CN106563176A - Atomic layer deposition-based preparation method for zinc oxide/carbon nanotube nano-antibacterial coating - Google Patents
Atomic layer deposition-based preparation method for zinc oxide/carbon nanotube nano-antibacterial coating Download PDFInfo
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- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
Abstract
The invention discloses an atomic layer deposition-based preparation method for a zinc oxide/carbon nanotube nano-antibacterial coating. The method is used for preparing a nano-antibacterial coating with good antibacterial property. The second purpose of the invention is to prepare a carbon nanotube and chitosan coating with bioactivity and a certain antibacterial property by applying an electro-deposition method. The third purpose of the invention is to prepare a zinc oxide nanostructure by utilizing an atomic layer deposition technology, obtain the zinc oxide/carbon nanotube nano-antibacterial coating, and enable nano-zinc oxide and carbon nanotubes to achieve a synergetic bactericidal effect.
Description
Technical field
The present invention relates to material science and technical field of nano material, more particularly to a kind of oxidation based on ald
The preparation method of zinc/CNT antimicrobial coating.
Background technology
Ald (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 and react to form film in material surface.Technique for atomic layer deposition has
Following advantage：First, relative to other traditional CVD methods, ald can be carried out at lower temperatures.
Secondly, ald has from restricted so as to which the amount that the material of material surface is deposited in each deposition cycle is one
Fixed.Again, because ald is from restricted, ald can on atomic layer precise control growing film
Thickness.Finally, the remarkable conformality of technique for atomic layer deposition allows film prepared by ald to retain the shape of substrate
Looks feature.
Surgical operation is often accompanied by bacterium infection, and inorganic antiseptic enters the antibacterial modified middle tool in body surface face under as medical mark
It is advantageous, than if effectively suppressing bacterium to adhere in implant surfaces, it is to avoid produce the drug-resistant bacteria that similar antibiotic causes.Oxygen
It is a kind of broad stopband (3.37eV) semiconductor substance with broad spectrum antibacterial to change zinc.The Antibacterial Mechanism bag of research report zinc oxide
Include digestion of metallic ion sterilization mechanism, i.e. zinc ion combined with the protease in bacterium body make its inactivation and kill bacterium；It is another
Kind of mechanism is then that zinc oxide produces electron hole pair under photocatalysis, so as to excite air in oxygen produce active oxygen,
Make bacterium local oxygen pressure rise or occur oxidation reaction and kill bacterium.CNT is a kind of to be widely used in each field
Nano material, by being combined with CNT, the probability that the electron hole pair that nano zine oxide is produced can be made compound is reduced, from
And strengthen the photo-catalysis capability of nano zine oxide.
In order to improve the antibacterial ability on medical implant surface.CNT can be passed through with shitosan and the association of zinc oxide
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 strengthen nano structure of zinc oxide antibiotic property CNT and shell
The composite coating of glycan.Antibacterial is separated out by the metal ion of zinc oxide and strengthens later nano zinc oxide photocatalysis antibacterial
Synergy, obtains the zinc oxide with good anti-microbial property/CNT antimicrobial coating.
The content of the invention
An object of the present invention is to provide a kind of system of the zinc oxide/CNT antimicrobial coating based on ald
Preparation Method, to prepare the surface of metal titanium coating with good antibiotic property.The second object of the present invention is with electro-deposition
Method prepares the titanium with surface porosity loose structure.The third object of the present invention is, with the method for ald, to obtain
To nano structure of zinc oxide coating, make nano zine oxide that there is Synergistic biocidal effect with CNT.
A kind of preparation method of the zinc oxide/CNT antimicrobial coating based on ald, it is characterised in that include
Following steps：
S1. CNT is added into the concentrated sulfuric acid/nitric acid mixed acid solution that weight multiple is 100-120 times, is increased after dispersed with stirring
Deionized water Jing miillpore filter suction filtration is measured, and deionized water is constantly cleaned, until the acid on surface is rinsed well；
S2. the CNT on filter membrane is collected, at 40-60 DEG C 24h is vacuum dried, shitosan, CNT are slowly added successively
Enter by absolute ethyl alcohol, in the mixed solution of acetic acid composition, ultrasonically treated 1-1.5h, the suspension for obtaining is with 600-1000r/min
Speed magnetic agitation 15-24h, Carbon Nanotubes/Chitosan mixing suspension is obtained；
S3. titanium alloy round abrasive sheet is polished step by step, is cleaned by ultrasonic in ethanol, deionized water successively, cleaned titanium sheet is done
Dry rear deionized water/nitric/hydrofluoric mixed acid solution etching 2-4min, afterwards deionized water cleaning；
S4. etched titanium alloy disk is put in reactor, NaOH solution is filled in reactor, then again put reactor
In entering baking oven, at 60-80 DEG C 2-3h is reacted, be obtained with porous coarse structure surface, after the completion of cleaning sample；
S5. step S3 is obtained into titanium alloy disk and makees negative electrode, CNT mixing suspension is made as electrodeposit liquid, platinum plate electrode
Anode is electrolysed, and prepares CNT figure layer, and electrode distance is 8-10mm, and voltage is 20-30V, and sedimentation time is 30-35s；
S6. atomic layer deposition cycles, 60-80 DEG C of depositing temperature are carried out to it again, cycle-index is 200-300, one cycle by
Diethyl zinc pulse 30ms, nitrogen cleaning 20s, deionized water pulse 30ms, nitrogen cleaning 20s compositions, obtain zinc-oxide nano
Antimicrobial coating.
The time of ultrasonic disperse is 3h in step S2, and the time of magnetic agitation is 18h；Step S1 suction filtration process is used
0.22 μm of miillpore filter；Acetic acid described in step S1 is 0.1% acetic acid；Nitration mixture etching liquid described in step S3 is consisted of
Volume ratio is 5:4:1 deionized water, nitric acid, the mixed solution of hydrofluoric acid；Electrode distance is 10mm in step S5, and voltage is
30V, sedimentation time is 30s；The parameter of ald is as follows in step S5：80 DEG C of depositing temperature, cycle-index is 300, one
Individual atomic layer deposition cycles are by diethyl zinc pulse 30ms, nitrogen cleaning 20s, deionized water pulse 30ms, nitrogen cleaning 20s groups
Into obtaining the zinc oxide/carbon nanotube antimicrobial coating based on ald.
Relative to prior art, the zinc oxide/CNT antimicrobial coating based on ald of the present invention
Preparation method, has the advantage that：
(1) using technique for atomic layer deposition Nano zinc oxide film is prepared suitable for various substrates；
(2) due to the photocatalytic activity that CNT is relevant with zinc oxide antibacterial, then compared to simple zinc oxide antibacterial, receive
Rice zinc oxide has more preferable antibiotic property with CNT synergy；
(3) preparation method is simple, and using the technology of the present invention a kind of zinc oxide/CNT based on ald is prepared
The preparation method of antimicrobial coating, equipment investment is few, and consumption resource is few, and enforcement difficulty is little.
Description of the drawings
Fig. 1 is the SEM figures of the titanium disk in embodiment 1 with zinc oxide/CNT antimicrobial coating；
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 describe in detail with reference to the accompanying drawings and examples, but
The scope of protection of present invention is not limited to the scope that embodiment is represented.
Embodiment 1：
(1) step one：It is 3 by the volume ratio that 1g CNTs (CNTs) are dissolved in 120mL:1 98% concentrated sulfuric acid/65% nitric acid
In mixed acid solution and ultrasonic disperse 3h, then magnetic agitation 36h.And then mixed liquor is added into 0.22 μm of a large amount of deionized waters Jing
Miillpore filter suction filtration, and deionized water constantly cleans, till pH=7.Collect the CNT on filter membrane, 60 DEG C of vacuum
It is dried 24h.75mg shitosans (CS), the CNT that 150mg is obtained are slowly added to successively by 7.5mL absolute ethyl alcohols,
In the mixed solution of the 0.1% acetic acid composition of 142.5mL, ultrasonically treated 1h, the suspension for obtaining is with the speed magnetic of 1000r/min
Power stirs 24h, and Carbon Nanotubes/Chitosan mixing suspension is obtained；
(2) step 2：Be equipped with 4mol/L NaOH solution it is standby, by titanium alloy disk (diameter 6mm, thickness 2.5mm) sand paper by
Level polishing, is cleaned by ultrasonic successively in ethanol, deionized water, and cleaned titanium sheet is after the drying 5 with volume ratio:4:1 goes
Ionized water/nitric/hydrofluoric mixed acid solution etching 2min, deionized water cleaning afterwards, and then by etched titanium alloy
Disk is put in reactor, and the NaOH solution of outfit is filled in reactor, and reactor is put in baking oven, is reacted at 80 DEG C
2h, be obtained with porous coarse structure surface, after the completion of cleaning sample；
(3) step 3：Step 2 is obtained titanium and is closed by the CNT mixing suspension obtained using in step one as electrodeposit liquid
Golden disk makees negative electrode, and platinum plate electrode makees anode, and electrode distance is 10mm, and voltage is 30V, and sedimentation time is 30s.The electricity for obtaining sinks
Product coating horse back deionized water is dried, and is dried at room temperature for afterwards.Made on electrodeposited coating using technique for atomic layer deposition
Standby to obtain nano structure of zinc oxide, the parameter of ald is as follows：80 DEG C of depositing temperature, cycle-index 300.One atomic layer
Deposition cycle is by diethyl zinc pulse 30ms, nitrogen cleaning 20s, deionized water pulse 30ms, nitrogen cleaning 20s compositions.Obtain
Zinc oxide based on ald/carbon nanotube antimicrobial coating.
Embodiment 2：
(1) step one：It is 3 by the volume ratio that 1.5g CNTs (CNTs) are dissolved in 150mL:1 98% concentrated sulfuric acid/67% nitre
In sour mixed acid solution and ultrasonic disperse 2.5h, then magnetic agitation 32h；And then mixed liquor is added into a large amount of deionized waters Jing
0.22 μm of miillpore filter suction filtration, and deionized water constantly cleans, till pH=7.CNT on collection filter membrane, 50
DEG C vacuum drying 28h.65mg shitosans (CS), the CNT that 135mg is obtained are slowly added to successively by 10mL absolute ethyl alcohols,
In the mixed solution of the 0.1% acetic acid composition of 150mL, ultrasonically treated 1.5h, the suspension for obtaining is with the speed magnetic of 1500r/min
Power stirs 20h, and Carbon Nanotubes/Chitosan mixing suspension is obtained；
(2) step 2：Be equipped with 5mol/L NaOH solution it is standby, by titanium alloy disk (diameter 6mm, thickness 2.5mm) sand paper by
Level polishing, is cleaned by ultrasonic successively in ethanol, deionized water, and cleaned titanium sheet is after the drying 5 with volume ratio:4:1 goes
Ionized water/nitric/hydrofluoric mixed acid solution etching 4min, deionized water cleaning afterwards, and then by etched titanium alloy
Disk is put in reactor, and the NaOH solution of outfit is filled in reactor, and reactor is put in baking oven, is reacted at 80 DEG C
2h, be obtained with porous coarse structure surface, after the completion of cleaning sample；
(3) step 3：Step 2 is obtained titanium and is closed by the CNT mixing suspension obtained using in step one as electrodeposit liquid
Golden disk makees negative electrode, and platinum plate electrode makees anode, and electrode distance is 15mm, and voltage is 25V, and sedimentation time is 35s.The electricity for obtaining sinks
Product coating horse back deionized water is dried, and is dried at room temperature for afterwards.Made on electrodeposited coating using technique for atomic layer deposition
Standby to obtain nano structure of zinc oxide, the parameter of ald is as follows：70 DEG C of depositing temperature, cycle-index 350.One atomic layer
Deposition cycle is by diethyl zinc pulse 25ms, nitrogen cleaning 35s, deionized water pulse 35ms, nitrogen cleaning 25s compositions.Obtain
Zinc oxide based on ald/carbon nanotube antimicrobial coating.
Embodiment 3：
(1) step one：It is 4 by the volume ratio that 2g CNTs (CNTs) are dissolved in 120mL:1 98% concentrated sulfuric acid/68% nitric acid
In mixed acid solution and ultrasonic disperse 3h, then magnetic agitation 22h；And then mixed liquor is added into 0.22 μm of a large amount of deionized waters Jing
Miillpore filter suction filtration, and deionized water constantly cleans, till pH=7.Collect the CNT on filter membrane, 60 DEG C of vacuum
It is dried 25h.55mg shitosans (CS), the CNT that 145mg is obtained are slowly added to successively by 8mL absolute ethyl alcohols, 125mL's
In the mixed solution of 0.1% acetic acid composition, ultrasonically treated 2h, the suspension for obtaining is with the speed magnetic agitation of 1200r/min
18h, is obtained Carbon Nanotubes/Chitosan mixing suspension；
(2) step 2：The NaOH solution for being equipped with 3.5mol/L is standby, by titanium alloy disk (diameter 6mm, thickness 2.5mm) sand paper
Polish step by step, be cleaned by ultrasonic in ethanol, deionized water successively, cleaned titanium sheet is after the drying 5 with volume ratio:4:1
And then deionized water/nitric/hydrofluoric mixed acid solution etching 4min, afterwards deionized water cleaning closes etched titanium
Golden disk is put in reactor, and the NaOH solution of outfit is filled in reactor, and reactor is put in baking oven, is reacted at 80 DEG C
2h, be obtained with porous coarse structure surface, after the completion of cleaning sample；
(3) step 3：Step 2 is obtained titanium and is closed by the CNT mixing suspension obtained using in step one as electrodeposit liquid
Golden disk makees negative electrode, and platinum plate electrode makees anode, and electrode distance is 12mm, and voltage is 35V, and sedimentation time is 25s.The electricity for obtaining sinks
Product coating horse back deionized water is dried, and is dried at room temperature for afterwards.Made on electrodeposited coating using technique for atomic layer deposition
Standby to obtain nano structure of zinc oxide, the parameter of ald is as follows：70 DEG C of depositing temperature, cycle-index 350.One atomic layer
Deposition cycle is by diethyl zinc pulse 25ms, nitrogen cleaning 35s, deionized water pulse 35ms, nitrogen cleaning 25s compositions.Obtain
Zinc oxide based on ald/carbon nanotube antimicrobial coating.
Embodiment 4：
(1) step one：It is 3.5 by the volume ratio that 1.2g CNTs (CNTs) are dissolved in 135mL:1 98% concentrated sulfuric acid/65%
In nitric acid mixed acid solution and ultrasonic disperse 2h, then magnetic agitation 15h；And then mixed liquor is added into a large amount of deionized waters Jing
0.22 μm of miillpore filter suction filtration, and deionized water constantly cleans, till pH=7.CNT on collection filter membrane, 70
DEG C vacuum drying 15h.80mg shitosans (CS), the CNT that 155mg is obtained are slowly added to successively by 10mL absolute ethyl alcohols,
In the mixed solution of the 0.1% acetic acid composition of 135mL, ultrasonically treated 2.5h, the suspension for obtaining is with the speed magnetic of 1300r/min
Power stirs 15h, and Carbon Nanotubes/Chitosan mixing suspension is obtained；
(2) step 2：The NaOH solution for being equipped with 4.5mol/L is standby, by titanium alloy disk (diameter 6mm, thickness 2.5mm) sand paper
Polish step by step, be cleaned by ultrasonic in ethanol, deionized water successively, cleaned titanium sheet is after the drying 5 with volume ratio:4:1
And then deionized water/nitric/hydrofluoric mixed acid solution etching 4min, afterwards deionized water cleaning closes etched titanium
Golden disk is put in reactor, and the NaOH solution of outfit is filled in reactor, and reactor is put in baking oven, is reacted at 60 DEG C
2.5h, be obtained with porous coarse structure surface, after the completion of cleaning sample；
(3) step 3：Step 2 is obtained titanium and is closed by the CNT mixing suspension obtained using in step one as electrodeposit liquid
Golden disk makees negative electrode, and platinum plate electrode makees anode, and electrode distance is 8mm, and voltage is 25V, and sedimentation time is 25s.The electricity for obtaining sinks
Product coating horse back deionized water is dried, and is dried at room temperature for afterwards.Made on electrodeposited coating using technique for atomic layer deposition
Standby to obtain nano structure of zinc oxide, the parameter of ald is as follows：70 DEG C of depositing temperature, cycle-index 350.One atomic layer
Deposition cycle is by diethyl zinc pulse 25ms, nitrogen cleaning 35s, deionized water pulse 35ms, nitrogen cleaning 25s compositions.Obtain
Zinc oxide based on ald/carbon nanotube antimicrobial coating.
Antibiotic property measure is carried out to antimicrobial coating：By step one obtain with zinc oxide/CNT antimicrobial coating
Titanium disk is immersed in 320 μ L phosphate buffer solutions, ultraviolet lighting 40min；Respectively ultraviolet lighting process after titanium
Staphylococcus aureus is cultivated in the culture medium of category disk immersion 25 hours, Escherichia coli detection bacterium survival rate after 10 hours,
By the bacteria adhension of the titanium disk after culture bacterium, the pattern of bacterium is observed under a scanning electron microscope afterwards.In figure
Grid is followed successively by pure titanium, alkali heat-treatment titanium, alkali heat-treatment titanium+CNT, alkali heat-treatment titanium+CNT/zinc oxide, determines
Data are as follows：For Escherichia coli group, almost without antibacterial ability, the titanium that Jing alkali heat-treatments are crossed, antibiotic rate is 10%, Jing to pure titanium
Alkali heat and CNT were processed, and antibiotic rate is that 16%, Jing alkali heat, CNT/zinc oxide were processed, and antibiotic rate is
72%；For staphylococcus aureus group, the titanium that titanium that pure titanium, Jing alkali heat-treatments are crossed, Jing alkali heat and CNT were processed is several
Without antibacterial ability, Jing alkali heat, CNT/zinc oxide were processed, and antibiotic rate is 98%, showed that it has good resisting
Bacterium effect.
Jing analysis tests, relative to prior art, it can be deduced that such as draw a conclusion：1) SEM tests are carried out to titanium disk,
The surface of metal titanium that alkali heat-treatment is obtained has loose porous bigger serface coarse structure, what technique for atomic layer deposition was obtained
Nano zine oxide/carbon nanotube structure distribution is uniform, and oxidation zinc concentration is higher, and the diameter of the nanometer rods for obtaining is got over
Greatly；2) staphylococcus aureus of the titanium disk surfaces not being modified through surface and Bacillus coli cells film are complete, table
Reveal bacterial growth not to be suppressed, the golden yellow of the titanium disk surfaces with zinc oxide/CNT antimicrobial coating
Staphylococcus and Bacillus coli cells film occur in that breakage or shrinkage, show good antibacterial ability, but just to golden yellow
Staphylococcic antibiotic rate, the antibacterial effect for adding CNT is better than the antibacterial effect for not adding CNT, and addition is received
The antibacterial effect of rice zinc oxide is better than the antibacterial effect for not adding nano zine oxide；3) prepared using technique for atomic layer deposition and received
Rice zinc-oxide film is applied to various substrates, due to the CNT photocatalytic activity relevant with zinc oxide antibacterial, then compares
In simple zinc oxide antibacterial, nano zine oxide has more preferable antibiotic property with CNT synergy, and preparation method is simple
It is easy, a kind of preparation method of the zinc oxide/CNT antimicrobial coating based on ald is prepared using the technology of the present invention,
Equipment investment is few, and consumption resource is few, and enforcement difficulty is little.
Certainly, the above is only the concrete application example of the present invention, protection scope of the present invention is not limited in any way.Remove
Outside above-described embodiment, the present invention can also have other embodiment.The technical side that all employing equivalents or equivalent transformation are formed
Case, all falls within scope of the present invention.
Claims (9)
1. a kind of preparation method of the zinc oxide/carbon nanotube antimicrobial coating based on ald, it is characterised in that bag
Include following steps：
S1. CNT is added into the concentrated sulfuric acid/nitric acid mixed acid solution that weight multiple is 100-120 times, is increased after dispersed with stirring
Deionized water Jing miillpore filter suction filtration is measured, and deionized water is constantly cleaned, until the acid on surface is rinsed well；
S2. the CNT on filter membrane is collected, at 40-60 DEG C 24h is vacuum dried, shitosan, CNT are slowly added successively
Enter by absolute ethyl alcohol, in the mixed solution of acetic acid composition, ultrasonically treated 1-1.5h, the suspension for obtaining is with 600-1000r/min
Speed magnetic agitation 15-24h, Carbon Nanotubes/Chitosan mixing suspension is obtained；
S3. titanium alloy round abrasive sheet is polished step by step, is cleaned by ultrasonic in ethanol, deionized water successively, cleaned titanium sheet is done
With volume ratio it is 3-6 after dry:3-5:1 deionized water/nitric/hydrofluoric mixed acid solution etching 2-4min, uses afterwards deionization
Water is cleaned；
S4. etched titanium alloy disk is put in reactor, NaOH solution is filled in reactor, then again put reactor
In entering baking oven, at 60-80 DEG C 2-3h is reacted, be obtained with porous coarse structure surface, after the completion of cleaning sample；
S5. step S3 is obtained into titanium alloy disk and makees negative electrode, CNT mixing suspension is made as electrodeposit liquid, platinum plate electrode
Anode is electrolysed, and prepares CNT figure layer, and electrode distance is 8-10mm, and voltage is 20-30V, and sedimentation time is 30-35s；
S6. atomic layer deposition cycles, 60-80 DEG C of depositing temperature are carried out to it again, cycle-index is 200-300, one cycle by
Diethyl zinc pulse 30ms, nitrogen cleaning 20s, deionized water pulse 30ms, nitrogen cleaning 20s compositions, obtain zinc-oxide nano
Antimicrobial coating.
2. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 1
Preparation Method, it is characterised in that the time of ultrasonic disperse is 1.5h in step S2, and the time of magnetic agitation is 18h.
3. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 1
Preparation Method, it is characterised in that the volume ratio of the concentrated sulfuric acid and nitric acid is 2 in step S1:1-5:1.
4. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 3
Preparation Method, it is characterised in that the volume ratio of the concentrated sulfuric acid and nitric acid is 3-1 in step S1.
5. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 1
Preparation Method, it is characterised in that step S1 suction filtration process uses 0.22 μm of miillpore filter.
6. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 1
Preparation Method, it is characterised in that the concentration of the concentrated sulfuric acid is 98%, the concentration of nitric acid is 65-68%.
7. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 1
Preparation Method, it is characterised in that the acetic acid described in step S1 is 0.1% acetic acid.
8. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 1
Preparation Method, it is characterised in that the volume ratio that consists of of the nitration mixture etching liquid described in step S3 is 5:4:1 deionized water, nitric acid,
The mixed solution of hydrofluoric acid.
9. the system of a kind of zinc oxide/carbon nanotube antimicrobial coating based on ald according to claim 1
Preparation Method, it is characterised in that electrode distance is 10mm in step S5, and voltage is 30V, and sedimentation time is 30s.
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| CN115501392A (en) * | 2022-09-28 | 2022-12-23 | 深圳先进技术研究院 | Zinc oxide/zinc phosphate nanorod composite antibacterial coating and preparation method and application thereof |
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