CN106756898B - Preparation method of antibacterial hydrophobic ZnO nanorods - Google Patents

Abstract

A method for preparing antibacterial hydrophobic ZnO nanorods, comprising the following steps: step 1, mechanically polishing titanium sheets, polishing the titanium sheets in turn until the surface is smooth, placing the polished titanium sheets in acetone, absolute ethanol and deionized Ultrasonic cleaning in water for 15 minutes, natural drying at room temperature, and subsequent use; Step 2, preparing a ZnO seed layer, using the polished titanium sheet obtained in Step 1 as a substrate, and coating a uniform ZnO seed layer; Step 3, preparing ZnO nanorods, Suspend the substrate coated with the ZnO seed layer obtained in step 2 upside down in the aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine, perform a hydrothermal reaction and cool naturally, take out the substrate, wash it with deionized water, and dry it. for ZnO nanorods. Its advantages are: good antibacterial effect, no need for high temperature heating, no harmful gas generation, economical and environmental protection; broad-spectrum, high-efficiency and long-lasting antibacterial properties, and certain biocompatibility.

Description

Preparation method of antibacterial hydrophobic ZnO nanorods

technical field

The invention relates to the technical field of titanium-based biomaterials, in particular to a method for preparing antibacterial hydrophobic ZnO nanorods.

Background technique

Titanium-based biomaterials have good biocompatibility, mechanical properties and excellent corrosion resistance, and have been widely used in orthopedic and dental implant materials. However, implant-associated infections often occur during or after surgery, leading to surgical implant failure, which is mainly caused by bacterial adhesion and biofilm formation. Once biofilms are formed on the implant surface, chronic infection will ensue, and traditional medical methods based on antibiotics are generally not very effective, because bacteria have certain resistance to antibiotics and chemical disinfection agents, which will eventually leading to removal of the implant. Removing the implant will increase the patient's hospital stay and medical expenses, bring great pain to the patient in the process, and even threaten the patient's life safety.

Therefore, titanium-based biomaterials should be endowed with self-antibacterial functions, and a large number of literatures have also reported various antibacterial modifications on the surface of medical bioimplant materials. Surface modification technology, especially coating technology, can endow the surface of titanium implants with good antibacterial properties, such as antibiotic-loaded coatings, bioactive antibacterial polymer coatings, inorganic bactericide-doped coatings, anti-adhesive coatings, etc. Attached coatings and non-antibiotic organic fungicide-loaded coatings, etc. Therefore, how to prepare an antibacterial and hydrophobic nanorod is an urgent problem to be solved.

Contents of the invention

The purpose of the present invention is in order to solve above-mentioned technical defect, the preparation method of a kind of antibacterial effect lasting, efficient, broad-spectrum antibacterial hydrophobic ZnO nanorod provided, specifically comprises the following steps:

Step 1, mechanical polishing of titanium sheet

Use 240, 600, 1200 and 2400 mesh emery on a polishing machine to polish the titanium sheet in turn until the surface is smooth. Place the polished titanium sheet in acetone, absolute ethanol and deionized water for 15 minutes, and then dry it naturally at room temperature. spare;

Step 2, preparing ZnO seed layer

The polished titanium sheet obtained in step 1 is used as a substrate, and a uniform ZnO seed layer is coated by a sol-gel method or an atomic layer deposition method or a high-vacuum magnetron sputtering method;

Step 3, preparing ZnO nanorods

The substrate coated with the ZnO seed layer obtained in step 2 is inverted and suspended in an aqueous solution containing 0.015-0.025mol/L zinc nitrate hexahydrate and 0.015-0.025mol/L hexamethylenetetramine, and the hydrothermal reaction temperature is 70- 90°C, the hydrothermal reaction time is 3-6 hours, naturally cool after the reaction, take out the substrate, wash it with deionized water, and dry it to form ZnO nanorods.

Preferably, the concentration of zinc nitrate hexahydrate in step 3 is 0.025 mol/L, and the concentration of hexamethylenetetramine is 0.025 mol/L.

The sol-gel method described in step 2, concrete steps are:

1) Prepare an ethanol solution of 0.35-0.85mol/L zinc acetate dihydrate and 0.35-0.85mol/L ethanolamine, then keep stirring for 2-4 hours to obtain a colorless transparent colloid and store it at room temperature for 20-24 hours until the sol is fully Aging, that is, obtaining the precursor solution;

2) Use a spin coater to coat 20-30 μL of the precursor solution onto the titanium sheet. The first stage is 500-1000 rotations for 10-15 seconds, and the later stage is 3000-5000 rotations for 20-30 seconds. After that, blow dry with nitrogen and spin coating process Repeat 2 times;

3) After that, the titanium sheet coated with the seed layer is fired at 400-500° C. for 40-60 minutes, and slowly lowered to room temperature.

Preferably, the concentration of zinc acetate dihydrate in step 1) is 0.75mol/L, and the concentration of ethanolamine is 0.75mol/L;

In step 2), the spin coating parameters are 1000 rpm for 15s in the early stage and 5000 rpm for 30s in the later stage;

The firing parameter in step 3) is 60 minutes at 500°C.

For the atomic layer deposition method, the specific method is:

1) Use diethyl zinc (DEZ) and water as the zinc source and oxygen source to prepare a zinc oxide solution as a precursor, and then deposit the substrate, specifically at a deposition temperature of 80-100°C and a deposition pressure of 20-40Pa , under the condition that the deposition flow rate is 10-20, the deposition is carried out as a cycle with water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s, high-purity nitrogen cleaning 20s (H ₂ O/N ₂ / DEZ/N ₂ =0.1:20:0.1:20s), the number of cycles is 200-300, and a ZnO seed layer is obtained on the substrate.

Preferably, in step 1), the reaction deposition temperature is 100° C., the deposition pressure is 40 Pa, the deposition flow rate is 20, and the number of reaction cycles is 300.

For the high vacuum magnetron sputtering method, the specific method is:

1) Using radio frequency magnetron sputtering, let the pressure drop below 6.0×10 ^-4 Pa first, and then pass high-purity argon as the working gas to a pressure of 2.0-3.0Pa, the sputtering temperature is 15-25°C, and the sputtering power It is 100-120W, and the sputtering time is 80-120 seconds.

Preferably, the sputtering temperature in step 1) is 25°C, the sputtering power is 120W, and the sputtering time is 120s; the concentration of zinc nitrate hexahydrate in step 3 is 0.025mol/L, and the concentration of hexamethylenetetramine is 0.025 mol/L.

The preparation method of antibacterial hydrophobic ZnO nanorod has the advantages of:

(1) Three methods of sol-gel method, atomic layer deposition method and high vacuum magnetron sputtering are used to uniformly plate ZnO seed layer on the substrate, and the thickness of ZnO seed layer can be controlled by adjusting related parameters, which has better Antibacterial effect, no need for high temperature heating, no harmful gas generation, economical and environmentally friendly;

(2) Compared with organic antibacterial agents such as antibiotics, ZnO nanorod arrays have broad-spectrum, high-efficiency and long-lasting antibacterial properties, and have certain biocompatibility. At the same time, the hydrophobic surface has anti-scaling and anti-pollution properties, which can be used To prepare titanium-based metal biomedical implant materials and medical devices, to prevent scaling and bacterial biofilm formation on the surface of implanted stent tube materials;

(3) The preparation method is simple and easy, no toxic and harmful gas is produced, economical and environmentally friendly, and the three preparation methods of ZnO nanorod arrays with excellent antibacterial properties on the surface are prepared by the technology of the present invention, and the implementation difficulty is small, the equipment investment is small, and the consumption of resources is small. ;

Description of drawings

Figure 1 is a columnar comparison chart of the antibacterial OD of ZnO seed layer and nanorods against Staphylococcus aureus.

Among them, ALD: atomic layer deposition; sol: sol-gel; spu: high vacuum magnetron sputtering; ZnOs: zinc oxide seed layer; ZnO: zinc oxide nanorod array;

FIG. 2 is an SEM image of the titanium sheet in Example 1 after mechanical polishing.

FIG. 3 is an SEM image of the ZnO seed layer obtained by the sol-gel method in Example 1. FIG.

FIG. 4 is an SEM image of the ZnO seed layer obtained by the atomic layer deposition method in Example 2. FIG.

5 is an SEM image of the ZnO seed layer obtained by high vacuum magnetron sputtering in Example 3.

Fig. 6 is the SEM picture of hydrothermal after sol-gel method in embodiment 1.

FIG. 7 is a SEM image of hydrothermal after atomic layer deposition in Example 2. FIG.

FIG. 8 is a SEM image of hydrothermal after high vacuum magnetron sputtering in Example 3.

FIG. 9 is a contact angle diagram of the polished titanium sheet in Example 1. FIG.

FIG. 10 is a diagram of the contact angle of the ZnO seed layer obtained by the sol-gel method in Example 1. FIG.

FIG. 11 is a diagram of the contact angle of the ZnO seed layer obtained by the atomic layer deposition method in Example 2. FIG.

12 is a contact angle diagram of the ZnO seed layer obtained by high vacuum magnetron sputtering in Example 3.

FIG. 13 is a diagram of the hydrothermal contact angle after the sol-gel method in Example 1. FIG.

FIG. 14 is a diagram of the hydrothermal contact angle after atomic layer deposition in Example 2. FIG.

Fig. 15 is a diagram of the hydrothermal contact angle after high vacuum magnetron sputtering in Example 3.

FIG. 16 is an SEM image of the ZnO seed layer obtained by the sol-gel method in Example 7. FIG.

17 is an SEM image of the ZnO seed layer obtained by the sol-gel method in Example 8.

Detailed ways:

In order to better understand the present invention, the present invention will be further described in detail below in conjunction with the accompanying drawings and examples, but the protection scope of the present invention is not limited to the range indicated by the examples.

Example 1:

(1) Titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing: use 240, 600, 1200 and 2400 mesh emery on the polishing machine to polish the titanium sheet in turn until the surface is smooth, then place the polished titanium sheet in acetone, no Ultrasonic cleaning in water, ethanol and deionized water for 15 minutes, then dry naturally at room temperature, and set aside;

(2) The polished titanium sheet obtained is used as a substrate, and a uniform ZnO seed layer is plated by a sol-gel method; the specific method is to prepare an ethanol solution of 0.75mol/L zinc acetate dihydrate and 0.75mol/L ethanolamine, Then keep stirring for 4 hours to obtain a colorless transparent colloid and store it at room temperature for 24 hours. After the sol is fully aged, the precursor solution is obtained. Use a spin coater to coat 30 μL of the precursor solution on the titanium sheet. 15 seconds, 5000 rpm for 30 seconds in the later stage, then blow dry with nitrogen, repeat the spin coating process twice, then fire the titanium sheet coated with the seed layer at 500°C for 60 minutes, and slowly cool down to room temperature;

(3) First prepare 60ml of aqueous solution of 0.025mol/L zinc nitrate hexahydrate (Zn(NO ₃ ) 2) 6H ₂ O) and 0.025mol/L hexamethylenetetramine (C ₆ H ₁₂ N ₄ ), and Pour it into a hydrothermal kettle with a capacity of 100ml, and suspend the substrate coated with the ZnO seed layer obtained in step 2 upside down in the solution. The hydrothermal reaction temperature is 90°C, and the hydrothermal reaction time is 6h. After the reaction, after natural cooling Remove the substrate, rinse it with deionized water immediately and dry it for later use.

Example 2:

(1) Titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing: use 240, 600, 1200 and 2400 mesh emery on the polishing machine to polish the titanium sheet until the surface is smooth, then place the polished titanium sheet in acetone and absolute ethanol in turn and deionized water for 15 minutes, then dry naturally at room temperature and set aside;

(2) The obtained polished titanium sheet is used as a substrate, and a uniform ZnO seed layer is plated by atomic layer deposition, specifically: a zinc oxide solution is prepared with diethyl zinc (DEZ) and water as a zinc source and an oxygen source As a precursor, the substrate is then deposited. Under the conditions of a deposition temperature of 100°C, a deposition pressure of 40 Pa, and a deposition flow rate of 20, pulse water for 0.1s, high-purity nitrogen for 20s, and diethylzinc for 0.1s 1. Cleaning with high-purity nitrogen for 20 s was performed as a cycle for deposition (H ₂ O/N ₂ /DEZ/N ₂ =0.1:20:0.1:20 s), the number of cycles was 300, and a ZnO seed layer was obtained on the substrate.

(3) First prepare 60ml of aqueous solution of 0.025mol/L zinc nitrate hexahydrate (Zn(NO ₃ ) 2) 6H ₂ O) and 0.025mol/L hexamethylenetetramine (C ₆ H ₁₂ N ₄ ), and Pour it into a hydrothermal kettle with a capacity of 100ml, and suspend the substrate coated with the ZnO seed layer obtained in step 2 upside down in the solution. The hydrothermal reaction temperature is 90°C, and the hydrothermal reaction time is 6h. After the reaction, after natural cooling Remove the substrate, rinse it with deionized water immediately and dry it for later use.

Example 3:

(1) Titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing: use 240, 600, 1200 and 2400 mesh emery on the polishing machine to polish the titanium sheet until the surface is smooth, then place the polished titanium sheet in acetone and absolute ethanol in turn and deionized water for 15 minutes, then dry naturally at room temperature and set aside;

(2) Use the obtained polished titanium sheet as a substrate, and apply a uniform ZnO seed layer by high-vacuum magnetron sputtering; specifically, use radio frequency magnetron sputtering to first let the pressure drop below 6.0×10-4Pa , and then pass high-purity argon as the working gas to a pressure of 3.0Pa, a sputtering temperature of 25°C, a sputtering power of 120W, and a sputtering time of 120s;

(3) First prepare 60ml of aqueous solution of 0.025mol/L zinc nitrate hexahydrate (Zn(NO ₃ ) 2) 6H ₂ O) and 0.025mol/L hexamethylenetetramine (C6H ₁₂ N ₄ ), and mix it Pour it into a hydrothermal kettle with a capacity of 100ml, and suspend the substrate coated with the ZnO seed layer obtained in step 2 upside down in the solution. The hydrothermal reaction temperature is 90°C, and the hydrothermal reaction time is 6h. After the reaction, take out the substrate after natural cooling , immediately rinsed with deionized water and dried for later use.

Example 4:

(1) Titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing: use 240, 600, 1200 and 2400 mesh emery on the polishing machine to polish the titanium sheet until the surface is smooth, then place the polished titanium sheet in acetone and absolute ethanol in turn and deionized water for 15 minutes, then dry naturally at room temperature and set aside;

(2) The obtained polished titanium sheet is used as a substrate, and a uniform ZnO seed layer is plated by a sol-gel method; the specific method is to prepare an ethanol solution of 0.35mol/L zinc acetate dihydrate and 0.35mol/L ethanolamine, Then keep stirring for 4 hours to obtain a colorless transparent colloid and store it at room temperature for 24 hours. After the sol is fully aged, the precursor solution is obtained. Use a spin coater to coat 20 μL of the precursor solution on the titanium sheet. 15 seconds, 3000 rpm in the later stage for 30 seconds, then blow dry with nitrogen, repeat the spin coating process twice, then fire the titanium sheet coated with the seed layer at 400°C for 60 minutes, and slowly cool down to room temperature;

(3) First prepare 60ml of aqueous solution of 0.025mol/L zinc nitrate hexahydrate (Zn(NO ₃ ) 2) 6H ₂ O) and 0.025mol/L hexamethylenetetramine (C6H ₁₂ N ₄ ), and mix it Pour it into a hydrothermal kettle with a capacity of 100ml, and suspend the substrate coated with the ZnO seed layer obtained in step 2 upside down in the solution. The hydrothermal reaction temperature is 90°C, and the hydrothermal reaction time is 6h. After the reaction, take out the substrate after natural cooling , immediately rinsed with deionized water and dried for later use.

Example 5:

(1) Titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing: use 240, 600, 1200 and 2400 mesh emery on the polishing machine to polish the titanium sheet until the surface is smooth, then place the polished titanium sheet in acetone and absolute ethanol in turn and deionized water for 15 minutes, then dry naturally at room temperature and set aside;

(2) The obtained polished titanium sheet is used as a substrate, and a uniform ZnO seed layer is plated by atomic layer deposition, specifically: a zinc oxide solution is prepared with diethyl zinc (DEZ) and water as a zinc source and an oxygen source As a precursor, the substrate is then deposited. Under the conditions of a deposition temperature of 100°C, a deposition pressure of 40 Pa, and a deposition flow rate of 20, pulse water for 0.1s, high-purity nitrogen for 20s, and diethylzinc for 0.1s 1. Cleaning with high-purity nitrogen for 20 s is used as a cycle for deposition (H ₂ O/N ₂ /DEZ/N ₂ =0.1:20:0.1:20 s), the number of cycles is 300, and a ZnO seed layer is obtained on the substrate.

(3) First prepare 60ml of aqueous solution of 0.035mol/L zinc nitrate hexahydrate (Zn(NO ₃ ) 2) 6H ₂ O) and 0.035mol/L hexamethylenetetramine (C6H ₁₂ N ₄ ), and mix it Pour it into a hydrothermal kettle with a capacity of 100ml, and suspend the substrate coated with the ZnO seed layer obtained in step 2 upside down in the solution. The hydrothermal reaction temperature is 90°C, and the hydrothermal reaction time is 6h. After the reaction, take out the substrate after natural cooling , immediately rinsed with deionized water and dried for later use.

Embodiment 6:

(1) Titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing: use 240, 600, 1200 and 2400 mesh emery on the polishing machine to polish the titanium sheet until the surface is smooth, then place the polished titanium sheet in acetone and absolute ethanol in turn and deionized water for 15 minutes, then dry naturally at room temperature and set aside;

(2) Use the obtained polished titanium sheet as a substrate, and apply a uniform ZnO seed layer by high-vacuum magnetron sputtering; specifically, use radio frequency magnetron sputtering to first reduce the pressure to 6.0×10-4Pa Below, then pass high-purity argon as the working gas to a pressure of 2.0Pa, a sputtering temperature of 15°C, a sputtering power of 100W, and a sputtering time of 80s;

(3) 60ml of an aqueous solution of 0.015mol/L zinc nitrate hexahydrate (Zn(NO ₃ ) 2) 6H ₂ O) and 0.015mol/L hexamethylenetetramine (C ₆ H ₁₂ N ₄ ) was first prepared, and Pour it into a hydrothermal kettle with a capacity of 100ml, and suspend the substrate coated with the ZnO seed layer obtained in step 2 upside down in the solution. The hydrothermal reaction temperature is 70°C, and the hydrothermal reaction time is 3h. After the reaction, after natural cooling Remove the substrate, rinse it with deionized water immediately and dry it for later use.

Embodiment 7:

(1) Place clean glass slides (1×1cm ² ) in acetone, absolute ethanol, and deionized water for 15 minutes, and then dry them naturally at room temperature for later use;

(2) Consistent with the specific method of the sol-gel in embodiment 1;

(3) with embodiment 1.

Embodiment 8:

(1) with embodiment 1;

(2) With the specific method of the sol-gel in embodiment 1 (2), only the number of repetitions of the spin coating process is changed to three times;

(3) with embodiment 1.

Carry out corresponding detection result analysis to embodiment 1-3: the ZnO seed layer that three kinds of methods prepare are all evenly distributed on the surface of titanium substrate, in addition, compare sol-gel method, through atomic layer deposition method, high vacuum magnetron sputtering The ZnO nanorod array after hydrothermal growth is almost perpendicular to the substrate, and the distribution is more uniform. The diameter of the ZnO nanorod is about 100nm and the length is about 2μm. Compared with the ZnO seed layer, the prepared ZnO nanorod array has a better antibacterial effect, such as The antibacterial OD bar chart of the ZnO seed layer and nanorods against Staphylococcus aureus shown in Figure 1 shows that pure Ti has almost no antibacterial activity, the antibacterial activity of ALD-ZnOs is 45.5%, and the antibacterial activity of ALD-ZnO The antibacterial activity of Sol-ZnOs is 97.0%, the antibacterial activity of Sol-ZnOs is 90.2%, the antibacterial activity of Sol-ZnO is 96.4%, the antibacterial activity of Spu-ZnOs is 45.0%, and the antibacterial activity of Spu-ZnO is 98.2%.

The surface morphology of the prepared ZnO seed layer and nanorods was analyzed, as shown in Figure 2-8. According to SEM analysis, the ZnO seed layers prepared by the three methods were evenly distributed on the surface of the titanium substrate. In addition, compared with the sol Gel method, the ZnO nanorod array grown by atomic layer deposition and high vacuum magnetron sputtering is almost perpendicular to the substrate, and the distribution is more uniform. The diameter of the ZnO nanorod is about 100nm and the length is about 2.5μm; 7 and 8 conducted SEM tests with glass substrates and analyzed the test results. As shown in Figures 16 and 17, compared with titanium substrates, the ZnO nanorods grown by hydrothermal method on glass substrates after sol-gel method are more vertical , denser; the analysis of the detection results of Example 8: compared with the spin-coating process repeated twice, the surface of the ZnO nanorod array grown three times became more uneven.

The hydrophobicity test of ZnO nanorods, the contact angle of the liquid on the surface of the solid material is an important parameter to measure the wettability of the liquid on the surface of the material, and then obtain many of the solid-liquid and solid-gas interface interactions on the surface of the material. Information, as shown in Figure 9-15, through the analysis and test of the contact angle diagram, the contact angle diagram of the polished titanium sheet is 78.3±1.1° (as shown in Figure 9), and the contact angle of the ZnO seed layer obtained by the sol-gel method The angle figure is 43.3 ± 4.8 ° (as shown in Figure 10), the contact angle figure of the ZnO seed layer obtained by atomic layer deposition is 80.7 ± 1.5 ° (as shown in Figure 11), the ZnO obtained by high vacuum magnetron sputtering The contact angle diagram of the seed layer is 93.8±1.4° (as shown in Figure 12), the contact angle diagram of hydrothermal after the sol-gel method is 95.0±1.7° (as shown in Figure 13), and the hydrothermal contact angle diagram after the atomic layer deposition method The thermal contact angle diagram is 140.2±1.2° (as shown in FIG. 14 ), and the hydrothermal contact angle diagram after high vacuum magnetron sputtering is 141.2±3.7° (as shown in FIG. 15 ). It can be seen from the contact angle diagram analysis that the prepared ZnO nanorods have good hydrophobic properties, and the ZnO nanorods treated by sol-gel method hydrothermal treatment, atomic layer deposition method and high vacuum magnetron sputtering method have good hydrophobic properties. Hydrophobic works best.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (7)

1. the preparation method of antibacterial hydrophobic ZnO nanorod, feature mainly include the following steps:

Step 1, titanium sheet mechanical polishing processing

Successively titanium sheet is polished with 240,600,1200 and 2400 mesh diamond dust on polishing machine, until surface is smooth, by polishing titanium Piece, which is sequentially placed into acetone, dehydrated alcohol and deionized water, to be respectively cleaned by ultrasonic 10-15 minutes, is spontaneously dried at room temperature, spare；

Step 2 prepares ZnO seed layer

The polishing titanium sheet that step 1 is obtained is as substrate, using sol-gel method or atomic layer deposition method or high vacuum magnetic control Sputtering method plates one layer of uniform ZnO seed layer；

Step 3 prepares ZnO nanorod

By step 2 obtain be coated with ZnO seed layer substrate inversion be suspended in 0.015-0.025mol/L zinc nitrate hexahydrate, In the aqueous solution of 0.015-0.025mol/L hexamethylenetetramine, hydrothermal temperature is 70 DEG C, and the hydro-thermal reaction time is 3 small When, natural cooling after reaction, take out it is dry after being cleaned with deionized water after substrate after be ZnO nanorod；

Sol-gel method described in step 2, specific steps are as follows:

1) ethanol solution for preparing 0.35-0.85mol/L acetic acid dihydrate zinc and 0.35-0.85mol/L ethanol amine, continues later Stirring obtains colorless and transparent colloid for 2-4 hours and saves 20-24 hours at room temperature, is sufficiently aged to colloidal sol, i.e. acquisition forerunner Liquid solution；

2) using on rotary coating instrument coating 20-30 μ L precursor solution to titanium sheet, 500-1000 early period turns to continue 10-15 seconds, Later period 3000-5000 turns to continue 20-30 seconds, and later with being dried with nitrogen, spin coating process is repeated 2 times；

3) be coated with after the titanium sheet of seed layer 400-500 DEG C firing 40-60 minutes, be slowly dropped to room temperature；

For atomic layer deposition method, method particularly includes:

Burnett's solution is prepared as presoma as zinc source and oxygen source using diethyl zinc and water, and then substrate is deposited, It is specially 80-100 DEG C, deposition pressure 20-40Pa in depositing temperature, under conditions of deposition flow is 10-20, with water flowing arteries and veins It rushes 0.1s, High Purity Nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s to be deposited as a circulation, recycle Number is 200-300, and ZnO seed layer is obtained in substrate；

For high vacuum magnetron sputtering method, method particularly includes:

Using rf magnetron sputtering, pressure is first allowed to drop to 6.0 × 10-4Pa hereinafter, then leading to high-purity argon as working gas to pressure Power is 2.0-3.0Pa, and sputter temperature is 15-25 DEG C, sputtering power 100-120W, sputtering time 80-120 seconds.

2. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, which is characterized in that described in step 2 Sol-gel method in acetic acid dihydrate zinc concentration 1) be 0.75mol/L, the concentration of ethanol amine is 0.75mol/L.

3. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, which is characterized in that the rotation of step 2) Apply parameter is to continue 15s 1000 turns of early period, and 5000 turns of the later period continue 30s.

4. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, which is characterized in that the burning of step 3) Parameter processed is 60 minutes at 500 DEG C.

5. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, which is characterized in that step 1) it is anti- Answering depositing temperature is 100 DEG C, deposition pressure 40Pa, deposition flow are 20, reaction cycle number is 300.

6. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, which is characterized in that step 1) is splashed Penetrate temperature be 25 DEG C, sputtering power 120W, sputtering time 120s.

7. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, which is characterized in that described in step 3 The concentration of zinc nitrate hexahydrate is 0.025mol/L, the concentration of hexamethylenetetramine is 0.025mol/L.