surface modification methods of titanium and titanium alloy mainly comprise chemical heat treatment, ion injection, micro-arc oxidation, electroplating, vapor deposition, thermal spraying, laser surface alloying, laser cladding method and the like, the modification technologies can obtain a bioactive surface and improve the biocompatibility of the titanium alloy surface, but the problem of weak bonding strength between a coating and a substrate often exists, in addition, the reaction conditions of the methods are relatively harsh, and the required equipment is expensive, so that the large-scale production is not facilitated, and the application of the methods is limited.

Compared with the hydrothermal treatment technology, the hydrothermal treatment technology not only can obtain better bioactivity, but also can be more tightly combined with the matrix, so that the hydrothermal treatment technology is widely applied. The hydrothermal method is to heat a reaction vessel in a specially-made closed reaction vessel (autoclave) by using an aqueous solution as a reaction medium to create a high-temperature and high-pressure reaction environment, thereby preparing materials with different properties. The method can realize local or overall surface modification of the implant. And the hydrothermal method has stable process and simple operation.

CN107903425A discloses a method for preparing a PVC composite material by modifying titanium dioxide/zinc oxide in situ. Adding graphite into the anthocyanin concentrated solution to perform oxidation-reduction reaction to obtain a graphene solution; fully mixing a titanium tetrachloride solution and a zinc sulfate heptahydrate solution under the condition of mechanical stirring to obtain a precursor; hydrothermal synthesis, mixing the prepared precursor with a graphene solution, adding the mixture into a high-pressure reaction kettle for hydrothermal synthesis, naturally cooling to room temperature, filtering, washing and drying a hydrothermal product; the product was coated on the PVC surface.

CN108385369A discloses a preparation method of a single-layer porous titanium dioxide modified textile based on a hydrothermal reaction, wherein F127 is added into tetrahydrofuran, butyl phthalate is added after dissolution, hydrochloric acid is added dropwise while stirring, and a gel material of a precursor coated with titanium is obtained; adding the titanium precursor into a mixed solvent of ethanol/glycerol to obtain a finishing solution, soaking the activated textile into the finishing solution, and soaking twice and rolling twice to obtain a textile modified by the titanium precursor; adding the mixture into a hydrothermal reaction kettle containing a polytetrafluoroethylene lining, carrying out hydrothermal treatment, and carrying out high-temperature heat treatment to obtain the single-layer porous titanium dioxide modified textile. The porous titanium dioxide layer on the surface of the textile prepared by the method is few in layer number, good in binding fastness with the textile, not easy to fall off, good in water washing resistance and long and stable in self-cleaning effect.

The current common technical method for preparing the porous titanium dioxide structure by using a hydrothermal method comprises the following steps: the method comprises the steps of heating precursor solutions such as titanium tetrachloride to a certain temperature, preserving heat for a certain time, and cooling to room temperature to prepare the titanium dioxide coating with the micro-nano structure on substrate materials such as silicon wafers. However, in the prior art, titanium dioxide coatings with different micro-nano structures are prepared on different substrate materials through a titanium precursor solution, the bonding strength between the coatings and the substrate materials cannot be guaranteed, and the application range of the titanium dioxide coatings is limited, so that the development of a biomedical material which is not easy to fall off from the surface of a substrate and has excellent antibacterial performance and tissue growth induction performance is very significant.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a surface modified metal material and a preparation method and application thereof, and particularly provides a surface modified titanium-based material (titanium and/or titanium alloy) and a preparation method and application thereof. The material has good tissue growth induction capability and antibacterial performance, and no obvious interface exists between an oxide film on the surface of the material and a substrate, so that the risk of falling off of the film from the substrate is greatly reduced.

In order to achieve the purpose, the invention adopts the following technical scheme:

in one aspect, the present invention provides a surface-modified metal material, which includes a metal material substrate and an oxide film having a nano-topology structure formed in situ on the surface of the substrate.

The oxide film of the invention has a nano topological structure, which is a multi-level micro-nano structure formed by a plurality of metal oxide nanorod crystal grains which are arranged in a staggered manner (the specific structure can be seen in a c diagram in an attached figure 2 in the specification).

The surface of the material has an oxide film with a nano topological structure formed in situ on a metal matrix, the formation of the oxide film can obviously improve the biocompatibility of the material, and the unique nano topological structure is favorable for the growth of soft tissues, namely, the proliferation of cells (particularly gingival fibroblasts and osteoblasts) can be promoted, so that the material has good tissue growth induction capability; the unique nano topological structure can effectively inhibit the adhesion of bacteria, namely, the antibacterial agent has good antibacterial performance; further, the oxide film has a special light absorption characteristic, and as is clear from fig. 7, the absorption peak of titanium oxide can be controlled from the ultraviolet region to the visible light region or the near-infrared region by controlling the structure of the oxide film on the surface of the titanium alloy substrate. Titanium oxide has wide application in photocatalytic degradation of organic matters, catalytic hydrogen production, dye-sensitized solar cells and the like at present, and importantly, the application is related to the light absorption performance of titanium oxide, so that the titanium oxide has high possibility of being applied in the aspect. In addition, the titanium oxide also has potential application in the aspect of Raman enhanced spectroscopy (SERS), in the invention, the inventor prepares a 5nm gold (Au) film on the surface of the sample obtained in the embodiment 1, and adopts rhodamine 6G (R6G) as Raman tag, so that the application of the material related to the invention in SERS is verified, and a good effect is obtained.

More importantly, the oxide film is formed in situ on the metal substrate, no obvious interface exists between the oxide film and the substrate material, the risk of falling off the oxide film from the substrate is greatly reduced, the bonding strength between the modification layer and the substrate material is ensured, and the application range of the oxide film is expanded.

Preferably, the metal material is titanium and/or a titanium alloy, and the oxide film is a titanium oxide film.

Preferably, the titanium oxide is single crystalline titanium oxide.

The monocrystalline silicon dioxide constructed in situ on the titanium and/or titanium alloy surface has higher crystallinity, and has higher surface energy due to the exposure of a high-crystalline-energy surface, so that the catalytic performance is stronger, and the monocrystalline silicon dioxide has extremely strong antibacterial capability under the irradiation of a proper waveband. In addition, because the titanium oxide single crystal has different active crystal faces and high surface energy, the titanium oxide single crystal is favorable for hydrolysis to form an active interface rich in hydroxyl, and the interface rich in hydroxyl can induce the formation of bone-like apatite and promote the adsorption of protein, thereby improving the adhesion of cells; secondly, the titanium oxide single crystal has well-developed appearance, and the multilayer topological structure formed by the single crystal can promote the proliferation and adhesion of cells.

In another aspect, the present invention provides a method for preparing the surface-modified metal material, the method comprising: and mixing the metal material with an acid solution, and then carrying out hydrothermal reaction to form a metal oxide film with a nano topological structure on the surface of the metal material in situ, so as to obtain the surface modified metal material.

The preparation method is simple and feasible, relatively loose in reaction conditions, inexpensive in required equipment, beneficial to large-scale production and capable of expanding application of the preparation method. And other additives are not introduced in the reaction process, so that the material has good biocompatibility, meanwhile, the in-situ formed oxide film with a topological structure has good cell proliferation promoting effect and antibacterial effect, the problem of weak combination with a matrix is avoided, and the long-term stability of the material is facilitated.

Preferably, the acid comprises any one of hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, boric acid, formic acid or acetic acid, or a combination of at least two thereof; combinations of the at least two such as a combination of hydrochloric acid and sulfuric acid, a combination of nitric acid and phosphoric acid, a combination of formic acid and acetic acid, and the like, preferably hydrochloric acid.

Preferably, the preparation method comprises the following steps: mixing titanium and/or titanium alloy with hydrochloric acid solution, and then carrying out hydrothermal reaction to form a titanium oxide film with a nano topological structure on the surface of the titanium and/or titanium alloy in situ, thereby obtaining the surface modified metal material.

Preferably, the hydrochloric acid solution is an aqueous hydrochloric acid solution.

Preferably, the concentration of the aqueous hydrochloric acid solution is 0.01 to 0.5mol/L, such as 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.18mol/L, 0.2mol/L, 0.25mol/L, 0.4mol/L, or 0.5mol/L, etc., preferably 0.05 to 0.4mol/L, and more preferably 0.15 to 0.18mol/L.

The concentration of the hydrochloric acid aqueous solution is one of key factors influencing the surface appearance of a final product and further influencing the performance of the product, and the appearance of acid corrosion is presented on the surface of a material with excessive concentration; too small a concentration of material surface will form many small particulate matter rather than the relatively intact nanotopography we need, so the acid concentration cannot be too high or too low.

Preferably, the ratio of the surface area of the titanium and/or titanium alloy to the volume of the hydrochloric acid solution is 90-120mm ² mL, e.g. 90mm ² /mL、95mm ² /mL、100mm ² /mL、105mm ² /mL、110mm ² /mL、115mm ² /mL or 120mm ² /mL。

The ratio of the surface area of the titanium and/or the titanium alloy to the volume of the hydrochloric acid solution is high or low, which has an important influence on the performance of the finally prepared product, specifically, if the volume of the hydrochloric acid solution is further increased, the surface of the prepared sample is in an acid corrosion shape, and if the volume of the hydrochloric acid solution is reduced on the basis, the surface of the prepared sample is in a small granular shape, which is not in a required shape.

Preferably, the temperature of the hydrothermal reaction is 100-300 ℃, such as 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 210 ℃, 240 ℃, 250 ℃, 260 ℃, 280 ℃ or 300 ℃ and the like; preferably 120 to 240 ℃; further preferably 180 to 210 ℃.

The temperature of the hydrothermal reaction is also one of the key factors influencing the surface appearance of the final product and further influencing the performance of the product, and most of the titanium dioxide nano rods are non-oriented although the titanium dioxide nano rods can be formed when the temperature is too low; when the temperature is too high, larger grains are generated on the surface of the material, probably because the grains grow up due to the too high temperature.

Preferably, the hydrothermal reaction time is 2-30h, such as 2h, 4h, 6h, 8h, 10h, 12h, 16h, 20h, 24h or 30h, etc.; preferably 4-24h; further preferably 4-8h.

The time of the hydrothermal reaction is also one of the key factors influencing the surface appearance of the final product and further influencing the performance of the product, and as the heat preservation time is prolonged, the crystal grains of the nano rods formed on the surface of the material grow gradually.

The special micro-nano topological structure on the surface of the material is determined by the size, orientation and shape of each nanorod crystal grain, and the size, orientation and shape of the oxide nanorod crystal grains can be controlled by changing the technical parameters (such as the type of acid, the concentration of the acid, the heat preservation time, the heat preservation temperature and the like), so that the topological structure can be regulated.

Preferably, the titanium and/or the titanium alloy is pretreated before the titanium and/or the titanium alloy is mixed with the hydrochloric acid solution and then subjected to the hydrothermal reaction, and the pretreatment operation is as follows: and cleaning the surface of the titanium and/or the titanium alloy by using acid liquor, cleaning by using deionized water, and drying. This treatment is for removing an oxide film formed on the surface of titanium and/or a titanium alloy.

Preferably, the acid solution is a mixed solution of deionized water, hydrofluoric acid and nitric acid.

Preferably, the acid solution is a mixed solution of deionized water, 48% hydrofluoric acid and 48% nitric acid, and the volume fractions of the deionized water, the 48% hydrofluoric acid and the 48% nitric acid are 66.7%, 20% and 13.3%, respectively.

Preferably, the acid cleaning time is 20-40s, such as 20s, 22s, 25s, 28s, 30s, 32s, 35s or 40 s.

Preferably, after the surface-modified metal material is obtained, it is cooled to 20 to 30 ℃, for example, 20 ℃, 22 ℃, 24 ℃, 25 ℃, 28 ℃ or 30 ℃, and the like, and is washed with deionized water and dried.

As a preferred technical scheme of the invention, the preparation method of the surface modified metal material specifically comprises the following steps:

(1) Cleaning the surface of titanium and/or titanium alloy with acid liquor for 20-40s, cleaning with deionized water for 2-5 times, and drying;

(2) Mixing titanium and/or titanium alloy with 0.01-0.5mol/L hydrochloric acid aqueous solution, carrying out hydrothermal reaction for 2-30h at 100-300 ℃ to enable a titanium oxide film with a nano topological structure to be formed on the surface of the titanium and/or titanium alloy in situ, taking out, cooling to 20-30 ℃, washing for 2-5 times by using deionized water, and drying to obtain the surface modified metal material.

In still another aspect, the present invention provides a use of the surface modified metal material as described above in biomedical materials, photocatalysis, solar cells.

Biomedical materials are particularly concerned with dental implants and bone implants. Because of the special light absorption characteristic, the material has potential application value in the field of optical treatment, photocatalysis, solar cells and the like.

Compared with the prior art, the invention has the following beneficial effects:

on one hand, the surface of the material has an oxide film with a nano topological structure formed in situ on a metal matrix, the formation of the oxide film can obviously improve the biocompatibility of the material, and the unique nano topological structure is favorable for the growth of soft tissues, namely, the proliferation of cells (particularly gingival fibroblasts and osteoblasts) can be promoted, so that the material has good tissue growth induction capability; the unique nano topological structure can effectively inhibit the adhesion of bacteria, namely, the antibacterial agent has good antibacterial performance; in addition, the oxide film has a special light absorption characteristic. More importantly, the oxide film is formed in situ on the metal substrate, no obvious interface exists between the oxide film and the substrate material, the risk of falling off the oxide film from the substrate is greatly reduced, the bonding strength between the modification layer and the substrate material is ensured, and the application range of the oxide film is expanded.

On the other hand, the preparation method is simple and feasible, the reaction conditions are relatively loose, and the required equipment is inexpensive, thereby being beneficial to large-scale production and expanding the application of the preparation method; and other additives are not introduced in the reaction process, so that the material has better biocompatibility.

Drawings

FIG. 1 is a surface topography of the acid washed titanium alloy of example 1;

FIG. 2 is a surface topography map of the surface modified titanium alloys obtained in example 1 and examples 4-8 (the scale in each figure is 100nm, and the figures a, b, c, d, e, f correspond to example 8, example 7, example 1, example 6, example 5, example 4, respectively);

FIG. 3 is a surface topography map of the surface modified titanium alloys obtained in example 1 and examples 9-12 (the scale in each figure is 100nm, and the maps a, b, c, d, e correspond to example 9, example 10, example 1, example 11, example 12, respectively);

FIG. 4 is a surface topography map of the surface modified titanium alloys obtained in example 1 and examples 13-17 (the scale of each map is 100nm, and the maps a, b, c, d, e, f correspond to example 1, example 13, example 14, example 15, example 16, example 17, respectively);

FIG. 5 is a graph showing the results of cell proliferation (HT 0, HT1, HT2, HT3, HT4 represent the control samples, example 10, example 1, example 11 and example 12 samples, respectively);

FIG. 6 is a graph showing the results of antibacterial properties (HT 0, HT1, HT2, HT3, HT4 represent the control samples, example 10, example 1, example 11, and example 12 samples, respectively);

FIG. 7 is a UV-NIR spectrum;

FIG. 8 is a Raman spectrum of evaluation test (5) (HT 1, HT2, HT3, HT4 represent samples of example 10, example 1, example 11, and example 12, respectively);

FIG. 9 is an EDS elemental analysis chart of evaluation test (5);

FIG. 10 is a Raman spectrum of the evaluation test (6).

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method comprises the following steps:

(1) Cleaning the surface of a titanium alloy (TC 4, junhang Metal materials Co., ltd., baoji city) with acid liquor for 30s, cleaning with deionized water for 3 times, and drying for later use; the preparation method of the acid liquor comprises the following steps: 20mL of deionized water, 6mL of 48% hydrofluoric acid and 4mL of 48% nitric acid were mixed and diluted 15-fold. The surface morphology of the pickled titanium alloy is observed by a scanning electron microscope, as shown in fig. 1.

(2) Mixing the above titanium alloy (surface area 2826 mm) ² ) Mixing the titanium alloy with 0.18mol/L hydrochloric acid aqueous solution (30 mL), carrying out hydrothermal reaction for 4h at 180 ℃ to form a titanium oxide film with a nano topological structure on the surface of the titanium alloy in situ, taking out the titanium oxide film, cooling to 25 ℃, washing for 3 times by using deionized water, and drying to obtain the surface modified metal material.

Example 2

(1) Cleaning the surface of the titanium alloy with acid liquor for 20s, cleaning with deionized water for 2 times, and drying for later use; the preparation method of the acid liquor comprises the following steps: 20mL of deionized water and 10mL of 48% hydrofluoric acid were mixed and diluted 15 times.

(2) Mixing the above titanium alloy (surface area 5652 mm) ² ) Mixing the titanium alloy with 0.01mol/L hydrochloric acid aqueous solution (50 mL), carrying out hydrothermal reaction at 300 ℃ for 30h to form a titanium oxide film with a nano topological structure on the surface of the titanium alloy in situ, taking out the titanium oxide film, cooling to 20 ℃, washing with deionized water for 5 times, and drying to obtain the surface modified metal material.

Example 3

(1) Cleaning the surface of the titanium alloy with acid liquor for 40s, cleaning with deionized water for 5 times, and drying for later use; the preparation method of the acid liquor comprises the following steps: 20mL of deionized water and 10mL of 48% nitric acid were mixed and diluted 15-fold.

(2) Mixing the above titanium alloy (surface area 5652 mm) ² ) Mixing the titanium alloy with 0.5mol/L hydrochloric acid aqueous solution (50 mL), carrying out hydrothermal reaction for 2h at 100 ℃ to form a titanium oxide film with a nano topological structure on the surface of the titanium alloy in situ, taking out the titanium oxide film, cooling to 30 ℃, washing for 5 times by using deionized water, and drying to obtain the surface modified metal material.

Example 4

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the concentration of the aqueous hydrochloric acid solution in the step (2) is 0.05mol/L, and the others are kept the same.

Example 5

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the concentration of the aqueous hydrochloric acid solution in the step (2) is 0.10mol/L, and the others are kept the same.

Example 6

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the concentration of the aqueous hydrochloric acid solution in the step (2) is 0.15mol/L, and the others are kept the same.

Example 7

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the concentration of the aqueous hydrochloric acid solution in the step (2) is 0.25mol/L, and the others are the same.

Example 8

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the concentration of the aqueous hydrochloric acid solution in the step (2) is 0.40mol/L, and the others are kept the same.

Example 9

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the temperature of the hydrothermal reaction in step (2) is 120 ℃, and the others are kept the same.

Example 10

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the temperature of hydrothermal reaction in step (2) is 150 ℃, and the others are kept the same.

Example 11

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the temperature of hydrothermal reaction in step (2) is 210 ℃, and the others are kept consistent.

Example 12

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of example 1 only in that the temperature of the hydrothermal reaction in step (2) is 240 ℃, and the others are kept the same.

Example 13

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of the example 1 only in that the hydrothermal reaction time in the step (2) is 8 hours, and the rest is consistent.

Example 14

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of the example 1 only in that the hydrothermal reaction time in the step (2) is 12 hours, and the rest is consistent.

Example 15

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of the example 1 only in that the hydrothermal reaction time in the step (2) is 16h, and the rest is consistent.

Example 16

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of the example 1 only in that the hydrothermal reaction time in the step (2) is 20h, and the rest is kept consistent.

Example 17

The embodiment provides a surface modified titanium alloy, which comprises a titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ. The preparation method is different from that of the example 1 only in that the hydrothermal reaction time in the step (2) is 24 hours, and the rest is consistent.

Evaluation test:

(1) And (3) observing the surface appearance:

the surface morphology of the surface-modified titanium alloys obtained in example 1 and examples 4 to 8 was observed by a scanning electron microscope, as shown in fig. 2 (fig. a, b, c, d, e, f correspond to example 8, example 7, example 1, example 6, example 5, example 4, respectively): the concentration of the hydrochloric acid aqueous solution has important influence on the surface morphology of the material, and when the concentration is more than 0.18mol/L, the surface of the titanium alloy is subjected to acid corrosion; when the concentration is lower than 0.1mol/L, small particle substances can appear on the surface of the titanium alloy; when the concentration is between 0.15mol/L and 0.18mol/L, a relatively complete titanium dioxide film with a multilevel topological structure is formed on the surface of the titanium alloy.

The surface morphology of the surface-modified titanium alloys obtained in example 1 and examples 9 to 12 was observed by a scanning electron microscope, as shown in FIG. 3 (FIGS. a, b, c, d, e correspond to example 9, example 10, example 1, example 11, and example 12, respectively): the temperature of the hydrothermal treatment has important influence on the surface appearance of the material, and when the temperature is lower than 180 ℃, most of topological structures formed on the surface of the titanium alloy are non-oriented titanium oxide nanorods; when the temperature is higher than 210 ℃, larger grains appear on the surface of the titanium alloy; when the temperature is 180-210 ℃, the topological structure formed on the surface of the titanium alloy is mostly in an oriented titanium oxide nanorod structure.

The surface morphologies of the surface-modified titanium alloys obtained in example 1 and examples 13 to 17 were observed by a scanning electron microscope, as shown in fig. 4 (fig. a, b, c, d, e, f correspond to example 1, example 13, example 14, example 15, example 16, and example 17, respectively): the time of the hydrothermal treatment also has an important influence on the surface appearance of the material, and as the time is prolonged, titanium oxide nanorod crystal grains grow gradually in a topological structure formed on the surface of the titanium alloy (the titanium oxide nanorod crystal grains are formed into nanoparticles due to undersize and cannot form a structure with staggered nano crystal grains, the titanium oxide nanorod crystal grains are too large and basically form a single crystal grain and cannot form a staggered multi-level structure, and the crystal grains are too large, so that the proliferation and antibacterial performance of cells are not improved), and the effect is optimal within the range of 4-8h.

(2) Cell proliferation assay:

the operation method comprises the following steps: samples from example 1 and examples 10-12 after hydrothermal treatment were autoclaved at 121 ℃ for 20min, placed in 24-well plates, and gingival fibroblasts (HGFs) at 5X 10 ⁴ The density of each well was inoculated on the material, and the percentage of CO was 5% at 37 ℃ using the pickled pure titanium alloy as a control ₂ After 1,3,5 and 7 days of culture in the incubator, the absorbance values were measured using CCK-8 to evaluate the proliferation of cells on different materials.

The cell proliferation results are shown in FIG. 5 (HT 0, HT1, HT2, HT3, HT4 represent control samples, example 10, example 1, example 11 and example 12 samples, respectively). As can be seen from the figure, the proliferation of HGF cells was promoted with the increase in culture time, and particularly the sample of example 1 showed the most significant effect of promoting proliferation, and the cell proliferation experiment showed that the material of the present invention was able to promote the proliferation of cells and had a significant tissue growth inducing ability.

(3) And (3) antibacterial experiments:

the operation method comprises the following steps: the materials obtained in example 1 and examples 10 to 12 were autoclaved at 121 ℃ for 20min, placed in 24-well plates, and Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus) were each sterilized at a density of 1X 10 ⁷ CFU/mL is inoculated on the material, the acid-washed pure titanium alloy is used as a control group, the material is placed in an incubator at 37 ℃ for 24 hours, and the activity of bacteria is detected by MTT to evaluate the antibacterial performance of the material.

The results of the antibacterial test are shown in FIG. 6 (HT 0, HT1, HT2, HT3, HT4 represent the control samples, example 10, example 1, example 11, and example 12, respectively). As can be seen from the figures, the material according to the present invention can significantly reduce the adhesion of e.coli and s.aureus, and exhibits good antibacterial performance. This indicates that the multilevel topology formed after hydrothermal treatment is effective in inhibiting adhesion of bacteria.

(4) Light absorption property test:

the operation method comprises the following steps: the materials obtained in examples 1 and 10 were subjected to an ultraviolet-near infrared test in a wavelength range of 365 to 2655nm to evaluate the light absorption properties of the materials, and the acid-washed pure titanium alloy was used as a control.

As shown in FIG. 7, it is understood that the pure titanium alloy has no light absorption between 365 and 2655nm, while the surface-modified titanium alloy obtained in example 10 has light absorption around 500nm, and the surface-modified titanium alloy obtained in example 1 also has light absorption around 800nm, and that the oxide film formed on the surface of the material mainly imparts the material with a specific light absorption property. The absorption peak of the titanium oxide can be adjusted from the ultraviolet range to the visible light range or the near infrared range by adjusting the structure of the oxide film on the surface of the titanium alloy substrate. Titanium oxide has wide application in photocatalytic degradation of organic matters, catalytic hydrogen production, dye-sensitized solar cells and the like, and importantly, the application is related to the light absorption performance of titanium oxide, so that the titanium oxide is very likely to be applied in the aspect.

(5) Material surface phase composition analysis and energy spectrum analysis:

the operation method comprises the following steps: the modified sample surface phase compositions obtained in example 10, example 1, example 11 and example 12 were analyzed and subjected to energy spectrum analysis using a Raman spectrometer (Raman, HORIBA Jobin Yvon, labRAM HR Evolution, france). As shown in FIG. 8 (HT 1, HT2, HT3, HT4 represent the samples of example 10, example 1, example 11, and example 12, respectively), it can be seen that anatase (144, 197,399,513,519, 639cm) appeared in all of HT1, HT2, HT3, and HT4 ^-1 ) And rutile (246, 444, 612cm) ^-1 ) Indicating that the film layer is mainly composed of anatase and rutile.

The EDS results of the modified sample obtained in example 1 are shown in FIG. 9, which shows that the film layer is mainly composed of Ti, O, al, V and C. Therefore, the experimental result shows that the film layer is a titanium oxide film layer. Therefore, the experiment shows that the film layer is the titanium dioxide film.

(6) Evaluation test of raman enhancement effect:

the operation method comprises the following steps: the modified sample obtained in the example 1 is quenched at a low temperature of 200 ℃, and 5nm gold nanoparticles are deposited on the surface. Rhodamine 6G is used as Raman tag to prepare rhodamine solutions (10) with different concentrations ^-9 M，10 ^-10 M and 10 ^-11 M) and dropped on the sample surface, and Raman signals are detected (μ -Raman spectrometer; λ =785nm; 5% of maximum laser power).

As a result, as shown in FIG. 10, it is understood from the graph that when the concentration of rhodamine is 10 ^-9 And when M is used, the intensity of the Raman signal displayed by the material is very strong, which indicates that the material has a Raman enhancement effect.

The applicant states that the present invention is illustrated by the above examples to a surface modified metal material and a preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims

1. A surface modified metal material is characterized in that the surface modified metal material comprises a titanium and/or titanium alloy substrate and a titanium oxide film with a nano topological structure formed on the surface of the substrate in situ;

the surface modified metal material is prepared by the following preparation method:

mixing titanium and/or titanium alloy with 0.15-0.18mol/L hydrochloric acid aqueous solution, and then carrying out hydrothermal reaction to form a titanium oxide film with a nano topological structure on the surface of the titanium and/or titanium alloy in situ, so as to obtain the surface modified metal material; the ratio of the surface area of the titanium and/or the titanium alloy to the volume of the hydrochloric acid solution is 90-120mm ² Per mL; the temperature of the hydrothermal reaction is 120-240 ℃; the time of the hydrothermal reaction is 4-8h.

2. The method of preparing a surface-modified metallic material of claim 1, wherein the method comprises: mixing titanium and/or titanium alloy with 0.15-0.18mol/L hydrochloric acid aqueous solution, and then carrying out hydrothermal reaction to form a titanium oxide film with a nano topological structure on the surface of the titanium and/or titanium alloy in situ, so as to obtain the surface modified metal material; the ratio of the surface area of the titanium and/or the titanium alloy to the volume of the hydrochloric acid solution is 90-120mm ² /mL。

3. The method of claim 2, wherein the titanium and/or titanium alloy is pretreated before the hydrothermal reaction after the titanium and/or titanium alloy is mixed with the hydrochloric acid solution, and the pretreatment comprises: and cleaning the surface of the titanium and/or the titanium alloy with acid liquor, cleaning with deionized water and drying.

4. The method of preparing a surface-modified metallic material of claim 3, wherein the acid solution is a mixed solution of deionized water, hydrofluoric acid, and nitric acid.

5. The method of claim 4, wherein the acid solution is a mixed solution of deionized water, 48% hydrofluoric acid and 48% nitric acid, and the volume fractions of the deionized water, the 48% hydrofluoric acid and the 48% nitric acid are 66.7%, 20%, and 13.3%, respectively.

6. The method of preparing a surface-modified metallic material of claim 3, wherein the acid cleaning time is 20-40 s.

7. The method of claim 2, wherein the surface-modified metal material is obtained and then cooled to 20-30 ℃, washed with deionized water, and dried.

8. Use of the surface modified metallic material of claim 1 in biomedical materials, photocatalysis and solar cells.