CN107034508B - A kind of UV auxiliary electrostatic is atomized the preparation method of formation system and coating of titanium dioxide - Google Patents

A kind of UV auxiliary electrostatic is atomized the preparation method of formation system and coating of titanium dioxide Download PDF

Info

Publication number
CN107034508B
CN107034508B CN201710176940.XA CN201710176940A CN107034508B CN 107034508 B CN107034508 B CN 107034508B CN 201710176940 A CN201710176940 A CN 201710176940A CN 107034508 B CN107034508 B CN 107034508B
Authority
CN
China
Prior art keywords
coating
titanium dioxide
titanium
titanium sheet
differential arc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710176940.XA
Other languages
Chinese (zh)
Other versions
CN107034508A (en
Inventor
李翔
方思懿
方明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Ke Hui Medical Treatment Equipment Co Ltd
Original Assignee
Zhejiang Ke Hui Medical Treatment Equipment Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Ke Hui Medical Treatment Equipment Co Ltd filed Critical Zhejiang Ke Hui Medical Treatment Equipment Co Ltd
Priority to CN201710176940.XA priority Critical patent/CN107034508B/en
Publication of CN107034508A publication Critical patent/CN107034508A/en
Application granted granted Critical
Publication of CN107034508B publication Critical patent/CN107034508B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/26Anodisation of refractory metals or alloys based thereon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/025Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/306Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104Silver, e.g. silver sulfadiazine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602Type of release, e.g. controlled, sustained, slow
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/24Materials or treatment for tissue regeneration for joint reconstruction

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses the preparation methods of a kind of UV auxiliary electrostatic atomization formation system and coating of titanium dioxide.The method is to combine differential arc oxidization technique and electrostatic atomization technology, basic step are as follows: the porous silica titanium coating mixed with silver nano-grain is prepared in electrolyte quota, differential arc oxidation, drying, heat treatment, electrostatic atomization, photoreduction.Research shows that the coating of titanium dioxide of silver nano-grain doping has good anti-microbial property and bioactivity.Preparation method of the present invention is simple, strong operability, low raw-material cost, and whole preparation process carries out in air atmosphere, is not necessarily to special device.

Description

A kind of UV auxiliary electrostatic is atomized the preparation method of formation system and coating of titanium dioxide
Technical field
The present invention relates to bone tissue engineer coating material, in particular to a kind of UV auxiliary electrostatic atomization formation system and (people Work articular prosthesis surface) preparation method of coating of titanium dioxide.
Background technique
In past half a century, due to biosynthesis new material continue to bring out with surgery operating technology it is continuous into Step, applications of all kinds of new materials in surgical field of significant boosting, and with the significant growth of all kinds of artificial joint prosthesis.With This also becomes increasingly conspicuous with complication such as the high infection rate of articular prosthesis and resulting prosthetic loosenings simultaneously.In the past Research have confirmed, cause the mechanism infected around articular prosthesis to be, adhere to the surface of prosthese by bacterioneuston first, with After form biomembrane.Therefore, how to inhibit bacterioneuston in the fixation of merging prosthetic surface in time, how to effectively improve prosthese week The effective antibiotics concentration enclosed is the important topic in the current field to effectively prevent the formation of bacterial biof iotalm.Therefore, The coating material on the artificial implant surface with bioactivity and anti-microbial property has broad application prospects.
Differential arc oxidation (micro arc oxidation, MAO) technology is retaining low-density, nothing possessed by titanium class alloy Magnetic, the excellent mechanical property such as high-intensitive, corrosion resistance is strong, performance is stable, elasticity modulus is good and excellent biocompatibility On the basis of, there is the nanometer scale ceramics coating of unique surface characteristic and high surface energy in surface of metal titanium preparation, and life can be mixed The long factor (bone morphogenetic protein, transforming growth factor-β, insulin-like growth factor etc.), metallic element (silver, copper etc.) or Nonmetalloid (nitrogen, silicon etc.) etc. forms composite ceramic coat.Coating using differential arc oxidization technique preparation has nanoscale table Face shape characteristic and high surface area can provide additional site for the absorption of protein, to promote Facing material and cell Interaction.High-pressure electrostatic atomization has many advantages, such as that mist droplet particle size is tiny, partial size scale is single, spatial dispersion degree is wide, extensively It is general to be applied to the fields such as the pesticide herd forestry prevention and control of plant diseases, pest control, industry spraying and material film preparation.High-pressure electrostatic reduces liquid Surface tension and viscosity resistance make liquid be easily broken into more tiny drop, make fog drop size distribution more evenly.Droplet lotus After electricity, Charged Droplet is easy to happen secondary-atomizing under the action of high-voltage electrostatic field, further decreases mist droplet particle size;It charges simultaneously Between charge under repulsion effect, disperse degree increases droplet, and can induce in object opposite with charge polarity itself Charge, to be easier to be captured by object under the polarization force, gravitation the effects of.
The implant surface antibiotic paint studied at present include vancomycin, gentamicin, nitric oxide releasing gel, Iodine and silver-colored (Ag) etc..In the active factors of incorporation titanium-based matter composite coating, has with metallic element and generated with matrix titanium elements Keyness bonding keeps surface modified more lasting and has attracted much attention.Silver has used for many years as the antibacterial agent of wide spectrum, is to study most For popular inorganic antiseptic.Document report, silver have stronger kill to gram-positive bacteria, Gram-negative bacteria and anaerobic bacteria Bacterium ability.In metal ion known today, anti-microbial property be only second to mercury come all inorganic metals second (mercury by It is huge in toxicity, it is not used in antibacterial agent).Studies have shown that silver is far longer than it for eukaryocyte for prokaryotic cell toxicity Toxicity, therefore relatively low cytotoxicity can be maintained while guaranteeing good antibacterial efficacy.However, conventional silver is antibacterial Agent is there are silver ion rate of release is too fast, the poor disadvantage of Durability of antimicrobial effect.With the rapid development of nano materials research, people Start sight turning to nano silver antibacterial material.The antibacterial effect of nanometer-level silver particle is 200 times of micro nanometer silver particle or more, The release dynamics of silver ion obviously slow down.Relative to traditional silver particles, the silver particles of nanoscale due to its high-specific surface area, Surface atom number increases and the contact probability of bacterium is significantly increased therewith.Nano silver particles have very strong chemical activity, table Easily with other chemical groups bonding reaction occurs for the atom in face, so as to prepare the nano silver composite material of rock-steady structure.Therefore, The silver-carrying nano particulate titanium dioxide structure coating on the artificial implant surface with bioactivity and anti-microbial property has wide Application prospect.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of UV auxiliary electrostatic atomization formation system and two The preparation method of titania coating.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of UV auxiliary electrostatic atomization formation system, including Cabinet, the cabinet lower end surface opening, top surface is equipped with static nozzle;Four sides of the cabinet are horizontally installed with ultraviolet Lamp.
A kind of preparation method of (artificial prosthesis surface) coating of titanium dioxide with biocompatibility and anti-microbial property, The following steps are included:
1) it is mixed using anhydrous sodium metasilicate and sodium hydroxide as electrolyte (wherein, Na2SiO3Concentration be 0.5mol/L, The concentration of NaOH is 0.05mol/L), using titanium sheet as anode, platinized platinum is cathode, and titanium sheet is in 220V, 1min;Point of 235V, 1min Differential arc oxidation 2 minutes under section voltage;
2) titanium sheet that step 1 differential arc oxidation obtains is placed on drying in 80 DEG C of baking ovens, is taken out after dry, be put into sintering furnace heat Processing keeps the temperature 3~4h with 5 DEG C/min heating rate to 450 DEG C.
3) step 2 treated titanium sheet immerses in Dopamine hydrochloride Tris-HCl buffer (10mM, pH=8.5), is put into 37 DEG C of constant-temperature table vibrates 24 hours under dark condition.
4) solution tank for being loaded with 0.1M silver nitrate solution is connected with static nozzle, titanium sheet is placed in cabinet, so that quiet Electric injector face titanium sheet, opens simultaneously ultraviolet lamp in cabinet, carries out atomization reduction treatment 30 minutes to the titanium sheet of step 3 processing: Wherein, the atomization voltage value between static nozzle and titanium sheet is 5-6kV, and the atomization flow velocity of silver nitrate solution is 6-8 μ L/min.
The beneficial effects of the present invention are:
The present invention realizes silver nano-grain in titanium dioxide by the spraying method of material surface modifying and UV auxiliary electrostatic The uniform and stable load on titanium coating surface, so that silver nano-grain slow sustained release in body fluid, is guaranteeing prolonged resist While bacterium performance, the biocompatibility of material ensure that, enrich bioactivity titanium dioxide nanostructure coating in bone group Knit the application of engineering field.
Detailed description of the invention
Fig. 1 UV auxiliary electrostatic atomization molding system schematic.
The SEM photograph of Fig. 2 Examples 1 to 3 coating of titanium dioxide.
The EDS power spectrum picture of the differential arc oxidation coating of titanium dioxide for the Ag nano particles doping that Fig. 3 is prepared.
The XRD spectrum of the differential arc oxidation coating of titanium dioxide for the Ag nano particles doping that Fig. 4 is prepared.
The Ag of the differential arc oxidation coating of titanium dioxide for the Ag nano particles doping that Fig. 5 Examples 1 to 3 is prepared+Release is bent Line chart
The antibacterial ring size photo for the Ag nano particles doping differential arc oxidation coating of titanium dioxide that Fig. 6 is prepared.
The cell compatibility MTT experiment result for the Ag nano particles doping differential arc oxidation coating of titanium dioxide that Fig. 7 is prepared.
Specific embodiment
Carry out the technical solution that the present invention will be described in detail in the following with reference to the drawings and specific embodiments, but the present invention is not limited to reality Example is applied, those skilled in the art can be adjusted according to the actual situation.
Example 1
1) by 0.5mol/L Na2SiO3Mixed solution with 0.05mol/L NaOH is as electrolyte;
2) using the titanium sheet after cleaning as anode, platinized platinum is cathode, and titanium sheet is in 220V, 1min;The segmentation voltage of 235V, 1min Lower differential arc oxidation 2 minutes;
3) the unformed coating of titanium dioxide material for obtaining step 2 differential arc oxidation is placed in 80 DEG C of baking ovens dry, dry After take out, be put into sintering furnace heat treatment, with 5 DEG C/min heating rate to 450 DEG C, heat preservation 3~4h remove organic principle.
4) under dark condition, the differential arc oxidation coating of titanium dioxide material after step 3 heat treatment is immersed into 0.1M nitric acid Silver-colored solution 4 hours.
5) by step 4 treated titanium sheet washing it is dry after, with ultraviolet light (wavelength is~250nm) irradiation 30 minutes, Titanium plate surface obtains the titanium dioxide nanostructure coating with biocompatibility and anti-microbial property.
Shown in the differential arc oxidation coating of titanium dioxide structure such as Fig. 2 (a) for the Ag nano particles doping that embodiment 1 obtains.
Example 2
Ag nano particles load on the differential arc oxidation coating of titanium dioxide obtained in view of use 1 method of embodiment is not It is enough uniform and stable.Therefore method is improved, the modified differential of the arc that Ag nano particles doping is prepared in surface is carried out to material Ferric oxide/titanium dioxide coating.
1) by 0.5mol/L Na2SiO3Mixed solution with 0.05mol/L NaOH is as electrolyte;
2) using the titanium sheet after cleaning as anode, platinized platinum is cathode, and titanium sheet is in 220V, 1min;The segmentation voltage of 235V, 1min Lower differential arc oxidation 2 minutes;
3) the unformed coating of titanium dioxide material for obtaining step 2 differential arc oxidation is placed in 80 DEG C of baking ovens dry, dry After take out, be put into sintering furnace heat treatment, with 5 DEG C/min heating rate to 450 DEG C, heat preservation 3~4h remove organic principle.
4) step 3 treated coating of titanium dioxide immerses Dopamine hydrochloride Tris-HCl buffer (10mM, pH=8.5) In, it is put into 37 DEG C of constant-temperature table and is vibrated 24 hours under dark condition.It takes out, washing, drying.
5) under dark condition, the differential arc oxidation coating of titanium dioxide material after step 4 heat treatment is immersed into 0.1M nitric acid Silver-colored solution 4 hours.
6) by step 5 treated titanium sheet washing it is dry after, with ultraviolet light (wavelength is~250nm) irradiation 30 minutes, Titanium plate surface obtains the titanium dioxide nanostructure coating with biocompatibility and anti-microbial property.
Shown in the differential arc oxidation coating of titanium dioxide structure such as Fig. 2 (b) for the Ag nano particles doping that embodiment 2 obtains.
Example 3
The Ag nano particles agglomeration on differential arc oxidation coating of titanium dioxide being prepared due to embodiment 2 is serious, Therefore a kind of UV auxiliary electrostatic atomization formation system is used to prepare nano particle containing Ag (artificial prosthesis surface) coating of titanium dioxide, The following steps are included:
1) it is mixed using anhydrous sodium metasilicate and sodium hydroxide as electrolyte (wherein, Na2SiO3Concentration be 0.5mol/L, The concentration of NaOH is 0.05mol/L), using titanium sheet as anode, platinized platinum is cathode, and titanium sheet is in 220V, 1min;Point of 235V, 1min Differential arc oxidation 2 minutes under section voltage;
2) titanium sheet that step 1 differential arc oxidation obtains is placed on drying in 80 DEG C of baking ovens, is taken out after dry, be put into sintering furnace heat Processing, with 5 DEG C/min heating rate to 450 DEG C, 3~4h of heat preservation removes organic principle.
3) step 2 treated titanium sheet immerses in Dopamine hydrochloride Tris-HCl buffer (10mM, pH=8.5), is put into 37 DEG C of constant-temperature table vibrates 24 hours under dark condition.
4) atomization process is carried out to titanium sheet using UV auxiliary electrostatic atomization formation system, wherein UV auxiliary electrostatic atomization molding System includes cabinet, and the cabinet lower end surface opening, top surface is equipped with static nozzle;The horizontal peace in four sides of the cabinet Equipped with ultraviolet lamp, as shown in Figure 1.The solution tank for being loaded with 0.1M silver nitrate solution is connected with static nozzle, titanium sheet is placed in case In vivo, so that static nozzle face titanium sheet, opens simultaneously ultraviolet lamp in cabinet, atomization reduction is carried out to the titanium sheet of step 3 processing Processing 30 minutes: where the atomization voltage value between static nozzle and titanium sheet is 5-6kV, and the atomization flow velocity of silver nitrate solution is 6-8μL/min。
Shown in the differential arc oxidation coating of titanium dioxide structure such as Fig. 2 (c) for the Ag nano particles doping that embodiment 3 obtains.Phase Than embodiment 1, obtained Ag nano particles more uniformly spread densification on coating of titanium dioxide, reduce the group of Argent grain It is poly-.Compared to embodiment 2, reunion of the Ag nano particles on coating of titanium dioxide is reduced.
The differential arc oxidation coating of titanium dioxide EDS for the Ag nano particles doping that embodiment 3 is prepared is to titanium dioxide The Elemental redistribution of the microcosmos area of coating material carries out qualitative and quantitative analysis.As shown in figure 3, in differential arc oxidation coating of titanium dioxide Element ti, tri- kinds of elements of O, Ag have, and (a) is silver element, (b) is oxygen element, (c) is Ti element, (d) are electronic image;Table Bright Ag element smoothly mixes differential arc oxidation coating of titanium dioxide.
X-ray diffractogram (Fig. 4) shows that the differential arc oxidation titanium dioxide for the Ag nano particles doping that embodiment 3 is prepared applies Containing silver-colored simple substance in layer, show that Ag element is that anodic oxidation titania nanotube knot is smoothly mixed in the form of Nano silver grain Structure coating.
The Ag of Examples 1 to 3+Releasing curve diagram is as shown in figure 5, compare example 1 (example1) and example 2 (example2), hence it is evident that it can be seen that release of embodiment 3 (example3) silver ion in PBS is more slow lasting.
Fig. 6 is that the antibacterial ring size of the differential arc oxidation coating of titanium dioxide for the Ag nano particles doping that embodiment 3 is prepared is shone Piece.The coating of titanium dioxide that differential arc oxidation is prepared, Dopamine hydrochloride treated differential arc oxidation coating of titanium dioxide, nanometer Differential arc oxidation coating of titanium dioxide and the pure titanium sheet of control sample after the doping of Ag particle carry out antibacterial ring size experiment.When activation It is that sorbitol-MacConkey agar is basic (culture medium), that when bacteria is Brain Heart Infusion (BHI) Culture medium.Steps are as follows:
(1) 1mL bacterium solution is taken to be added in 9mL BHI culture medium from -80 DEG C, shaking table shakes 20h activation;
(2) being rule of thumb gradually diluted to concentration is 10^9,10^8,10^7,10^6,10^5,10^4, takes 10^5 concentration bacterium Ti piece is gently attached to media surface by 100 μ L of liquid, even spread to planar surface;
(3) 37 DEG C of constant incubator culture observations.
Antibacterial ring size experiment can whether there is or not the analyses of bacteriostasis property to the coating of titanium dioxide progress after Ag nano particles doping.Such as Shown in Fig. 6, there is antibacterial ring size (d) in the differential arc oxidation coating of titanium dioxide sample periphery for having Ag nano particles to adulterate, and control group is pure Titanium sheet (a), the differential arc oxidation coating of titanium dioxide sample (b) without Ag nano particles doping, Dopamine hydrochloride treated the differential of the arc There is not antibacterial ring size in ferric oxide/titanium dioxide coating sample (c) periphery.Experiment shows Ag nano particles doping prepared by embodiment 3 Differential arc oxidation coating of titanium dioxide have anti-microbial property.
Fig. 7 is the cytocompatibility of the differential arc oxidation coating of titanium dioxide for the Ag nano particles doping that embodiment 3 is prepared Property MTT experiment result.Specific step is as follows: (1) taking MG-63 cell, cell suspension is prepared in digestion and degree of thickening is 4x 104/ ml.(2) Ti, MAO, MAO/PD, MAO/PD/Ag sample are placed in 24 orifice plates, above-mentioned concentrations of cells suspension 1ml is added simultaneously in every hole It blows even.(3) culture termination in 24 hours is cultivated and is cleaned 3 times using PBS in incubator, and 200 μ l MTT liquid (5mg/ are added in every hole Ml) and 800 μ l continue to cultivate 4h without phenol red DMEM culture solution.(4) the micro concussion dissolution institute's shape of 1ml DMSO room temperature is added in every hole (being protected from light operation) is crystallized at formazan, every hole takes 200 μ l mixed liquors to be added in 96 orifice plates, and microplate reader is used under 490nm wavelength Measurement OD value simultaneously sets zeroing hole.It can thus be seen that the differential arc oxidation titanium dioxide for the Ag nano particles doping that embodiment 3 is prepared Titanium coating is while with relatively stable anti-microbial property, it may have preferable biocompatibility.

Claims (1)

1. a kind of using the atomization formation system preparation of UV auxiliary electrostatic there is the titanium dioxide of biocompatibility and anti-microbial property to apply The method of layer, the UV auxiliary electrostatic atomization formation system includes cabinet, and the cabinet lower end surface opening, top surface is equipped with electrostatic Spray head;Four sides of the cabinet are horizontally installed with ultraviolet lamp, which comprises the following steps:
1) it is mixed using anhydrous sodium metasilicate and sodium hydroxide as electrolyte, wherein Na2SiO3Concentration be 0.5mol/L, NaOH Concentration be 0.05mol/L, using titanium sheet as anode, platinized platinum is cathode, and titanium sheet is in 220V, 1min;The segmentation voltage of 235V, 1min Lower differential arc oxidation 2 minutes;
2) titanium sheet that step 1 differential arc oxidation obtains is placed on drying in 80 DEG C of baking ovens, is taken out after dry, is put into sintering furnace treatment Reason keeps the temperature 3 ~ 4h with 5 DEG C/min heating rate to 450 DEG C;
3) step 2 treated titanium sheet immerses in Dopamine hydrochloride Tris-HCl buffer, Dopamine hydrochloride Tris-HCl buffering Liquid concentration is 10mM, and pH=8.5 are put into 37 DEG C of constant-temperature table and vibrate 24 hours under dark condition;
4) solution tank for being loaded with 0.1M silver nitrate solution is connected with the static nozzle of UV auxiliary electrostatic atomization formation system, by titanium Piece is placed in the cabinet of UV auxiliary electrostatic atomization formation system, so that static nozzle face titanium sheet, opens simultaneously ultraviolet in cabinet Lamp carries out atomization reduction treatment 30 minutes to the titanium sheet of step 3 processing: where the atomization voltage between static nozzle and titanium sheet Value is 5-6kV, and the atomization flow velocity of silver nitrate solution is 6-8 μ L/min.
CN201710176940.XA 2017-03-22 2017-03-22 A kind of UV auxiliary electrostatic is atomized the preparation method of formation system and coating of titanium dioxide Active CN107034508B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710176940.XA CN107034508B (en) 2017-03-22 2017-03-22 A kind of UV auxiliary electrostatic is atomized the preparation method of formation system and coating of titanium dioxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710176940.XA CN107034508B (en) 2017-03-22 2017-03-22 A kind of UV auxiliary electrostatic is atomized the preparation method of formation system and coating of titanium dioxide

Publications (2)

Publication Number Publication Date
CN107034508A CN107034508A (en) 2017-08-11
CN107034508B true CN107034508B (en) 2019-01-25

Family

ID=59534226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710176940.XA Active CN107034508B (en) 2017-03-22 2017-03-22 A kind of UV auxiliary electrostatic is atomized the preparation method of formation system and coating of titanium dioxide

Country Status (1)

Country Link
CN (1) CN107034508B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108939149A (en) * 2018-07-18 2018-12-07 西南交通大学 Prepare the method and PEEK biomaterial of PEEK biological coating

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101703798A (en) * 2009-11-05 2010-05-12 上海纳米技术及应用国家工程研究中心有限公司 Nano hydroxyapatite coating and preparation method thereof and electrostatic atomization device
CN101862719A (en) * 2010-05-21 2010-10-20 东莞市铭丰包装品制造有限公司 Electrostatic spraying system for ultraviolet solidified paint
CN102058904A (en) * 2010-12-31 2011-05-18 重庆大学 Biological functionalized nano titanium material and preparation method thereof
CN104357814A (en) * 2014-11-24 2015-02-18 重庆大学 Titanium alloy containing antibacterial coating as well as preparation method and application thereof
CN105506711A (en) * 2016-01-25 2016-04-20 东北农业大学 Method for preparing double-side TiO2 nanotube array material with surface modified by silver nanoparticles through ultrasonic atomization-ultraviolet reduction combination
CN106421907A (en) * 2016-10-14 2017-02-22 湖北大学 Preparation method of graphene oxide-based hybrid biological functional coating

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2329498C (en) * 2000-01-10 2009-02-24 Brasscorp Limited Method of applying liquid fluorescent dyes to the internal parts of air conditioning or refrigeration systems
US7297397B2 (en) * 2004-07-26 2007-11-20 Npa Coatings, Inc. Method for applying a decorative metal layer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101703798A (en) * 2009-11-05 2010-05-12 上海纳米技术及应用国家工程研究中心有限公司 Nano hydroxyapatite coating and preparation method thereof and electrostatic atomization device
CN101862719A (en) * 2010-05-21 2010-10-20 东莞市铭丰包装品制造有限公司 Electrostatic spraying system for ultraviolet solidified paint
CN102058904A (en) * 2010-12-31 2011-05-18 重庆大学 Biological functionalized nano titanium material and preparation method thereof
CN104357814A (en) * 2014-11-24 2015-02-18 重庆大学 Titanium alloy containing antibacterial coating as well as preparation method and application thereof
CN105506711A (en) * 2016-01-25 2016-04-20 东北农业大学 Method for preparing double-side TiO2 nanotube array material with surface modified by silver nanoparticles through ultrasonic atomization-ultraviolet reduction combination
CN106421907A (en) * 2016-10-14 2017-02-22 湖北大学 Preparation method of graphene oxide-based hybrid biological functional coating

Also Published As

Publication number Publication date
CN107034508A (en) 2017-08-11

Similar Documents

Publication Publication Date Title
Hadidi et al. Electrophoretic-deposited hydroxyapatite-copper nanocomposite as an antibacterial coating for biomedical applications
Wang et al. NanoZnO-modified titanium implants for enhanced anti-bacterial activity, osteogenesis and corrosion resistance
Liu et al. Nano-modified titanium implant materials: a way toward improved antibacterial properties
Mokabber et al. Antimicrobial electrodeposited silver-containing calcium phosphate coatings
Fathima et al. Synthesis and characterization of ZrO2 nanoparticles-antimicrobial activity and their prospective role in dental care
Massa et al. Synthesis of new antibacterial composite coating for titanium based on highly ordered nanoporous silica and silver nanoparticles
Gunputh et al. Anodised TiO2 nanotubes as a scaffold for antibacterial silver nanoparticles on titanium implants
Pang et al. Multifunctional ZnO/TiO2 nanoarray composite coating with antibacterial activity, cytocompatibility and piezoelectricity
Li et al. Antibacterial activity of TiO2 nanotubes: influence of crystal phase, morphology and Ag deposition
CN103015166B (en) Nano-silver antibacterial fabric and preparation method thereof
Jadalannagari et al. Antimicrobial activity of hemocompatible silver doped hydroxyapatite nanoparticles synthesized by modified sol–gel technique
De Giglio et al. An innovative, easily fabricated, silver nanoparticle-based titanium implant coating: development and analytical characterization
Yang et al. Cytocompatibility and antibacterial activity of titania nanotubes incorporated with gold nanoparticles
Zhang et al. A functionalized Sm/Sr doped TiO2 nanotube array on titanium implant enables exceptional bone-implant integration and also self-antibacterial activity
Zhang et al. Sr/ZnO doped titania nanotube array: an effective surface system with excellent osteoinductivity and self-antibacterial activity
Di et al. Ag nanoparticles incorporated tannic acid/nanoapatite composite coating on Ti implant surfaces for enhancement of antibacterial and antioxidant properties
Patel et al. Surface functionalization of electrospun PAN nanofibers with ZnO–Ag heterostructure nanoparticles: Synthesis and antibacterial study
Gunputh et al. Multilayered composite coatings of titanium dioxide nanotubes decorated with zinc oxide and hydroxyapatite nanoparticles: controlled release of Zn and antimicrobial properties against Staphylococcus aureus
Zhang et al. Novel ternary vancomycin/strontium doped hydroxyapatite/graphene oxide bioactive composite coatings electrodeposited on titanium substrate for orthopedic applications
CN107022782A (en) A kind of preparation method of the titania nanotube structure coating with biocompatibility and anti-microbial property
Jiang et al. Fabrication of silver nanowires-loaded polydimethylsiloxane film with antimicrobial activities and cell compatibility
Wang et al. Osteogenic and antiseptic nanocoating by in situ chitosan regulated electrochemical deposition for promoting osseointegration
Huang et al. Enhanced antibacterial activity and biocompatibility of zinc-incorporated organic-inorganic nanocomposite coatings via electrophoretic deposition
CN109097760B (en) Preparation method of medical titanium material
Hsueh et al. Synergistic effects of collagen and silver on the deposition characteristics, antibacterial ability, and cytocompatibility of a collagen/silver coating on titanium

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A UV Assisted Electrostatic Atomization Molding System and Preparation Method of Titanium Dioxide Coating

Effective date of registration: 20221205

Granted publication date: 20190125

Pledgee: Industrial and Commercial Bank of China Limited Jinhua Branch

Pledgor: CANWELL MEDICAL Co.,Ltd.

Registration number: Y2022330003493

PE01 Entry into force of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20231205

Granted publication date: 20190125

Pledgee: Industrial and Commercial Bank of China Limited Jinhua Branch

Pledgor: CANWELL MEDICAL Co.,Ltd.

Registration number: Y2022330003493

PC01 Cancellation of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A UV assisted electrostatic atomization molding system and preparation method of titanium dioxide coating

Granted publication date: 20190125

Pledgee: Industrial and Commercial Bank of China Limited Jinhua Branch

Pledgor: CANWELL MEDICAL Co.,Ltd.

Registration number: Y2024980000673

PE01 Entry into force of the registration of the contract for pledge of patent right