CN102864425A - Method for attaching nitrogen doped TiO<2-x>Nx films on metal bracket surface by radio frequency magnetron sputtering method - Google Patents
Method for attaching nitrogen doped TiO<2-x>Nx films on metal bracket surface by radio frequency magnetron sputtering method Download PDFInfo
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Abstract
The invention relates to a method for attaching nitrogen doped TiO<2-x>Nx films on the metal bracket surface by a radio frequency magnetron sputtering method. The method comprises the following steps that firstly, a metal bracket is cleaned by mixing liquid prepared by 40g of LNaOH, 25g of LNaCO3, 50g of LNA3PO4.12H2O and 7.5g of LNa2SO3, and then the bracket is put into a beaker containing acetone solution; and the TiO2 photocatalysis antibacterial performance is utilized, and the nitrogen doped TiO<2-x>Nx film metal bracket is prepared through adopting the radio frequency magnetron sputtering. The prepared TiO<2-x>Nx films have the advantages that the bracket surface is uniform and compact, the thickness of the TiO<2-x>Nx films is about 500nm, the crystallinity is good, and the influence on the bracket size is low. The crystal particle size is 30nm, an anatase phase structure is adopted, and in addition, good preferred orientation is realized in the (101) direction.
Description
Technical field
The present invention relates to a kind of medicine mouth cavity orthodontic specialty metal bracket modification, is a kind ofly to prepare nitrating TiO with radio-frequency magnetron sputter method
2-xN
xThe method of film metal bracket.
Background technology
Patho-occlusion is common oral disease, and fixedly rescuing technology is one of present topmost correcting method, and orthodontic bracket is the core apparatus of fixedly rescuing technology.Yet when rescuing patho-occlusion and improving patient's face, also successive exposure is out for the complication in the orthodontic treatment.
The patient who wears fixed appliance is difficult for safeguarding oral hygiene; the physiology self-cleaning ability descends simultaneously; causing local bacterial plaque to be piled up significantly increases; the bracket below that fixed appliance is bonding and the demineralization of enamel appearance on every side even dental caries are bad and then have influence on periodontal health, and this problem has caused the great attention of Chinese scholars.The scholars such as external Gorelick L nineteen eighty-two U.S.'s Orthodontics magazine report use among the just abnormal patient of fixed appliance treatment 49.6% people or 10.8% tooth the different enamel decalcification of degree to occur.The scholars such as domestic Hu Wei compare observation by dental enamel demineralization disease damage before and after 165 patients being used the fixed appliance treatment, and finding has 98 people enamel decalcification to occur in the orthodontic treatment, and sickness rate is 59.4%.Enamel demineralization is apt to occur in premanillary teeth district and mandibular posterior area, and wherein the enamel around the bracket is again predilection site.
Use fixed appliance, periodontal tissue health problem in various degree can appear in just abnormal patient, and modal is exactly gingivitis.Investigation shows that gingivitis appears in about adolescent patient more than 50% in orthodontic treatment, and the grownup is lower.External report, the destruction of periodontal tissue has occured in 10% patient.(study course of Fu Min chief mouth cavity orthodontic training .) first cause is the variation of bacterial plaque delay and little ecology, is that unnecessary binding agent is to the hormesis of gum secondly.
Alleviate or eliminate the generation of fixedly rescuing enamel decalcification in the process, oulitis and secondary caries, caused scholars' attention.At present have the prevention of report and solution to have both at home and abroad:
(1) when the acid etching facing, as far as possible only the contacted enamel of needs and bracket base district is carried out acid etching, try not to enlarge the acid etching face.
(2) fluoridize matrix material: include fluorine exchange resin and aluminosilicate polyacrylate, wherein the former not only self can be for a long time constant releasing fluoride ion, but also can from surrounding environment, absorb fluorion and then be released to facing by ion-exchange.
(3) the fluorine protective material is filmed: effectively prevent and stopped acidic substance that bacterium produces to adamantine erosion, and sustainable in the enamel surface releasing fluoride ion, play the effect that enamel decalcification promotes remineralization that suppresses.But its action time is shorter, needs coating in per 3 months once.
(4) fluorine-containing collutory: fluorine-containing collutory can reduce the enamel decalcification around band and the bracket and strengthen remineralization.Chen Ya has just waited the patient who selects at random 40 routine Upper Anterior Teeth to clarify a diagnosis as enamel demineralization from the permanent dentition patient who accepts orthodontic treatment to use fluoride mouthwash.The result shows that under the good prerequisite of patient's compliance, test group enamel decalcification degree had reduced by 73.5% to test group in the time of 3 months (using the fluoride mouthwash group) when the enamel decalcification degree had reduced by 17.6%, 6 month.
(5) adopt specific form toothbrush and toothpaste with fluoride to brush teeth.Use toothpaste with fluoride, can increase adamantine remineralization degree.A result of study shows that the trouble dental caries score that just abnormal patient's use contains the acid phosphatase gel dentifrice of 1.1% Sodium Fluoride is starkly lower than fluorine-containing 0.243% silicon-dioxide toothpaste.And commercially available toothpaste mostly is fluorine-containing 0.243% silicon-dioxide toothpaste.
(6) regularly periodontal scaling: can effectively remove soft dirt and bacterial plaque, obviously alleviate fixed appliance to the detrimentally affect of periodontal tissue, alleviate the gingivitis reaction.
Above research mainly concentrates on fluorine-containing caking agent and the protectant use of fluorine.But exist notable difference aspect the effect of above method enamel demineralization in the prevention orthodontic treatment.Control for acid etching facing area needs doctor's skilled operation, belongs to uncontrollable factor.Have the foreign scholar to report once that the effect of various novel fluorine adhesivess in the control enamel demineralization was not quite similar, there were significant differences for the hickie degree of depth and demineralization degree.The research method of fluorine-containing adhesives substantially all is experiment in vitro, can't comprehensive and accurate Mouthsimulator in complex environment, and experiment in vitro can only carry out research in a short time, therefore also requires further study for the long-term clinical effectiveness of fluorine-containing adhesives.The fluorine protective material mainly contains toothpaste with fluoride, fluoride mouthwash, fluorine gel etc., therefore has anti-enamel decalcification ability owing to all contain fluorine in its composition, but needs simultaneously additionally to take other operating time of chair, the factor that the Existence dependency patient cooperates.
(7) bracket of selection unlike material.Gao Xiaohui in 2002, Wu Jing, Yang Shenghui etc. studies show that the clearance rate of metal stainless steel bracket is better than ceramic bracket, and the clearance rate of plastic bracket is the poorest.The scholars such as Yu Zhe use high speed handpiece, silicon carbide car pin, prepare the cylindrical grooves of diameter 113mm, degree of depth 017mm 100 pieces of metal bracket lip sides.The NaF (first NaF and glass ion powder are mixed well, mix well with liquid, powder, liquor ratio by specification carry out) of adding 15% in a certain amount of glass ionomer, it is concordant to the edge that the glass ion after mixing well is inserted groove, and the solid light of light is according to 40s.The bracket placement for preparing is preserved 24h in 37 ℃ of thermostat containers, material is solidified fully.This type of novel fluorine bracket needs regularly to add fluorion, and long-term antibacterial effect needs to observe.Bundle Lei in 2005 etc. research and develop TiO2 film bracket, the enamel demineralization that utilizes its antibacterial effect to prevent orthodontic treatment to cause first.
1972, Fujishima was since n-N-type semiconductorN TiO2 electrode has been found the lasting redox reaction of water, and TiO2 is the extensive concern that the photocatalyst material of representative has begun to cause scholars.TiO
2As a kind of photocatalysis antibacterial agent, have good anti-physiology corrodibility, self-cleaning property and antibacterial effect and to the security of organism.
But, TiO
2Absorption bands is confined to wavelength less than the ultraviolet region of 387nm, can only utilize in sunlight, to account for 4% UV-light, and TiO
2Anti-microbial property from its photocatalytic activity, so TiO
2To lose antibiotic and bactericidal effect in the dark, and under Weak ultraviolet excited, photocatalytic activity was not enough, anti-microbial property descends, and has so also limited TiO
2The application of photocatalysis technology.Calendar year 2001 Ashai has reported nitrating TiO at Science
2Has excellent visible light activity on the basis that does not reduce the ultraviolet catalytic activity.Doping vario-property is to realize TiO
2One of important means of visible light activity.Although metal ion mixing can be realized visible light catalysis activity, become easily the center of catching light induced electron, reduce photocatalysis efficiency; Nonmetal doping can be realized visible light catalytic on the basis that does not reduce the ultraviolet catalytic activity.The nonmetal doping element of research mainly contains C, P, N, S, F etc. at present, and is wherein ideal with N doping effect.Therefore, nitrating TiO
2Under radiation of visible light, have than pure TiO
2More superior catalytic capability and anti-microbial property.
Summary of the invention
Purpose of the present invention aims to provide a kind of radio-frequency magnetron sputter method of using at metal bracket surface attachment nitrating TiO
2-xN
xThe method of film.Utilize TiO2 photocatalysis antibacterial performance, prepare nitrating TiO by adopting rf magnetron sputtering
2-xN
xThe film bracket is in the hope of utilizing nitrating TiO
2-xN
xFilm improves the bracket surface property, can bring into play TiO again simultaneously
2-xN
xPhotocatalysis antibacterial, and then flora adheres to around reducing bracket, the generation of the orthodontic treatment complication such as prevention enamel decalcification, gingivitis, periodontitis.
The object of the present invention is achieved like this:
A kind ofly prepare nitrating TiO with rf magnetron sputtering
2-xN
xThe method of film metal bracket, its step comprises:
(1) pre-treatment of substrate
1. the precleaning of vacuum chamber
At first, will check vacuum chamber before thin film sputtering, remove the dirt settling on its lumen wall and the substrate disc, then use the careful wiping of alcohol cotton yarn, until cotton yarn is when white substantially, then residual alcohol is wherein taken out in baking;
2.. the processing of substrate
Bracket is immersed in 40g/L NaOH, 25g/L NaCO
3, 50g/L Na
3PO
412H
2O and 7.5g/LNa
2SO
3Formulated mixed solution constant temperature cleans 25min at 90 ℃, observe the surface without the globule, then bracket is put into the beaker that fills 99.5% acetone soln, ultrasonic cleaning 20min, take out the post-drying sample also blows substrate surface off with the elevated pressure nitrogen air gun dust, then put into vacuum chamber;
3.. the reverse sputtering of bracket
The substrate of cleaning is put into vacuum chamber, vacuumize and reach 3.0 * 10
-4During Pa, pass into Ar gas, regulate push-pull valve to gas pressure in vacuum and reach 2Pa, then open the ionization power supply that is connected on the substrate disc, substrate is carried out reverse sputtering 20min with the zone of oxidation of removal substrate surface and some residual dirts, reverse sputtering power is 30W;
(2) nitrating TiO
2-xN
xThe preparation of film metal bracket
After bracket has been carried out clean operation, with high-purity Ti O
2Ceramic target (purity is 99.99%) is installed on JZCK-580 high vacuum multifunctional magnetic control sputtering machine, connects the radio-frequency sputtering power supply, TiO
2Target is of a size of 75mm*5mm, blocks target with the target baffle plate, carries out the pre-sputter of 20min, and power is 100W, removes TiO
2The impurity layer on target surface; TiO
2The pre-sputter of target is removed the target baffle plate after finishing, and bracket is moved on to begin TiO below the target
2The sputter of film; The substrate vacuum degree is 1.0 * 10
-3Pa, operating air pressure 1.0Pa passes into two kinds of gases of argon gas and nitrogen, and argon gas and nitrogen mass flux ratio are 30: 1, radio-frequency sputtering power 300W, 300 ℃ of underlayer temperatures were metal bracket surface sputtering 4 hours; To make TiO
2-xN
xFilm places the inherent nitrogen atmosphere of high temperature box type resistance furnace to carry out anneal, and the time kept 2 hours, and annealing temperature is controlled at 450 ℃, after the annealing, gets nitrating TiO
2-xN
xThe film metal bracket.
Advantage of the present invention:
1, the present invention is take TiO2 as target, and nitrogen and argon gas adopt radio-frequency magnetron sputter method to prepare nitrogen doped Ti O as sputter gas
2-xN
xThe film bracket.Radio-frequency magnetron sputter method is more flexible in the selection of mode of deposition, by changing RF-Sputtering Parameters control membrane structure and optical parametric, can be easy to as required adjust preparation condition,
2, the present invention adopts rf magnetron sputtering successfully to prepare nitrogen doped Ti O
2-xN
xThe film bracket adopts respectively X-ray diffractometer, scanning electron microscope and Noran energy spectrometer that sample is carried out XRD, SEM, EDS analysis.The result shows the TiO of preparation
2-xN
xFilm bracket surface uniform, densification, TiO
2-xN
xFilm thickness 490nm～510nm, good crystallinity is little to the bracket size impact.Size of microcrystal 30nm is the Anatase structure, and in (101) direction good preferred orientation is arranged.
3, the present invention is at stainless steel bracket surface preparation TiO
2-xN
xFilm, thickness are 500nm, in order to improve TiO
2-xN
xFilm bracket catalytic activity becomes Anatase through subzero treatment, and scanning electron microscope shows that particle diameter is at nano level, and even compact carries out simultaneously nitrogen and mixes, and the EDS analysed film only has nitrogen element, oxygen element and titanium elements to form, wherein nitrogen element mass ratio is 0.13%, thereby is TiO
2-xN
xThe film bracket possesses good photochemical catalysis and germ resistance provides foundation.
4, the present invention is to TiO
2-xN
xThe mechanical property of film bracket is tested, and shows TiO
2-xN
xThe tack of film and bracket is good, and the bracket surfaceness has certain reduction, and the frictional force between bracket and arch wire reduces, and has improved the mechanical property of original bracket, and above result carries out anti-microbial property for next step and clinical application research provides theoretical basis.
Description of drawings
Fig. 1 is the nitrogen doped Ti O that the present invention prepares
2-xN
xFilm bracket figure.
Fig. 2 is the XRD analysis synoptic diagram on Fig. 1 bracket surface.
Fig. 3 is Fig. 1 bracket surface TiO
2-xN
xThe SEM Analysis of Surface Topography figure of film, wherein: (a) be annealing forestock rooved face shape appearance figure; (b) be 450 ℃ of annealing butt rooved face shape appearance figures.
Fig. 4 is Fig. 1 bracket surface TiO
2-xN
xThe EDS energy spectrum analysis figure of film.
Fig. 5 is streptococcus mutans, lactobacillus, actinomyces viscosus, Candida albicans enumeration cultivation figure, and wherein (a) is common straight silk bow supporting groove, (b) is TiO
2-xN
xThe film bracket.
Fig. 6 is the bacterial adhesion lab diagram, and wherein (a) is common straight silk bow supporting groove;
(b) be TiO
2-xN
xThe film bracket.
Embodiment
Below, by 1. nitrating TiO
2-xN
xThe preparation of film bracket; 2. nitrating TiO
2-xN
xFilm bracket Structure analysis; 3. nitrating TiO
2-xN
xThe anti-microbial property of film bracket; 4. nitrating TiO
2-xN
xFour aspects of the mechanical property of film bracket are described in detail the present invention again:
1. nitrating TiO
2-xN
xThe preparation of film bracket
The present invention adopts radio-frequency magnetron sputter method to prepare nitrogen doped Ti O on stainless steel straight silk bow supporting groove (Hangzhou three produces than medicine equipment company limited, 0.022 " standard type) surface
2-xN
xFilm obtains nitrogen doped Ti O
2-xN
xThe film bracket.
1.1 material and experimental installation
Straight silk bow supporting groove (Hangzhou three is than medicine equipment company limited, 0.022 " standard type)
(the ultrapure company in Chengdu, purity is 99.99%, 75mm * 5mm) to the titanium oxide ceramics target
Magnetic control sputtering system (Liaoning JuZhi Science Development Co., Ltd, JZCK-580 high vacuum multifunctional magnetic control sputtering equipment)
High temperature box type resistance furnace
Reagent is all adopted by Shanghai chemical reagent work and is produced.
1.2 experimental procedure
1. the precleaning of vacuum chamber
1.2.1a the precleaning of vacuum chamber
At first, will check vacuum chamber before thin film sputtering, remove the dirt settling on its lumen wall and the substrate disc, then use the careful wiping of alcohol cotton yarn, until cotton yarn is when white substantially, then residual alcohol is wherein taken out in baking;
1.2.1b. the processing of substrate
Bracket is immersed in 40g/L NaOH, 25g/L NaCO
3, 50g/L Na
3PO
412H
2O and 7.5g/LNa
2SO
3Formulated mixed solution constant temperature cleans 25min at 90 ℃, observe the surface without the globule, then bracket is put into the beaker that fills 99.5% acetone soln, ultrasonic cleaning 20min, take out the post-drying sample also blows substrate surface off with the elevated pressure nitrogen air gun dust, then put into vacuum chamber;
1.2.1c. the reverse sputtering of bracket
The substrate of cleaning is put into vacuum chamber, vacuumize and reach 3.0 * 10
-4During Pa, pass into Ar gas, regulate push-pull valve to gas pressure in vacuum and reach 2Pa, then open the ionization power supply that is connected on the substrate disc, substrate is carried out reverse sputtering 20min with the zone of oxidation of removal substrate surface and some residual dirts, reverse sputtering power is 30W;
2. nitrating TiO
2-xN
xThe preparation of film metal bracket
After bracket has been carried out clean operation, with high-purity Ti O
2Ceramic target (purity is 99.99%) is installed on JZCK-580 high vacuum multifunctional magnetic control sputtering machine, connects the radio-frequency sputtering power supply, TiO
2Target is of a size of 75mm*5mm, blocks target with the target baffle plate, carries out the pre-sputter of 20min, and power is 100W, removes TiO
2The impurity layer on target surface; TiO
2The pre-sputter of target is removed the target baffle plate after finishing, and bracket is moved on to begin TiO below the target
2The sputter of film; The substrate vacuum degree is 1.0 * 10
-3Pa, operating air pressure 1.0Pa passes into two kinds of gases of argon gas and nitrogen, and argon gas and nitrogen mass flux ratio are 30: 1, radio-frequency sputtering power 300W, 300 ℃ of underlayer temperatures were stainless steel straight silk bow supporting groove surface sputtering 4 hours; To make TiO
2-xN
xFilm places the inherent nitrogen atmosphere of high temperature box type resistance furnace to carry out anneal, and the time kept 2 hours, and annealing temperature is controlled at 450 ℃, after the annealing, gets nitrogen doped Ti O
2-xN
xThe film bracket.
The present invention adopts radio-frequency magnetron sputter method to prepare nitrogen doped Ti O
2-xN
xThe film bracket prepares TiO than existing liquid phase preparation process, physical vaporous deposition, chemical Vapor deposition process and electrochemical method
2-xN
xThe advantage that has of film:
Wet chemical methods has the purity height, homogeneity is strong, synthesis temperature is low, reaction conditions is easy to the characteristics such as control, particularly preparation process is relatively simple, need not special valuable instrument, the advantages such as the little and narrow pore size distribution range of the membrane pore size that makes simultaneously, but its shortcoming is that the masking cost compare is large, and film base poor adhesive force, the TiO that makes
2Film needs comparatively high temps to heat-treat, and the transparency is relatively poor
[62,63]
Chemical vapour deposition is a kind of chemical vapor-phase growing method, this method is the reactant gasification containing one or more compounds, the elementary gas that consist of the film element, send in the reaction chamber and react, generate solid film by gas phase action and the chemical reaction on substrate surface.This method can apply at the article surface of any complex geometry, film base sticking power is good, therefore develop very fast, it is higher that but the method required equipment requires, cost is also higher, and the film microcosmic surface that makes is uneven, and (50～150nm) differ the granularity size, and the film surfaceness is larger.
The physical vaporous deposition of film refers to use the high temperature heat sources such as electric arc, high frequency or plasma body with heating raw materials, makes it gasification or forms plasma body, and then quenching makes it to prepare in the substrate deposition a kind of method of film.The depositing temperature of physical vaporous deposition is lower, is difficult for causing that the distortion, cracking of substrate and coating performance descend, and the film that makes is even, and the structure and properties of film easy to control is the film-forming method of widespread use on a kind of engineering.Physical vaporous deposition commonly used mainly contains at present: arc ion plating, radio-frequency sputtering, d.c. sputtering, magnetron sputtering etc.Sputtering method especially magnetron sputtering method is more flexible in the selection of mode of deposition, because sputtering method can be easy to adjust preparation condition as required, can reduce substrate temperature simultaneously, thereby be easy to control structure and the character of film.Therefore rf magnetron sputtering is a kind of very effective preparation TiO
2-xN
xThe method of film.
The present invention adopts TiO
2Carry out sputter as target.Sputter plating TiO
2-xN
xDuring film, the target of selecting has Ti, TiO
2And TiO
2-xEtc. dissimilar.Because the TiO that plates
2-xN
xFilm, so when making the target plated film with metal titanium, a chemical reaction process is arranged, atmosphere is the mixed gas of oxygen, nitrogen and argon gas, can oxidized surface for the metal base bracket, affect the bracket surface property, and process is difficult for stablizing, sputter rate is lower.With TiO
2Be target, generally adopt nitrogen and argon gas as sputter gas, can be by changing RF-Sputtering Parameters control membrane structure and optical parametric, the reaction process of complexity is converted into better simply physical process.
The nitrogen doped Ti O for preparing
2-xN
xThe film bracket places the inherent nitrogen atmosphere anneal of high temperature box type resistance furnace, and annealing temperature is controlled at 450 ℃.For the TiO that needing to obtain
2-xN
xFilm, the lift velocity of control annealing temperature prevents that temperature variation is too fast and causes substrate to break or film separation.Behind the insulation 2h, substrate is lowered the temperature with stove, so that film has the time enough sufficient crystallising.Use the nitrating TiO of scanning electron microscope (SEM) to preparing
2-xN
xThe film bracket is observed, surface uniform, densification.
2. nitrating TiO
2-xN
xFilm bracket Structure analysis
1.1 material and experimental installation
Nitrating TiO
2-xN
xThe film bracket
Straight silk bow supporting groove (Hangzhou three is than medicine equipment company limited, 0.022 " standard type)
Stainless steel substrate
Surface profiler (Micro XAM)
X-ray diffractometer (Riguku D/MAX-2400 type)
Scanning electron microscope (SEM) (Hitachi, Ltd, Hitachi S-4800, resolving power 1.4nm, 30kv)
Noran energy spectrometer (EDS) (U.S. power ﹠ light company, resolving power 12keV)
1.2 experimental procedure
1.2.1 measure the thickness of film with Micro XAM surface profiler
Experiment one preparation TiO
2-xN
xDuring the film bracket, in the sputter stove, put into stainless steel substrate.Because the restriction of bracket shape is by test stainless steel substrate surface TiO
2-xN
xThe thickness of film obtains bracket surface film thickness.The bracket surface TiO
2-xN
xFilm thickness is 500nm, and this thickness does not have impact substantially on the bracket surface size.
1.2.2X x ray diffractometer x carries out XRD analysis
Use Rigaku Riguku D/MAX-2400 type X-ray diffractometer to TiO
2-xN
xFilm bracket surface TiO
2-xN
xFilm carries out structural analysis, and investigates TiO
2-xN
xThe crystal formation of film and grain fineness number.Fig. 2-the 1st, the XRD on bracket surface spectrum before and after the annealing.See that from XRD spectra a is the sample that does not pass through anneal, Anatase and Rutile Type characteristic peak do not occur, interpret sample (a) surface TiO
2-xN
xFilm is undefined structure.B is the sample through 450 ℃ of annealing 2h, through 450 ℃ of annealing 2h, bracket surface TiO
2-xN
xThe film crystal structure is by the unformed Detitanium-ore-type structure (b) that changes into, in 2 θ=25.120 ° and 2 θ=37.689 ° located obvious diffraction peak, corresponding (101) and (004) face of Detitanium-ore-type, and show preferred orientation.According to Scherrer (Scherrer) formula:
d＝0.89λ/βcosθ (1)
Wherein the wavelength X of X ray is 0.15406nm, the halfwidth (radian) of the X diffraction of β after for deduction instrument broadening, θ be diffraction angle corresponding to X-ray diffraction peak (°), obtain through 450 ℃ of annealing butt rooved face TiO
2-xN
xThe median size of film is 30nm, and TiO is described
2-xN
xFilm is nanometer scale.
1.2.3 scanning electron microscope (SEM) is observed TiO
2-xN
xFilm bracket surface topography
With the Hitachi S-4800 of Hitachi, Ltd field emission microscopy observation TiO
2-xN
xThe surface topography of film bracket.Fig. 2-the 2nd, the bracket surface TiO before and after the anneal
2-xN
xThe SEM microscopic appearance figure of film.Can find out that from Fig. 2 (a), (b) film surface is even, fine and close, but compare with Fig. 2 (a) that the basic crystallization of Fig. 3 (b) film has the Anatase crystalline structure.
1.2.4EDS energy spectrum analysis
With the EDS energy depressive spectroscopy bracket surface elementary composition carried out the quantitative and semi-quantitative analysis.Fig. 2-3 be Fig. 2-2 with the EDS EDAX results under the condition of visual field, illustrate that film surface only has nitrogen element, oxygen element and titanium elements to form, wherein nitrogen element mass ratio is 0.13%.
TiO
2As a kind of photocatalysis antibacterial agent, have good anti-physiology corrodibility, self-cleaning property and antibacterial effect and to the security of organism, thereby obtain extensive concern.TiO
2Germ resistance come from its photocatalytic activity, (Ew＞Eg), TiO under the UV-irradiation of certain wavelength
2The valence band electronics be subjected to optical excitation, transit to conduction band, form the separation of current carrier (e-h+), under the effect of electric field, current carrier is diffused to the surface mutually by the body of catalyzer, the light induced electron that is diffused into the surface can be by TiO
2Surface sorption oxygen is captured, and generates the superoxide anion (O with certain oxidation capacity
2-), organic pollutant that can Direct Catalytic Oxidation agent surface also can be oxidized to hydroxyl radical free radical to planar water (OH), then by the hydroxyl radical free radical organic pollutant in the deoxidation water again, by this ceaselessly redoxomorphism, TiO
2Photocatalysis technology can make most oxidation operation degradeds, until be inorganic molecules CO
2And H
2O.The bracket that therefore will obtain to have the high-efficiency antimicrobial activity will improve the photocatalytic activity of bracket surface film.
Affect TiO
2The factor of film catalytic activity is a lot, such as crystal formation, degree of crystallinity, specific surface area, absorption situation and ion doping modification etc.TiO
2Mainly contain brookite, anatase octahedrite and three kinds of structural forms of rutile, anatase octahedrite and rutile are rock steady structures, and the photocatalytic activity of anatase octahedrite is 200-3000 times of Rutile Type.Experimental results demonstrate, at normal temperatures, the degraded large amount of organic that anatase titania can non-selectivity
[68]Size also directly affects photocatalytic activity.Particle diameter is less, TiO
2The specific surface area of photocatalyst is larger, and the probability that reacts on the unit surface is larger, so just is conducive to improve photocatalysis efficiency, and especially catalytic activity is stronger when particle diameter reaches nanometer scale.Experiment showed, that at the Anatase particle diameter photocatalysis performance is the strongest during less than 50nm.Thermal treatment temp is to TiO
2Crystalline phase composition and the degree of crystallinity impact of film are very large, the low temperature crystallized formation that is conducive to Anatase, and the processing of the crystallization of high-temperature can obtain Rutile Type.The bracket of the present invention after to sputter adopts 450 ℃ of subzero treatment, nanocrystal TiO
2-xN
xFilm has desirable anatase phase structure, and particle diameter is at nano level, and better crystallinity degree has improved catalytic effect to greatest extent.
But, TiO
2Absorption bands is confined to wavelength less than the ultraviolet region of 387nm, can only utilize in sunlight, to account for 4% UV-light, and TiO
2Anti-microbial property from its photocatalytic activity, so TiO
2To lose antibiotic and bactericidal effect in the dark, and under Weak ultraviolet excited, photocatalytic activity was not enough, anti-microbial property descends, and has so also limited TiO
2The application of photocatalysis technology.Calendar year 2001 Ashai has reported nitrating TiO at Science
2Has excellent visible light activity on the basis that does not reduce the ultraviolet catalytic activity.Doping vario-property is to realize TiO
2One of important means of visible light activity.Although metal ion mixing can be realized visible light catalysis activity, become easily the center of catching light induced electron, reduce photocatalysis efficiency; Nonmetal doping can be realized visible light catalytic on the basis that does not reduce the ultraviolet catalytic activity.The nonmetal doping element of research mainly contains C, P, N, S, F etc. at present, and is wherein ideal with N doping effect.Therefore, nitrating TiO
2Under radiation of visible light, have than pure TiO
2More superior catalytic capability and anti-microbial property.
(3) nitrating TiO
2-xN
xThe anti-microbial property of film bracket
Patho-occlusion is one of common problem of oromaxillo-facial region, and sickness rate is up to 47.8%, and fixedly rescuing technology is present modal methods for the treatment of.After fixed appliance was worn entrance cavity, bacterial plaque, swill were detained on the facing of appliance, caused oral cavity flora to occur to form and changed, and caused the generation of gingivitis, tooth demineralization or carious tooth.Nano-TiO
2The photochemical catalysis inorganic antibacterial material has photocatalytic activity height, stable chemical nature, nontoxic odorless and advantage with low cost, is maximum photocatalyst of tool development potentiality and research.The present invention is developing nitrating TiO
2-xN
xOn the basis of film bracket, take Candida albicans, streptococcus mutans, lactobacillus, actinomyces viscosus as strain subject, by colony counting method to nitrating TiO
2-xN
xThe anti-microbial property of film bracket is studied.
1 materials and methods
1.1 material
Straight silk bow supporting groove (Hangzhou three is than medicine equipment company limited, 0.022 " standard type)
Nitrating TiO
2-xN
xThe film bracket
Tryptones, yeast extract (Oxoid)
Peptone, glucose, agar, KH
2PO
4, K
2HPO
4, NaCO
3, glycerine (Shanghai chemical reagent work)
Distilled water (laboratory)
1.2 laboratory apparatus
Super clean bench, constant incubator, illumination shaking table (constant temperature), opticmicroscope, pressure steam sterilization boiler, triangular flask, plate, test tube, liquid-transfering gun, EP pipe
1.3 strain subject
Streptococcus mutans ATCC25175 (oral cavity key lab of Sichuan University)
Lactobacillus ATCC4356 (oral cavity key lab of Sichuan University)
Actinomyces viscosus ATCC15987 (oral cavity key lab of Sichuan University)
Candida albicans ATCC10231 (oral cavity key lab of Sichuan University)
1.3 experimental procedure
1.3.1 preparation substratum
1.3.1.1 sabouraud culture medium (Candida albicans)
Table 1 sabouraud culture medium component list
1.3.1.2TPY substratum (streptococcus mutans, lactobacillus, actinomyces viscosus)
Table 2TPY medium component table
The liquid and the solid medium that prepare are put into the pressure sterilization pot, and 121 ℃ of heating 15 minutes naturally cool to 55 ℃, and the solid medium of liquid state is poured into plate, and about 17ml is for subsequent use.
1.3.2 recovery bacterial strain
The ampoule that 4 kinds of freeze-drying bacterial strains are housed is cleaned with the absorbent cotton of 75% alcohol respectively, with ampoule bottleneck heat sterilization, dripped stroke-physiological saline solution at ampoule neck with flame, with tweezers bottleneck is opened.Draw the corresponding liquid nutrient medium of 0.3-0.4ml with liquid-transfering gun, splash in the ampoul tube, gently vibration piping and druming makes the dissolving of freeze-drying thalline be suspension.Whole bacteria suspensions is moved into test tube, and liquid nutrient medium is diluted to 5ml, and Candida albicans is in 25 ℃, and streptococcus mutans, lactobacillus, actinomyces viscosus were cultivated 48 hours in 37 ℃ temperature shaking table.
The bacterial strain of recovery is seeded in respectively on the corresponding culture medium flat plate, and accordingly respectively at cultivating 24 hours in the constant incubator under the temperature of 25 ℃ and 37 ℃, getting single bacterium colony Morphological Identification that dyes is culture.
1.3.3 bracket sterilization
With common bracket and nitrating TiO
2-xN
xThe film bracket is put into container with gauze parcel, and 110 ℃ of high-pressure sterilizing pots 15 minutes are for subsequent use.
1.3.4. in-vitro antibacterial performance test
1.3.4.1 colony number experiment
It is 1.5 * 10 that Candida albicans, streptococcus mutans, lactobacillus, actinomyces viscosus are mixed with concentration
6The bacteria suspension of CFU/ml is got 100 μ L and is added in the 3ml liquid nutrient medium, and puts into respectively positive group (nitrating TiO in vitro
2-xN
xThe film bracket) and 2 of negative group (common straight silk bow supporting groove) brackets, radiation of visible light cultivation 24 hours in 25 ℃ and the 37 ℃ of lower shaking tables.
Take out fully vibration, draw bacteria suspension 10 μ L from every test tube, stroke-physiological saline solution is diluted to 10ml, drawing 10 μ L joins in the solid medium that is cooled to 55 ℃ again, fully shake up, pour into plate, cultivated 24 hours enumeration under 25 ℃ of Candida albicanss and streptococcus mutans, lactobacillus, 37 ℃ of conditions of actinomyces viscosus.
Calculation result
1.3.4.2 adhesion experiment
Get TiO
2-xN
xFilm bracket and common straight silk bow supporting groove are soaked in and contain 1.5 * 10
6In the streptococcus mutans suspension of CFU/ml, in 37 ℃ of constant incubators, cultivate 3h.After the taking-up bracket washes with PBS liquid, place fixedly 2h of 2.5% glutaraldehyde solution, Gradient elution using ethanol after the flushing of PBS liquid, be placed on again replacement Treatment 25min in the 100% Isoamyl Acetate FCC solution, carry out critical point drying in the CO2 critical point drying machine, under scanning electron microscope, observe the bacterial adhesion feelings behind the metal spraying
2.1 colony number experiment
The enumeration of table 3 bracket germ resistance
Table 3 experimental result shows that the experimental group bracket all shows certain germ resistance.Antibiotic rate to oral cavity Main Pathogenic Bacteria streptococcus mutans, lactobacillus, actinomyces viscosus and Candida albicans is respectively 95.19%, 91.00%, 69.44% and 98.86%.Wherein there is larger difference in the anti-microbial activity of facultative anaerobe, between 95.19-69.44%, and the antimicrobial efficiency of fungi is reached 98.86%.With TiO
2-xN
xThe film bracket and be soaked in streptococcus mutans after, SEM observes visible common straight silk bow supporting rooved face a large amount of bacterial adhesions; And TiO
2-xN
xThe bacterium of film bracket surface adhesion obviously is less than common straight silk bow supporting groove, distributes to disperse (Fig. 4-2).
In Orthodontic Treatment, fixed appliance is widely applied clinical because of the accuracy of its high efficiency and moving teeth.Yet some complication such as enamel demineralization, sick, the gingivitis of dental caries have appearred in fixed appliance in clinical use procedure.The common flora that causes enamel demineralization and dental caries disease is streptococcus mutans, and lactobacillus and actinomyces viscosus often cause the inflammation of gum and periodontal.Candida albicans is as conditioned pathogen, and the recall rate in the orthodontic treatment patient is 24-40%, and teenager's oral Candida bacterial bearing rate has considerable change before and after fixedly rescuing.Therefore, this research selects streptococcus mutans, lactobacillus, actinomyces viscosus, Candida albicans as strain subject.
Standard GB/T 23763-2009 has done standard code to " evaluation of photocatalysis antibacterial material and goods anti-microbial property ".The present invention carries out in strict accordance with the test method of this standard code, and anti-microbial property is estimated.
The most frequently used bacteriostatic experiment comprises Bactericidal test and bacterial counting.Inhibition zone method is a kind of common method of qualitative test bacteriostasis property, and the diameter that characterizes the bacteriostasis property inhibition zone commonly used of antibacterial material represents.Inhibition zone is more simple and clear than counting process, but because sample of the present invention is square bracket, can't obtain obvious inhibition zone, therefore considers the usage count method.The ordinary method of bacterial count has plate dilution method, MPN method, blood cell plate counting process, bacterium is counted determinator method, nephelometry, dry cell weight method etc. automatically, and front 4 kinds of methods are direct-counting methods, and rear 2 kinds is indirect counting process.Turbidimetry is for measuring the method for determining suspended sediment concentration through the light intensity of particle in suspension medium.We reflect the biocidal property of the soak solution that soaks antibiotic body different time by the optical density(OD) OD value of bacteria suspension, and the less anti-microbial property of OD value is stronger, but are subjected to easily the impact of solid substance in the substratum, dead thalline.The present invention combines turbidimetry and colony counting method, will soak common bracket and TiO
2-xN
xThe bacteria suspension of film bracket is coated solid medium and is cultivated, and carries out direct enumeration again, two kinds of methods is combined obtain TiO
2-xN
xThe antibiotic rate of film bracket.
This research experiment result shows, TiO
2-xN
xThe more common bracket of film bracket has good antimicrobial property, and streptococcus mutans, lactobacillus, actinomyces viscosus, Candida albicans are all shown good anti-microbial activity.TiO
2-xN
xThe anti-microbial activity that the film bracket has and TiO
2-xN
xFilm is relevant.At straight silk bow supporting groove plated surface TiO
2-xN
xBehind the film, the one side nano-TiO
2-xN
xBe a kind of photocatalysis antibacterial agent, under illumination condition, produce hydroxyl radical free radical (OH) and atomic oxygen (O), hydroxyl radical free radical has strong oxidizing property, is CO with various organism (comprising in harmful microbe) oxygenolysis
2And H
2O plays bacteriostatic action; In addition on the one hand, TiO
2-xN
xThe film bracket is less than common straight silk bow supporting groove surfaceness, is unfavorable for the adhesion of bacterium, has effectively reduced the gathering of bacterium on the bracket surface, thereby has reduced the possibility that infects.
4. nitrating TiO
2-xN
xThe mechanical property of film bracket
The stainless steel straight silk bow supporting groove is to use at present maximum a kind of brackets, utilizes coating technique after its surface forms nano thin-film, can have influence on the performance on this bracket surface.To this present invention to TiO
2-xN
xThe sticking power of film and substrate bracket is tested, and to nitrogen doped Ti O
2-xN
xThe performances such as the roughness on the common bracket surface before film bracket and the plated film and friction resistance compare research.
1 materials and methods
1.1 material
Straight silk bow supporting groove (Hangzhou three is than medicine equipment company limited, 0.022 " standard type) nitrating TiO
2-xN
xThe film bracket
Artificial saliva (prescription: 0.26%NaH2PO4H2O, 2.17%NaHPO47H2O, 0.9%NaCl, use
PH value to 6.75 is adjusted in HCl and NaOH titration
1.2 experimental installation
Atomic force microscope (AFM) (Asylum Reserch MFP-3D AFM)
Multifunctional material surface tester (MFT-4000)
Frictional force trier (14FW reciprocating friction trier, Japanese Xin Dong Co., Ltd.)
1.3 experimental procedure
1.3.1 bracket surfaceness test
Scanning electron microscopic observation nitrogen doped Ti O
2-xN
xFilm bracket surface tissue, and get common bracket (Hangzhou three is than medicine equipment company limited, 0.022 " standard type) and nitrogen doped Ti O
2-xN
xEach 12 of film brackets utilize atomic force microscope (Asylum Reserch MFP-3D AFM) test surfaces RMS (rootmean-square) roughness, and the statistics of the RMS roughness on two class bracket surfaces is assessed.
Table 4. surfaceness
Table 4 is common bracket and nitrogen doped Ti O
2-xN
xThe statistics of surperficial RMS (rootmean-square) roughness of film bracket.Both are carried out paired t-test, t=2.521 as a result, P＜0.05 illustrates common bracket and nitrogen doped Ti O
2-xN
xFilm bracket difference in surface roughness has statistical significance, nitrogen doped Ti O
2-xN
xFilm bracket roughness is lower.Common bracket and TiO
2-xN
xFilm bracket surface RMS roughness (nm) * P＜0.05.
1.3.2 the sticking power of bracket surface film test
Adopt scratch method test TiO
2-xN
xFilm is to the adhesion strength of substrate bracket.MFT-4000 multifunctional material surface tester is adopted in experiment, and pressure head is that 120 ° of taperings, radius are the diamond tip of 0.2mm, Ending Load 60N, loading velocity 60N/m, cut 5mm.Experiment is got the mean value of 6 tests with 6 samples, obtains the threshold value of adhesive force.
Shown in the table 5, TiO
2-xN
xFilm is 40.87N to the adhesion strength of substrate bracket.Experimental result shows, TiO
2-xN
xFilm and stainless steel bracket have stronger sticking power.
Table 5 adhesive force
1.3.3 friction testing
Utilize 14FW reciprocating friction trier to measure stiction and the kinetic force of friction of respectively organizing under moisture state and the drying regime between arch wire and bracket.Fig. 4 is the trier synoptic diagram.
Clean bracket and arch wire before the experiment, dry up rear for subsequent use.Arch wire is fixed on the anchor clamps two ends, and bracket is fixed on the sole platform of frictional testing machines, adjust arch wire and Bracket placement, arch wire is only contacted and keeping parallelism with bracket groove bottom, avoid the groove sidewall on the impact of experimental data.The call through test machine, loading counterweight power value is 200g, arch wire moves 5mm with the speed of 6mm/min in the bracket groove, measure kinetic force of friction and stiction.When measuring under the moisture state, the artificial saliva for preparing is dripped in the bracket surface, again the arch wire that places is placed in the groove.
Arch wire is got titanium-nickel wire circle silk 0.012,0.014,0.016 and Rectangular SS archwires 0.017*0.025,0.018*0.025, experiment straight silk bow supporting groove and nitrating TiO
2-xN
xThe film bracket.Every group 5 parallel, will change bracket when dripping artificial saliva or conversion arch wire.
Table 6 and table 7 are common bracket and TiO
2-xN
xThe film bracket is the maximum static friction force under drying regime and moisture state and kinetic force of friction respectively.
The common bracket of table 6 and TiO
2-xN
xFilm bracket maximum static friction coefficient on surface (Cofs)
1) * compares with feminine gender, P＜0.05
2) △ compares with drying regime, P＜0.05
Positive in feminine gender, but relatively do not have statistical significance
The common bracket of table 7 and TiO
2-xN
xFilm bracket surface dynamic friction coefficient (Cofk)
1) * compares with feminine gender, P＜0.05
2) △ compares with drying regime, P＜0.05
Table 4 and table 5 are common bracket and TiO2-xNx film bracket skin friction coefficient table.The t assay shows, titanium-nickel wire and bracket combination under the drying regime, coefficient of maximum static friction and the kinetic friction coefficient of TiO2-xNx film bracket all are greater than common bracket, difference has statistical significance (P＜0.05), and under the moisture state, coefficient of maximum static friction and the kinetic friction coefficient of TiO2-xNx film bracket all are less than common bracket, but relatively do not have statistical significance (P＞0.05); No matter be moisture state or drying regime, Stainless Steel Wire and bracket combination, coefficient of maximum static friction and the kinetic friction coefficient of TiO2-xNx film bracket all are less than common bracket, and difference has statistical significance (P＜0.05); Coefficient of maximum static friction and kinetic friction coefficient are greater than drying regime under the moisture state, and difference has statistical significance (P＜0.05).
The result shows that TiO2-xNx film bracket has obviously reduced the bracket skin friction coefficient, and artificial saliva has increased the frictional coefficient of bracket.
Adhesive force refers to film to the size of the adhesive capacity of substrate, i.e. film and the substrate material bonding strength under Chemical bonding or the effect of physics snap-in force.Because thin-film material and base material belong to diverse material, so the adhesion problem between thin-film material and the substrate is most important.Simultaneously, the power of sticking power directly affects the performance of thin-film material.For TiO
2-xN
xThe film bracket, bring the oral cavity into after, can be subject to the friction from food and toothbrush, because the difference of surface film sticking power can cause it to strip off, so surface TiO
2-xN
xThe sticking power of film and substrate bracket seems extremely important.This experiment adopts the most frequently used scratch method to test TiO
2-xN
xThe adhesion strength of film and bracket obtains film surface failure value and film-primary surface stale value, and the latter is exactly the sticking power of film and substrate, and namely sticking power is 40.87N.This experiment employing purity is 99.99% target, the substrate bracket is the stainless steel of high rigidity, test the strict pre-treatment of front process to improve surface energy, strict control vacuum tightness in the preparation thin-film process, suitable raising base reservoir temperature in sputter simultaneously, the result shows that bracket and film have stronger sticking power.
Secondly, the bracket surfaceness also is an important indicator that affects the bracket performance.The bracket surfaceness directly affects the size of frictional force in the orthodontic treatment, and frictional force is to need the power that overcomes in the orthodontic treatment, reduces friction and can obtain more effectively that tooth moves.Simultaneously, shaggy bracket is compared the easier absorption bacterial plaque of ganoid bracket, causes the oral hygiene situation to descend.The present invention passes through at bracket plated surface TiO
2-xN
xFilm has improved the bracket surface property, and the bracket surfaceness is descended, and is conducive to reduce in the Tooth Movement process probability that the bacterial plaque of frictional force between bracket and arch wire and reduction adheres to.
Moreover sliding mechanism is the core of modern straight wire appliance.In the process of arch wire and bracket relatively sliding, can produce frictional force, the size of frictional force directly has influence on the efficient of rescuing.Frictional force when how to reduce orthodontic treatment between bracket and the arch wire is the key that obtains efficient result for the treatment of.The present invention utilizes five groups of arch wires to common bracket and TiO
2-xN
xMaximum static friction force and the force of sliding friction of film bracket under moistening and drying regime compares.For fear of the impact of ligature type on frictional force, in test arch wire is not done ligation and process.When orthodontic treatment, the power between bracket and arch wire is generally 50-300g, and the present invention selects afterburning 150g, allows arch wire and bracket groove level keep zero degree, eliminates sidewall for the impact of frictional force.The result shows, moistening or drying regime no matter, TiO
2-xN
xThe sound frictional force of film bracket is respectively organized the frictional force of arch wire all significantly greater than the frictional force under the drying conditions all less than common bracket when saliva is arranged.
Claims (1)
- One kind with radio-frequency magnetron sputter method at metal bracket surface attachment nitrating TiO 2-xN xThe side of film, its step comprises:(1) pre-treatment of substrate1. the precleaning of vacuum chamberAt first, will check vacuum chamber before thin film sputtering, remove the dirt settling on its lumen wall and the substrate disc, then use the careful wiping of alcohol cotton yarn, until cotton yarn is when white substantially, then residual alcohol is wherein taken out in baking;2.. the processing of substrateBracket is immersed in 40g/L NaOH, 25g/L NaCO 3, 50g/L Na 3PO 412H 2O and 7.5g/LNa 2SO 3Formulated mixed solution constant temperature cleans 25min at 90 ℃, observe the surface without the globule, then bracket is put into the beaker that fills 99.5% acetone soln, ultrasonic cleaning 20min, take out the post-drying sample also blows substrate surface off with the elevated pressure nitrogen air gun dust, then put into vacuum chamber;3.. the reverse sputtering of bracketThe bracket of cleaning is put into vacuum chamber, vacuumize and reach 3.0 * 10 -4During Pa, pass into Ar gas, regulate push-pull valve to gas pressure in vacuum and reach 2Pa, then open the ionization power supply that is connected on the substrate disc, substrate is carried out reverse sputtering 20min with the zone of oxidation of removal substrate surface and some residual dirts, reverse sputtering power is 30W;(2) nitrating TiO 2-xN xThe preparation of film metal bracketAfter bracket has been carried out clean operation, with high-purity Ti O 2Ceramic target (purity is 99.99%) is installed on JZCK-580 high vacuum multifunctional magnetic control sputtering machine, connects the radio-frequency sputtering power supply, TiO 2Target is of a size of 75mm*5mm, blocks target with the target baffle plate, carries out the pre-sputter of 20min, and power is 100W, removes TiO 2The impurity layer on target surface; TiO 2The pre-sputter of target is removed the target baffle plate after finishing, and bracket is moved on to begin TiO below the target 2The sputter of film; The substrate vacuum degree is 1.0 * 10 -3Pa, operating air pressure 1.0Pa passes into two kinds of gases of argon gas and nitrogen, and argon gas and nitrogen mass flux ratio are 30: 1, radio-frequency sputtering power 300W, 300 ℃ of underlayer temperatures were metal bracket surface sputtering 4 hours; To make TiO 2-xN xFilm places the inherent nitrogen atmosphere of high temperature box type resistance furnace to carry out anneal, and the time kept 2 hours, and annealing temperature is controlled at 450 ℃, after the annealing, gets nitrating TiO 2-xN xThe film metal bracket.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637117A (en) * | 2016-12-21 | 2017-05-10 | 蚌埠玻璃工业设计研究院 | High-efficiency preparation method for nitrogen-doped titanium dioxide film |
| CN108039317A (en) * | 2017-12-21 | 2018-05-15 | 苏州赛源微电子有限公司 | A kind of high-cleanness integrated circuit plate |
| CN111381302A (en) * | 2020-04-20 | 2020-07-07 | 深圳市秉兴光电技术有限公司 | Blue-light-preventing and sterilizing anti-dazzle protection sheet for display screen |
| CN111424236A (en) * | 2020-04-29 | 2020-07-17 | 缙云县太极科技有限公司 | Preparation method of antibacterial titanium product |
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2011
- 2011-07-08 CN CN2011101924728A patent/CN102864425A/en active Pending
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| 束嫘 等: "纳米陶瓷涂层托槽的研制", 《实用口腔医学杂志》 * |
| 陈顺利 等: "射频磁控溅射制备TiO2-xNx薄膜及其光催化性能研究", 《功能材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637117A (en) * | 2016-12-21 | 2017-05-10 | 蚌埠玻璃工业设计研究院 | High-efficiency preparation method for nitrogen-doped titanium dioxide film |
| CN108039317A (en) * | 2017-12-21 | 2018-05-15 | 苏州赛源微电子有限公司 | A kind of high-cleanness integrated circuit plate |
| CN111381302A (en) * | 2020-04-20 | 2020-07-07 | 深圳市秉兴光电技术有限公司 | Blue-light-preventing and sterilizing anti-dazzle protection sheet for display screen |
| CN111424236A (en) * | 2020-04-29 | 2020-07-17 | 缙云县太极科技有限公司 | Preparation method of antibacterial titanium product |
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