CN106563176B - A kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating - Google Patents
A kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating Download PDFInfo
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Abstract
A kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating of the present invention, to prepare the nanometer antibacterium coating with good antibiotic property.The second object of the present invention is to have the carbon nanotube of bioactivity and certain antibiotic property and the coating of chitosan with electrodeposition process preparation.The third object of the present invention is to prepare nano structure of zinc oxide using technique for atomic layer deposition, obtains zinc oxide/carbon nanotube antimicrobial coating, nano zine oxide and carbon nanotube is made to play Synergistic biocidal effect.
Description
Technical field
The present invention relates to material science and technical field of nano material, in particular to a kind of oxidation based on atomic layer deposition
Zinc/carbon nanotube antimicrobial coating preparation method.
Background technique
Atomic layer deposition (ALD) technology is a kind of new technology for preparing film.By being accurately controlled vaporous precursors arteries and veins
Punching and nitrogen scavenging period make reaction gas alternately deposit on the surface of the material and react to form film.Technique for atomic layer deposition has
Following advantage: firstly, relative to other traditional vapor deposition methods, atomic layer deposition can carry out at lower temperatures.
Secondly, atomic layer deposition has from restricted, make to be deposited on the amount of the substance of material surface in each of which deposition cycle to be one
Fixed.Again, since atomic layer deposition is from restricted, atomic layer deposition can accurately control growing film on atomic layer
Thickness.Finally, the film that the conformality of technique for atomic layer deposition brilliance prepares atomic layer deposition retains the shape of substrate
Looks feature.
Often along with bacterium infection, inorganic antiseptic has surgical operation in being modified as medical implant antibacterial surface
Advantage, than as can effectively inhibition bacterium in implant surfaces adherency, avoids drug-resistant bacteria caused by generating similar antibiotic.Oxidation
Zinc is a kind of broad stopband (3.37eV) semiconductor substance with broad spectrum antibacterial.Research report zinc oxide Antibacterial Mechanism include
Digestion of metallic ion sterilization mechanism, i.e. zinc ion make it inactivate and kill bacterium in conjunction with the intracorporal protease of bacterium;It is another
Mechanism is then that zinc oxide generates electron hole pair under photocatalysis, so that the oxygen in air be excited to generate active oxygen, is made
Bacterium part oxygen pressure rises or occurs oxidation reaction and kills bacterium.Carbon nanotube is a kind of to be widely used in receiving for each field
Rice material is reduced by the compound probability of the electron hole pair that in conjunction with carbon nanotube, nano zine oxide can generate, thus
Enhance the photo-catalysis capability of nano zine oxide.
In order to improve the antibacterial ability on medical implant surface.The association of carbon nanotube and chitosan and zinc oxide can be passed through
Same-action obtains the material with antibacterial surface.Make surface of metal titanium that there is loose porous Large ratio surface by alkali heat-treatment
Product structure, then having surface of metal titanium by electro-deposition can be enhanced nano structure of zinc oxide antibiotic property carbon nanotube and shell
The composite coating of glycan.Antibacterial is precipitated by the metal ion of zinc oxide and enhances later nano zinc oxide photocatalysis antibacterial
Synergistic effect, obtains the zinc oxide with good anti-microbial property/carbon nanotube antimicrobial coating.
Summary of the invention
An object of the present invention is to provide a kind of system of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating
Preparation Method, to prepare the surface of metal titanium coating with good antibiotic property.The second object of the present invention is to electro-deposition
Method preparation has the titanium of surface porosity porous structure.The third object of the present invention is the method with atomic layer deposition, is obtained
To nano structure of zinc oxide coating, make nano zine oxide and carbon nanotube that there is Synergistic biocidal effect.
A kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating, it is characterised in that including
Following steps:
S1. the concentrated sulfuric acid/nitric acid mixed acid solution that weight multiple is 100-120 times is added in carbon nanotube, after being dispersed with stirring
Increasing amount deionized water is filtered through miillpore filter, and is constantly cleaned with deionized water, until the acid on surface is rinsed well;
S2. the carbon nanotube on filter membrane is collected, is dried in vacuo for 24 hours at 40-60 DEG C, chitosan, carbon nanotube is successively delayed
Slow to be added in the mixed solution being made of dehydrated alcohol, acetic acid, ultrasonic disperse 1-1.5h, obtained suspension is with 600-1000r/
Carbon Nanotubes/Chitosan mixing suspension is made in the rate magnetic agitation 15-24h of min;
S3. titanium alloy round abrasive sheet is polished step by step, is successively cleaned by ultrasonic in ethyl alcohol, deionized water, cleaned titanium
2-4min is etched with deionized water/nitric/hydrofluoric mixed acid solution after piece is dry, is cleaned later with deionized water;
S4. etched titanium alloy disk is put into reaction kettle, NaOH solution is filled in reaction kettle, it then again will reaction
Kettle is put into baking oven, reacts 2-3h at 60-80 DEG C, the surface with porous coarse structure is made, after the completion cleaning sample;
S5. step S4 is obtained into titanium alloy disk and makees cathode, Carbon Nanotubes/Chitosan mixing suspension is as electro-deposition
Liquid, platinum plate electrode are electrolysed as anode, prepare carbon nanotube coating, electrode distance 8-10mm, voltage 20-30V, when deposition
Between be 30-35s;
S6. atomic layer deposition cycles are carried out to it again, 60-80 DEG C of depositing temperature, cycle-index 200-300 is once followed
For ring by diethyl zinc pulse 30ms, nitrogen cleans 20s, deionized water pulse 30ms, and nitrogen cleans 20s composition, obtains zinc oxide
Nanometer antibacterium coating.
The time of ultrasonic disperse is 1.5h in step S2, and the time of magnetic agitation is 18h;Step S1 filters what process used
It is 0.22 μm of miillpore filter;The acetic acid that acetic acid described in step S1 is 0.1%;The composition of nitration mixture etching liquid described in step S3
The deionized water for being 5:4:1 for volume ratio, nitric acid, the mixed solution of hydrofluoric acid;Electrode distance is 10mm in step S5, and voltage is
30V, sedimentation time 30s;The parameter of atomic layer deposition is as follows in step S5: 80 DEG C of depositing temperature, cycle-index 300, and one
For a atomic layer deposition cycles by diethyl zinc pulse 30ms, nitrogen cleans 20s, deionized water pulse 30ms, and nitrogen cleans 20s group
At obtaining the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating.
Compared with the existing technology, the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating of the present invention
Preparation method has the advantages that
(1) Nano zinc oxide film is prepared suitable for a variety of substrates using technique for atomic layer deposition;
(2) then anti-compared to simple zinc oxide due to carbon nanotube photocatalytic activity related with zinc oxide antibacterial
Bacterium, nano zine oxide and carbon nanotube synergistic effect have better antibiotic property;
(3) preparation method is simple, prepares a kind of zinc oxide/carbon based on atomic layer deposition using the technology of the present invention and receives
The preparation method of mitron antimicrobial coating, equipment investment is few, and consumption resource is few, and enforcement difficulty is small.
Detailed description of the invention
Fig. 1 is that the SEM in embodiment 1 with zinc oxide/carbon nanotube antimicrobial coating titanium disk schemes;
Fig. 2 is the antimicrobial efficiency figure of different disposal titanium disk in embodiment 1.
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) step 1: 98% concentrated sulfuric acid/65% for being 3:1 by the volume ratio that 1g carbon nanotube (CNTs) is dissolved in 120mL
In nitric acid mixed acid solution and ultrasonic disperse 3h, then magnetic agitation 36h.And then mixed liquor increasing amount deionized water is passed through
0.22 μm of miillpore filter filters, and is constantly cleaned with deionized water, until pH=7.Carbon nanotube on collection filter membrane, 60
DEG C vacuum drying for 24 hours.By 75mg chitosan (CS), the carbon nanotube that 150mg is obtained successively is slowly added to by the anhydrous second of 7.5mL
Alcohol, 142.5mL 0.1% acetic acid composition mixed solution in, be ultrasonically treated 1h, obtained suspension is with 1000r/min's
For 24 hours, Carbon Nanotubes/Chitosan mixing suspension is made in rate magnetic agitation.
(2) step 2: the NaOH solution for being equipped with 4mol/L is spare, by titanium alloy disk (diameter 6mm, thickness 2.5mm) sand
Paper is polished step by step, is successively cleaned by ultrasonic in ethyl alcohol, deionized water, and cleaned titanium sheet is after the drying 5:4:1 with volume ratio
Deionized water/nitric/hydrofluoric mixed acid solution etch 2min, cleaned later with deionized water, and then by etched titanium
Alloy disk is put into reaction kettle, and the NaOH solution of outfit is filled in reaction kettle, reaction kettle is put into baking oven, anti-at 80 DEG C
2h is answered, the surface with porous coarse structure is made, after the completion cleaning sample.
(3) step 3: step 2 is obtained as electrodeposit liquid using carbon nanotube mixing suspension obtained in step 1
Titanium alloy disk makees cathode, and platinum plate electrode makees anode, electrode distance 10mm, voltage 30V, sedimentation time 30s.Obtained electricity
Depositing coating is at once dry with deionized water, is dried at room temperature for later.Using technique for atomic layer deposition on electrodeposited coating
Nano structure of zinc oxide is prepared, the parameter of atomic layer deposition is as follows: 80 DEG C of depositing temperature, cycle-index 300.One atom
For layer deposition cycle by diethyl zinc pulse 30ms, nitrogen cleans 20s, deionized water pulse 30ms, and nitrogen cleans 20s composition.?
To the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating.
Embodiment 2:
(1) step 1: by 1.5g carbon nanotube (CNTs) be dissolved in 150mL volume ratio be 3:1 98% concentrated sulfuric acid/
In 67% nitric acid mixed acid solution and ultrasonic disperse 2.5h, then magnetic agitation 32h;And then by mixed liquor increasing amount deionization
Water is filtered through 0.22 μm of miillpore filter, and is constantly cleaned with deionized water, until pH=7.Collect the carbon nanometer on filter membrane
Pipe, 50 DEG C of vacuum drying 28h.By 65mg chitosan (CS), the carbon nanotube that 135mg is obtained successively is slowly added to anhydrous by 10mL
Ethyl alcohol, 150mL 0.1% acetic acid composition mixed solution in, be ultrasonically treated 1.5h, obtained suspension is with 1500r/min's
Carbon Nanotubes/Chitosan mixing suspension is made in rate magnetic agitation 20h.
(2) step 2: the NaOH solution for being equipped with 5mol/L is spare, by titanium alloy disk (diameter 6mm, thickness 2.5mm) sand
Paper is polished step by step, is successively cleaned by ultrasonic in ethyl alcohol, deionized water, and cleaned titanium sheet is after the drying 5:4:1 with volume ratio
Deionized water/nitric/hydrofluoric mixed acid solution etch 4min, cleaned later with deionized water, and then by etched titanium
Alloy disk is put into reaction kettle, and the NaOH solution of outfit is filled in reaction kettle, reaction kettle is put into baking oven, anti-at 80 DEG C
2h is answered, the surface with porous coarse structure is made, after the completion cleaning sample.
(3) step 3: step 2 is obtained as electrodeposit liquid using carbon nanotube mixing suspension obtained in step 1
Titanium alloy disk makees cathode, and platinum plate electrode makees anode, electrode distance 15mm, voltage 25V, sedimentation time 35s.It obtains
Electrodeposited coating is at once dry with deionized water, is dried at room temperature for later.Using technique for atomic layer deposition in electrodeposited coating
On nano structure of zinc oxide is prepared, the parameter of atomic layer deposition is as follows: 70 DEG C of depositing temperature, cycle-index 350.One original
For sublayer deposition cycle by diethyl zinc pulse 25ms, nitrogen cleans 35s, deionized water pulse 35ms, and nitrogen cleans 25s composition.
Obtain the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating.
Embodiment 3:
(1) step 1: 98% concentrated sulfuric acid/68% for being 4:1 by the volume ratio that 2g carbon nanotube (CNTs) is dissolved in 120mL
In nitric acid mixed acid solution and ultrasonic disperse 3h, then magnetic agitation 22h;And then mixed liquor increasing amount deionized water is passed through
0.22 μm of miillpore filter filters, and is constantly cleaned with deionized water, until pH=7.Carbon nanotube on collection filter membrane, 60
DEG C vacuum drying 25h.By 55mg chitosan (CS), the carbon nanotube that 145mg is obtained successively is slowly added to by 8mL dehydrated alcohol,
In the mixed solution of the 0.1% acetic acid composition of 125mL, it is ultrasonically treated 2h, obtained suspension is with the rate magnetic force of 1200r/min
18h is stirred, Carbon Nanotubes/Chitosan mixing suspension is made.
(2) step 2: the NaOH solution for being equipped with 3.5mol/L is spare, by titanium alloy disk (diameter 6mm, thickness 2.5mm)
Sand paper is polished step by step, is successively cleaned by ultrasonic in ethyl alcohol, deionized water, and cleaned titanium sheet is after the drying 5:4 with volume ratio:
1 deionized water/nitric/hydrofluoric mixed acid solution etches 4min, is cleaned later with deionized water, and then by etched titanium
Alloy disk is put into reaction kettle, and the NaOH solution of outfit is filled in reaction kettle, reaction kettle is put into baking oven, anti-at 80 DEG C
2h is answered, the surface with porous coarse structure is made, after the completion cleaning sample.
(3) step 3: step 2 is obtained as electrodeposit liquid using carbon nanotube mixing suspension obtained in step 1
Titanium alloy disk makees cathode, and platinum plate electrode makees anode, electrode distance 12mm, voltage 35V, sedimentation time 25s.It obtains
Electrodeposited coating is at once dry with deionized water, is dried at room temperature for later.Using technique for atomic layer deposition in electrodeposited coating
On nano structure of zinc oxide is prepared, the parameter of atomic layer deposition is as follows: 70 DEG C of depositing temperature, cycle-index 350.One original
For sublayer deposition cycle by diethyl zinc pulse 25ms, nitrogen cleans 35s, deionized water pulse 35ms, and nitrogen cleans 25s composition.
Obtain the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating.
Embodiment 4:
(1) step 1: by 1.2g carbon nanotube (CNTs) be dissolved in 135mL volume ratio be 3.5:1 98% concentrated sulfuric acid/
In 65% nitric acid mixed acid solution and ultrasonic disperse 2h, then magnetic agitation 15h;And then by mixed liquor increasing amount deionized water
It filters through 0.22 μm of miillpore filter, and is constantly cleaned with deionized water, until pH=7.The carbon nanotube on filter membrane is collected,
70 DEG C of vacuum drying 15h.By 80mg chitosan (CS), the carbon nanotube that 155mg is obtained successively is slowly added to by the anhydrous second of 10mL
Alcohol, 135mL 0.1% acetic acid composition mixed solution in, be ultrasonically treated 2.5h, obtained suspension is with the speed of 1300r/min
Carbon Nanotubes/Chitosan mixing suspension is made in rate magnetic agitation 15h.
(2) step 2: the NaOH solution for being equipped with 4.5mol/L is spare, by titanium alloy disk (diameter 6mm, thickness 2.5mm)
Sand paper is polished step by step, is successively cleaned by ultrasonic in ethyl alcohol, deionized water, and cleaned titanium sheet is after the drying 5:4 with volume ratio:
1 deionized water/nitric/hydrofluoric mixed acid solution etches 4min, is cleaned later with deionized water, and then by etched titanium
Alloy disk is put into reaction kettle, and the NaOH solution of outfit is filled in reaction kettle, reaction kettle is put into baking oven, anti-at 60 DEG C
2.5h is answered, the surface with porous coarse structure is made, after the completion cleaning sample.
(3) step 3: step 2 is obtained as electrodeposit liquid using carbon nanotube mixing suspension obtained in step 1
Titanium alloy disk makees cathode, and platinum plate electrode makees anode, electrode distance 8mm, voltage 25V, sedimentation time 25s.It obtains
Electrodeposited coating is at once dry with deionized water, is dried at room temperature for later.Using technique for atomic layer deposition in electrodeposited coating
On nano structure of zinc oxide is prepared, the parameter of atomic layer deposition is as follows: 70 DEG C of depositing temperature, cycle-index 350.One original
For sublayer deposition cycle by diethyl zinc pulse 25ms, nitrogen cleans 35s, deionized water pulse 35ms, and nitrogen cleans 25s composition.
Obtain the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating.
Antibiotic property measurement is carried out to antimicrobial coating: there is zinc oxide/carbon nanotube antimicrobial coating by what step 1 obtained
Titanium disk is immersed in 320 μ L phosphate buffer solutions, ultraviolet lighting 40min;Respectively in ultraviolet lighting treated titanium
Belong to detection bacterium survival rate after cultivating staphylococcus aureus 25 hours, Escherichia coli 10 hours in the culture medium that disk impregnates,
By the bacteria adhension of the titanium disk after culture bacterium, the pattern of bacterium is observed under a scanning electron microscope later.In figure
Grid is followed successively by pure titanium, alkali heat-treatment titanium, alkali heat-treatment titanium+carbon nanotube, alkali heat-treatment titanium+carbon nanotube/zinc oxide, measurement
Data are as follows: for Escherichia coli group, pure titanium is almost without antibacterial ability, the titanium crossed through alkali heat-treatment, antibiotic rate 10%, warp
What alkali heat and carbon nanotube were handled, antibiotic rate 16%, processed through alkali heat, carbon nanotube/zinc oxide, antibiotic rate is
72%;For staphylococcus aureus group, pure titanium, the titanium crossed through alkali heat-treatment, the titanium handled through alkali heat and carbon nanotube are several
There is no antibacterial ability, antibiotic rate 98% processed through alkali heat, carbon nanotube/zinc oxide shows it with good anti-
Bacterium effect.
It is tested through analysis, compared with the existing technology, it can be deduced that such as draw a conclusion: 1) SEM test is carried out to titanium disk,
The surface of metal titanium that alkali heat-treatment obtains has loose porous bigger serface coarse structure, what technique for atomic layer deposition obtained
Nano zine oxide/carbon nanotube structure distribution is uniform, and oxidation zinc concentration is higher, and the diameter of obtained nanometer rods is got over
Greatly;2) the staphylococcus aureus by the modified titanium disk surfaces in surface and Bacillus coli cells film be not complete, table
Reveal bacterial growth not to be suppressed, the golden yellow with zinc oxide/carbon nanotube antimicrobial coating titanium disk surfaces
There is damaged or shrinkage in staphylococcus and Bacillus coli cells film, show good antibacterial ability, but just to golden yellow
Staphylococcic antibiotic rate, the antibacterial effect that carbon nanotube is added are better than the antibacterial effect that carbon nanotube is not added, and addition is received
The antibacterial effect of rice zinc oxide is better than the antibacterial effect that nano zine oxide is not added;3) it is received using technique for atomic layer deposition preparation
Rice zinc-oxide film is suitable for a variety of substrates and is then compared due to carbon nanotube photocatalytic activity related with zinc oxide antibacterial
In simple zinc oxide antibacterial, nano zine oxide and carbon nanotube synergistic effect have better antibiotic property, and preparation method is simple
It is easy, a kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating is prepared using the technology of the present invention,
Equipment investment is few, and consumption resource is few, and enforcement difficulty is small.
Certainly, the above is only specific application example of the invention, protection scope of the present invention is not limited in any way.It removes
Outside above-described embodiment, the present invention can also have other embodiment.All technical sides formed using equivalent substitution or equivalent transformation
Case is all fallen within scope of the present invention.
Claims (7)
1. a kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating, which is characterized in that packet
Include following steps:
S1. the concentrated sulfuric acid/nitric acid mixed acid solution that weight multiple is 100-120 times is added in carbon nanotube, is increased after being dispersed with stirring
Amount deionized water is filtered through miillpore filter, and is constantly cleaned with deionized water, until the acid on surface is rinsed well;
S2. the carbon nanotube on filter membrane is collected, is dried in vacuo for 24 hours at 40-60 DEG C, chitosan, carbon nanotube are successively slowly added
Enter in the mixed solution being made of dehydrated alcohol, acetic acid, ultrasonic disperse 1-1.5h, obtained suspension is with 600-1000r/min
Rate magnetic agitation 15-24h, be made Carbon Nanotubes/Chitosan mixing suspension;
S3. titanium alloy round abrasive sheet is polished step by step, is successively cleaned by ultrasonic in ethyl alcohol, deionized water, cleaned titanium sheet is dry
2-4min is etched with the deionized water of volume ratio 3-6:3-5:1/nitric/hydrofluoric mixed acid solution after dry, uses deionized water later
Cleaning;
S4. etched titanium alloy disk is put into reaction kettle, NaOH solution is filled in reaction kettle, then again puts reaction kettle
Enter in baking oven, react 2-3h at 60-80 DEG C, the surface with porous coarse structure is made, after the completion cleaning sample;
S5. step S4 is obtained into titanium alloy disk and makees cathode, Carbon Nanotubes/Chitosan mixing suspension is as electrodeposit liquid, platinum
Plate electrode is electrolysed as anode, prepares carbon nanotube coating, electrode distance 8-10mm, voltage 20-30V, sedimentation time
For 30-35s;
S6. carry out atomic layer deposition cycles to it again, 60-80 DEG C of depositing temperature, cycle-index 200-300, one cycle by
Diethyl zinc pulse 30ms, nitrogen clean 20s, deionized water pulse 30ms, and nitrogen cleans 20s composition, obtains zinc-oxide nano
Antimicrobial coating.
2. a kind of system of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating according to claim 1
Preparation Method, which is characterized in that the time of ultrasonic disperse is 1.5h in step S2, and the time of magnetic agitation is 18h.
3. a kind of system of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating according to claim 1
Preparation Method, which is characterized in that the volume ratio of the concentrated sulfuric acid and nitric acid is 3:1-4:1 in step S1.
4. a kind of system of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating according to claim 3
Preparation Method, which is characterized in that the volume ratio of the concentrated sulfuric acid and nitric acid is 3:1 in step S1.
5. a kind of system of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating according to claim 1
Preparation Method, which is characterized in that step S1 filters the miillpore filter that process uses 0.22 μm.
6. a kind of system of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating according to claim 1
Preparation Method, which is characterized in that the deionized water that the group of nitration mixture etching liquid described in step S3 is 5:4:1 as volume ratio, nitric acid,
The mixed solution of hydrofluoric acid.
7. a kind of system of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating according to claim 1
Preparation Method, which is characterized in that electrode distance is 10mm, voltage 30V, sedimentation time 30s in step S5.
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