CN106756898B - The preparation method of antibacterial hydrophobic ZnO nanorod - Google Patents
The preparation method of antibacterial hydrophobic ZnO nanorod Download PDFInfo
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
Abstract
A kind of preparation method of antibacterial hydrophobic ZnO nanorod includes the following steps: step 1, titanium sheet mechanical polishing processing, successively titanium sheet is polished, until surface is smooth, polishing titanium sheet is sequentially placed into acetone, dehydrated alcohol and deionized water and is respectively cleaned by ultrasonic 15 minutes, it spontaneously dries at room temperature, it is spare；Step 2, prepares ZnO seed layer, and the polishing titanium sheet that step 1 is obtained plates one layer of uniform ZnO seed layer as substrate；Step 3, prepare ZnO nanorod, the substrate inversion for being coated with ZnO seed layer that step 2 is obtained is suspended in the aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine, carries out natural cooling after hydro-thermal reaction, is ZnO nanorod after dry after being cleaned after taking-up substrate with deionized water.Its advantage is that: there is preferable antibacterial effect, generated without high-temperature heating, also without pernicious gas, it is economic and environment-friendly；Wide spectrum, efficient and persistent antibiotic property, and there is certain biocompatibility.
Description
Technical field
The present invention relates to titanium-based technical field of biological materials, specifically a kind of system of antibacterial hydrophobic ZnO nanorod
Preparation Method.
Background technique
Titanium-based biomaterial possesses good biocompatibility, mechanical property and excellent corrosion resistance, and
It is widely used in orthopedic and dental implant material.However, implant it is relevant infection frequent occurrence in the course of surgery or
After operation, lead to implant operative failure, this is mainly caused by the formation of bacterium sticked with biomembrane.Once biomembrane is being planted
Enter body surface face to be formed, chronic infection can occur therewith, and traditional medical method based on antibiotic is typically no well
Effect, because bacterial antibiotic and chemical sterilants have certain drug resistance, this will eventually lead to the removal of implant.
Removing implant will increase hospital stays and the medical expense of patient, bring huge pain to patient in this process, very
The life security of patient can extremely be threatened.
Therefore, titanium-based biomaterial should be endowed from antibacterial functions, and lot of documents was also reported various to medical bio
Implantation material surface it is antibacterial modified.Process for modifying surface especially coating technology can assign titanium implants surface with good anti-
Bacterium performance, for example, the coating of antibiotic-loaded, the polymer coating of the antibacterial of bioactivity, inorganic fungicide doping coating,
The coating etc. of the organic bactericide load of the coating and non-antibiotic of anti-adhesive.Therefore, a kind of antibacterial, hydrophobic how is prepared
Nanometer rods are current urgent problems to be solved.
Summary of the invention
The purpose of the present invention is to solve above-mentioned technological deficiency, a kind of durable antibacterial effect for providing, efficiently, wide spectrum
The preparation method of antibacterial hydrophobic ZnO nanorod, specifically comprises 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, will be thrown
Light titanium sheet, which is sequentially placed into acetone, dehydrated alcohol and deionized water, to be respectively cleaned by ultrasonic 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
Magnetron sputtering method plates one layer of uniform ZnO seed layer；
Step 3 prepares ZnO nanorod
The substrate inversion for being coated with ZnO seed layer that step 2 is obtained is suspended in containing six water nitric acid of 0.015-0.025mol/L
Zinc, 0.015-0.025mol/L hexamethylenetetramine aqueous solution in, hydrothermal temperature be 70-90 DEG C, the hydro-thermal reaction time
Be 3-6 hours, natural cooling after reaction, take out it is dry after being cleaned with deionized water after substrate after be ZnO nanorod.
Preferably, the concentration of zinc nitrate hexahydrate is 0.025mol/L in step 3, the concentration of hexamethylenetetramine is
0.025mol/L。
Sol-gel method described in step 2, specific steps are as follows:
1) ethanol solution of 0.35-0.85mol/L acetic acid dihydrate zinc and 0.35-0.85mol/L ethanol amine is prepared, later
It persistently stirs and obtains within 2-4 hours colorless and transparent colloid and save 20-24 hours at room temperature, be sufficiently aged, that is, obtain to colloidal sol
Precursor 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
Second, 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.
Preferably, acetic acid dihydrate zinc concentration is 0.75mol/L in step 1), the concentration of ethanol amine is 0.75mol/L；
Spin coating parameters are to continue 15s 1000 turns of early period in step 2), and 5000 turns of the later period continue 30s；
It is 60 minutes at 500 DEG C that parameter is fired in step 3).
For atomic layer deposition method, method particularly includes:
1) burnett's solution is prepared as presoma, then to base as zinc source and oxygen source using diethyl zinc (DEZ) and water
Bottom is deposited, and is specially 80-100 DEG C, deposition pressure 20-40Pa in depositing temperature, the condition that deposition flow is 10-20
Under, using water flowing pulse 0.1s, High Purity Nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen clean 20s as one recycle into
Row deposition (H2O/N2/DEZ/N2=0.1:20:0.1:20s), cycle-index 200-300 obtains ZnO seed layer in substrate.
Preferably, reactive deposition temperature is 100 DEG C in step 1), deposition pressure 40Pa, deposition flow are 20, reaction follows
Ring number is 300.
For high vacuum magnetron sputtering method, method particularly includes:
1) rf magnetron sputtering is utilized, first pressure is allowed to drop to 6.0 × 10-4Then Pa is hereinafter, lead to high-purity argon as work gas
Body is 2.0-3.0Pa to pressure, and sputter temperature is 15-25 DEG C, sputtering power 100-120W, sputtering time 80-120 seconds.
Preferably, in step 1) sputter temperature be 25 DEG C, sputtering power 120W, sputtering time 120s；Six water of step 3
Nitric acid zinc concentration is 0.025mol/L, the concentration of hexamethylenetetramine is 0.025mol/L.
The preparation method of antibacterial hydrophobic ZnO nanorod, its advantage is that:
(1) it is uniformly plated in substrate using three kinds of sol-gel method, atomic layer deposition method, high vacuum magnetron sputtering methods
ZnO seed layer, while the thickness of ZnO seed layer can be controlled by regulation relevant parameter, there is preferable antibacterial effect, without height
Temperature heats, also without pernicious gas generation, economic and environment-friendly；
(2) organic antibacterial agents such as antibiotic are compared to, ZnO nano-rod array has wide spectrum, efficient and persistent antibacterial
Property, and there is certain biocompatibility, meanwhile, hydrophobic surface has antiscale and pollution-proof performance, can be used to prepare titanium-based gold
Belong to biomedical implant material and Medical instruments Appliances, prevents the fouling and bacterial biof iotalm shape of implantation stand tube material surface
At；
(3) preparation method is simple, and no toxic and harmful gas generates, economic and environment-friendly, prepares table using the technology of the present invention
Face has three kinds of preparation methods of the ZnO nano-rod array of excellent antibacterial, and enforcement difficulty is small, and equipment investment is few, consumes resource
It is few；
Detailed description of the invention
Fig. 1 is the antibacterial OD column comparison diagram of ZnO seed layer and nanometer rods to staphylococcus aureus.
Wherein, ALD: atomic layer deposition；Sol: collosol and gel；Spu: high vacuum magnetron sputtering；ZnOs: zinc oxide seed
Layer；ZnO: nanometic zinc oxide rod array；
Fig. 2 is titanium sheet mechanical polishing treated SEM figure in embodiment 1.
Fig. 3 is the ZnO seed layer SEM figure that sol-gel method obtains in embodiment 1.
Fig. 4 is the ZnO seed layer SEM figure that atomic layer deposition method obtains in embodiment 2.
Fig. 5 is the ZnO seed layer SEM figure that high vacuum magnetron sputtering obtains in embodiment 3.
Fig. 6 is the SEM figure of hydro-thermal after sol-gel method in embodiment 1.
Fig. 7 is the SEM figure of hydro-thermal after atomic layer deposition method in embodiment 2.
Fig. 8 is the SEM figure of hydro-thermal after high vacuum magnetron sputtering in embodiment 3.
Fig. 9 is the contact angle figure that titanium sheet is polished in embodiment 1.
Figure 10 is the contact angle figure for the ZnO seed layer that sol-gel method obtains in embodiment 1.
Figure 11 is the contact angle figure for the ZnO seed layer that atomic layer deposition method obtains in embodiment 2.
Figure 12 is the contact angle figure for the ZnO seed layer that high vacuum magnetron sputtering obtains in embodiment 3.
Figure 13 is the contact angle figure of hydro-thermal after sol-gel method in embodiment 1.
Figure 14 is the contact angle figure of hydro-thermal after atomic layer deposition method in embodiment 2.
Figure 15 is the contact angle figure of hydro-thermal after 3 high vacuum magnetron sputtering of embodiment.
Figure 16 is the ZnO seed layer SEM figure that sol-gel method obtains in embodiment 7.
Figure 17 is the ZnO seed layer SEM figure that sol-gel method obtains in embodiment 8.
Specific embodiment:
To be best understood from the present invention, the present invention is done further be described in detail with reference to the accompanying drawings and examples, still
The scope of protection of present invention is not limited to the range of embodiment expression.
Embodiment 1:
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing is handled: with 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively polishes titanium sheet, until polishing titanium sheet is sequentially placed into acetone, dehydrated alcohol and deionized water after surface is smooth
Each ultrasonic cleaning 15 minutes, spontaneously dries at room temperature, spare；
(2) using obtained polishing titanium sheet as substrate, one layer of uniform ZnO seed layer is plated using sol-gel method；Specifically
Method is to prepare the ethanol solution of 0.75mol/L acetic acid dihydrate zinc and 0.75mol/L ethanol amine, and persistently stirring 4h is obtained later
It saves for 24 hours, is sufficiently aged to colloidal sol to colorless and transparent colloid and at room temperature, is i.e. acquisition precursor solution, use rotary coating
Instrument coats on 30 μ L precursor solutions to titanium sheet, and parameter is that 1000 turns of early period is for 15 seconds, and 5000 turns of the later period continue 30 seconds, it
Afterwards with being dried with nitrogen, spin coating process is repeated 2 times, and the titanium sheet for being coated with seed layer later is fired 60 minutes at 500 DEG C, is slowly dropped
To room temperature；
(3) 0.025mol/L zinc nitrate hexahydrate (Zn (NO is prepared first3)2)·6H2) and six methine four of 0.025mol/L O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettle, be coated with ZnO seed for what step 2 obtained
The substrate of layer, which is inverted, to suspend in the solution, and hydrothermal temperature is 90 DEG C, the hydro-thermal reaction time 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned immediately with deionized water.
Embodiment 2:
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing is handled: with 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, dehydrated alcohol and deionized water respectively
Ultrasonic cleaning 15 minutes, spontaneously dries at room temperature, spare；
(2) using obtained polishing titanium sheet as substrate, one layer of uniform ZnO seed layer, tool are plated using atomic layer deposition method
Body are as follows: burnett's solution is prepared as presoma as zinc source and oxygen source using diethyl zinc (DEZ) and water, then substrate is carried out
Deposition is 100 DEG C, deposition pressure 40Pa in depositing temperature, under conditions of deposition flow is 20, with water flowing pulse 0.1s, height
Purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited (H as a circulation2O/N2/DEZ/N2=
0.1:20:0.1:20s), cycle-index 300 obtain ZnO seed layer in substrate.
(3) 0.025mol/L zinc nitrate hexahydrate (Zn (NO is prepared first3)2)·6H2) and six methine four of 0.025mol/L O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettle, be coated with ZnO seed for what step 2 obtained
The substrate of layer, which is inverted, to suspend in the solution, and hydrothermal temperature is 90 DEG C, the hydro-thermal reaction time 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned immediately with deionized water.
Embodiment 3:
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing is handled: with 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, dehydrated alcohol and deionized water respectively
Ultrasonic cleaning 15 minutes, spontaneously dries at room temperature, spare；
(2) using obtained polishing titanium sheet as substrate, one layer of uniform ZnO seed is plated using high vacuum magnetron sputtering method
Layer；Specifically, first allowing pressure to drop to 6.0 × 10-4Pa hereinafter, then leading to high-purity argon is working gas using rf magnetron sputtering
It is 3.0Pa to pressure, sputter temperature is 25 DEG C, sputtering power 120W, sputtering time 120s；
(3) 0.025mol/L zinc nitrate hexahydrate (Zn (NO is prepared first3)2)·6H2) and six methine four of 0.025mol/L O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettle, be coated with ZnO seed for what step 2 obtained
The substrate of layer, which is inverted, to suspend in the solution, and hydrothermal temperature is 90 DEG C, the hydro-thermal reaction time 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned immediately with deionized water.
Embodiment 4:
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing is handled: with 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, dehydrated alcohol and deionized water respectively
Ultrasonic cleaning 15 minutes, spontaneously dries at room temperature, spare；
(2) using obtained polishing titanium sheet as substrate, one layer of uniform ZnO seed layer is plated using sol-gel method；Specifically
Method is to prepare the ethanol solution of 0.35mol/L acetic acid dihydrate zinc and 0.35mol/L ethanol amine, and persistently stirring 4h is obtained later
It saves for 24 hours, is sufficiently aged to colloidal sol to colorless and transparent colloid and at room temperature, is i.e. acquisition precursor solution, use rotary coating
Instrument coats on 20 μ L precursor solutions to titanium sheet, and parameter is that 500 turns of early period is for 15 seconds, and 3000 turns of the later period continue 30 seconds, it
Afterwards with being dried with nitrogen, spin coating process is repeated 2 times, and the titanium sheet for being coated with seed layer later is fired 60 minutes at 400 DEG C, is slowly dropped
To room temperature；
(3) 0.025mol/L zinc nitrate hexahydrate (Zn (NO is prepared first3)2)·6H2) and six methine four of 0.025mol/L O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettle, be coated with ZnO seed for what step 2 obtained
The substrate of layer, which is inverted, to suspend in the solution, and hydrothermal temperature is 90 DEG C, the hydro-thermal reaction time 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned immediately with deionized water.
Embodiment 5:
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing is handled: with 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, dehydrated alcohol and deionized water respectively
Ultrasonic cleaning 15 minutes, spontaneously dries at room temperature, spare；
(2) using obtained polishing titanium sheet as substrate, one layer of uniform ZnO seed layer, tool are plated using atomic layer deposition method
Body are as follows: burnett's solution is prepared as presoma as zinc source and oxygen source using diethyl zinc (DEZ) and water, then substrate is carried out
Deposition is 100 DEG C, deposition pressure 40Pa in depositing temperature, under conditions of deposition flow is 20, with water flowing pulse 0.1s, height
Purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited (H as a circulation2O/N2/DEZ/N2=
0.1:20:0.1:20s), cycle-index 300 obtain ZnO seed layer in substrate.
(3) 0.035mol/L zinc nitrate hexahydrate (Zn (NO is prepared first3)2)·6H2) and six methine four of 0.035mol/L O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettle, be coated with ZnO seed for what step 2 obtained
The substrate of layer, which is inverted, to suspend in the solution, and hydrothermal temperature is 90 DEG C, the hydro-thermal reaction time 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned immediately with deionized water.
Embodiment 6:
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing is handled: with 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, dehydrated alcohol and deionized water respectively
Ultrasonic cleaning 15 minutes, spontaneously dries at room temperature, spare；
(2) using obtained polishing titanium sheet as substrate, one layer of uniform ZnO seed is plated using high vacuum magnetron sputtering method
Layer；Specifically, first allowing pressure to drop to as 6.0 × 10-4Pa hereinafter, then leading to high-purity argon is work gas using rf magnetron sputtering
Body is 2.0Pa to pressure, and sputter temperature is 15 DEG C, sputtering power 100W, sputtering time 80s；
(3) 0.015mol/L zinc nitrate hexahydrate (Zn (NO is prepared first3)2)·6H2) and six methine four of 0.015mol/L O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettle, be coated with ZnO seed for what step 2 obtained
The substrate of layer, which is inverted, to suspend in the solution, and hydrothermal temperature is 70 DEG C, the hydro-thermal reaction time 3h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned immediately with deionized water.
Embodiment 7:
(1) by clean sheet glass (1 × 1cm2) be sequentially placed into acetone, dehydrated alcohol and deionized water and be respectively cleaned by ultrasonic
15min is spontaneously dried at room temperature, spare；
(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 spin coating process number of repetition is changed to three times；
(3) with embodiment 1.
Carry out corresponding Analysis of test results to embodiment 1-3: the ZnO seed layer of three kinds of methods preparation is all evenly distributed on
Titanium-based bottom surface, in addition, the sol-gal process that compares, passes through hydrothermal growth after atomic layer deposition method, high vacuum magnetron sputtering
ZnO nano-rod array is almost vertical with substrate, be distributed more uniform, the diameter of ZnO nanorod about 100nm, about 2 μm of length, with
ZnO seed layer compares, and the ZnO nano-rod array of preparation has a more excellent antibacterial effect, ZnO seed layer as shown in Figure 1 and
Nanometer rods are to the antibacterial OD column comparison diagram of staphylococcus aureus, and to analyzing in figure, pure Ti is almost without antibiotic property, ALD-
The antibiotic property that the antibiotic property that the antibiotic property of ZnOs is 45.5%, ALD-ZnO is 97.0%, Sol-ZnOs is 90.2%, Sol-ZnO
Antibiotic property be 96.4%, Spu-ZnOs antibiotic property be 45.0%, Spu-ZnO antibiotic property be 98.2%.
Carrying out Analysis of Surface Topography to prepared ZnO seed layer and nanometer rods as illustrated in figs. 2 through 8 can through sem analysis
Know, the ZnO seed layer of three kinds of methods preparation is all evenly distributed on titanium-based bottom surface, in addition, the sol-gal process that compares, passes through original
The ZnO nano-rod array of hydrothermal growth is almost vertical with substrate after sublayer sedimentation, high vacuum magnetron sputtering, is distributed more equal
It is even, the diameter of ZnO nanorod about 100nm, about 2.5 μm of length；Embodiment 7,8 test simultaneously by the SEM of substrate of glass
The analysis for carrying out testing result compares titanium substrate as shown in Figure 16,17, passes through hydro-thermal after sol-gel method on the glass substrate
The ZnO nanorod of growth is more vertical, more dense；The analysis of testing result is carried out to embodiment 8: comparison spin coating process is repeated 2 times,
The ZnO nano-rod array surface for being repeated 3 times growth becomes more out-of-flatness.
Hydrophobic type test is carried out to ZnO nanorod, contact angle of the liquid on solid material surface is to measure the liquid pair
The important parameter of material surface wettability, and many letters of material surface solid-liquid, solid-air interface interaction are obtained in turn
Breath, as shown in Fig. 9-15, the analysis test through contact angle figure, the contact angle figure for polishing titanium sheet is 78.3 ± 1.1 ° (such as Fig. 9 institute
Show), the contact angle figure for the ZnO seed layer that sol-gel method obtains is 43.3 ± 4.8 ° (as shown in Figure 10), atomic layer deposition method
The contact angle figure of obtained ZnO seed layer is 80.7 ± 1.5 ° (as shown in figure 11), the ZnO seed that high vacuum magnetron sputtering obtains
The contact angle figure of layer is 93.8 ± 1.4 ° (as shown in figure 12), and the contact angle figure of hydro-thermal is 95.0 ± 1.7 ° after sol-gel method
(as shown in figure 13), the contact angle figure of hydro-thermal is 140.2 ± 1.2 ° (as shown in figure 14), high vacuum magnetic control after atomic layer deposition method
The contact angle figure of hydro-thermal is 141.2 ± 3.7 ° (as shown in figure 15) after sputtering.It can be seen that from contact angle map analysis prepared
ZnO nanorod has good hydrophobic performance, and passes through sol-gel method hydro-thermal process, atomic layer deposition method, high vacuum magnetic
The hydrophobic effect for controlling sputtering method treated ZnO nanorod is best.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the 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.
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