CN108144112A - A kind of preparation method in composite coating of the surface of metal titanium with synergetic antibacterial effect - Google Patents

A kind of preparation method in composite coating of the surface of metal titanium with synergetic antibacterial effect Download PDF

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Publication number
CN108144112A
CN108144112A CN201810178709.9A CN201810178709A CN108144112A CN 108144112 A CN108144112 A CN 108144112A CN 201810178709 A CN201810178709 A CN 201810178709A CN 108144112 A CN108144112 A CN 108144112A
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hap
titanium
lys
composite coating
coating
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刘想梅
张演哲
吴水林
李朝阳
朱胜利
崔振铎
杨贤金
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Hubei University
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Hubei University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L27/56—Porous materials, e.g. foams or sponges
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract

This hair provides a kind of method for preparing lysozyme/chitosan/silver/hydroxyapatite (Lys/CS/Ag/HAp) composite coating in surface of metal titanium.The electrodeposit liquid of silver nitrate/chitosan/hydroxyapatite is first prepared as solvent with 1% acetic acid.Meanwhile 90 minutes alkali heat-treatments are carried out to titanium plate surface at 80 DEG C with the KOH solution of 4mol/L.Then using electrochemical workstation to the titanium plate surface electrochemical deposition CS/Ag/HAp coatings of alkali heat.Finally using sol evenning machine in one layer of lysozyme of CS/Ag/HAp coating surfaces spin coating, it is prepared into tool Lys/CS/Ag/HAp composite coatings.Lys/CS/Ag/HAp composite coatings can play quick sterilization effect using Lys dissolution of bacteria cell walls, and the Ag and CS of slow release can carry out long-acting bactericidal effect, coating made to have both shot and long term antibacterial effect.Also, the HAp in Lys/CS/Ag/HAp composite coatings has excellent biocompatibility, allows the titanium implants that preparation has Lys/CS/Ag/HAp composite coatings that can play osteogenic action.

Description

A kind of preparation method in composite coating of the surface of metal titanium with synergetic antibacterial effect
Technical field
The present invention relates to material science and technical field of nano material, and in particular to a kind of to have collaboration in surface of metal titanium The preparation method of the composite coating of antibacterial action, this method electrochemical deposition in a manner that spin coating is combined in titanium table Face prepares nanoscale lysozyme/chitosan/silver/hydroxyapatite (Lys/ with long-term antibacterial and superior bio compatibility CS/Ag/HAp) composite coating.
Background technology
Titanium as implant material have excellent toughness, intensity and be widely used in surgical operation.But Since the inertia of its own cannot promote the reparation of bone tissue to cure, and the postoperative sense as caused by extraneous factor in implantation process Dye can usually make operative failure, and patient is forced to carry out second operation, increases patient suffering and financial burden.So titanium implants need Solve the problems, such as two aspect of bioactivity and antibacterial.And with fracture caused by the aggravation of Chinese population aging, traffic accident etc. Phenomenon increases.The implant of research and development function admirable just seems increasingly urgent.Traditional antibacterial means such as injection of antibiotics etc. can be led Bacterial drug resistance is caused to increase, the super drug resistance bacterium that any antibiotic can not all be eliminated occurs.Therefore it must develop and be different from The anti-biotic material of traditional antibiotic treatment.The antimicrobial coating of nano-particle is exactly the hot spot and following development side researched and developed now To.
The preparation means numerous and complicated of antimicrobial coating.Including all good effect such as laser pulse, chemical graft.But hand The postoperative period for bacterium infection occur is indefinite from one day by one month.So the standby coating of unitary system, which does not have, takes into account length sterilization Timeliness.
Invention content
In view of this, the present invention in surface of metal titanium by preparing lysozyme/chitosan/silver/hydroxyapatite (Lys/ CS/Ag/HAp) composite coating imparts the excellent long-term antimicrobial efficiency of titanium and outstanding biocompatibility.Preparing Lys/ During CS/Ag/HAp composite coatings, the present invention carries out alkali heat-treatment to surface of metal titanium first, then sinks with electrochemistry Product method prepares CS/Ag/HAp composite coatings in surface of metal titanium, finally by sol evenning machine in above-mentioned one layer of sample surfaces spin coating Lys is prepared into Lys/CS/Ag/HAp composite coatings.Wherein, Ag nano particles are by AgNO by electrochemical deposition3In silver Ion reduction comes out what is formed, and the Ag nano particles restored have excellent antibiotic property, because containing in electrochemical deposition CS so that Ag in coating has a slow rate of release, thus antibiotic property has a long-term effect, in simultaneous electrochemical depositing coating HAp have very prominent biocompatibility, the calcium P elements that HAp contains have good osteogenic action.Pass through spin coating method Coating after preparation more one layer of Lys, Lys can quickly kill bacterium as a kind of hydrolase of hydrolytic bacteria cell wall.Cause This, the Lys/CS/Ag/HAp composite coatings prepared in a manner that electrochemical deposition and spin coating are combined have long-acting resist Bacterium property and biocompatibility.
First aspect present invention provides a kind of preparation of the composite coating in surface of metal titanium with synergetic antibacterial effect Method, step include：
S1, alkali heat-treatment is carried out to titanium sheet；
It is prepared by S2, chitosan/silver/carboxy apatite composite coating：Weigh AgNO3, chitosan, hydroxyapatite is dissolved in second As electrochemical deposition liquid in acid solution, the titanium sheet after alkali heat is put into electrochemical deposition liquid and carries out electrochemical deposition, in titanium Prepare chitosan/silver/carboxy apatite composite coating in piece surface；
It is prepared by S3, lysozyme/chitosan/silver/carboxy apatite composite coating：It is revolved after lysozyme is dissolved in acetic acid solution Being coated in surface obtained by step S2 and preparing has in the titanium sheet of chitosan/silver/carboxy apatite composite coating, is prepared in titanium sheet Lysozyme/chitosan/silver/carboxy apatite composite coating.
Second aspect of the present invention is provided using the above-mentioned composite coating in surface of metal titanium with synergetic antibacterial effect The product that preparation method is prepared.
The beneficial effects of the invention are as follows：
(1) surface of metal titanium is made to form rough porous structure using alkali heat-treatment, there is larger specific surface area, it can jail Admittedly load more coating；
(2) for general coating, the coating energy of the invention being prepared under the conditions of specific electrochemical deposition Play the role of slow release, the Ag in composite coating can slow release play antibacterial action, calcium P elements play long-term skeletonization Effect；
(3) Lys of spin coating can play the role of quick sterilization as the zymoprotein of hydrolytic bacteria cell wall and not have to cell There is damage, compared to antibiotic, drug resistance will not be generated；
(4) raw material sources in Lys/CS/Ag/HAp composite coatings are extensive and cheap, to cytotoxic.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention Some embodiments, for those of ordinary skill in the art, without creative efforts, can also basis These attached drawings obtain other attached drawings.
Fig. 1 is SEM figure of the titanium sheet after alkali heat-treatment in embodiment 1.
Fig. 2 is the SEM figures of the CS/Ag/HAp composite coatings formed in embodiment 2 by electrochemical deposition.
Fig. 3 is the SEM figures of the Lys/CS/Ag/HAp composite coatings formed after spin coating in embodiment 3.
Fig. 4 is immersed in silver ion elution profiles figure in SBF solution for 3 floating coat of embodiment.
Fig. 5 is the SEM figures of the Escherichia coli on Lys/CS/Ag/HAp composite coatings surface in embodiment 4.
Fig. 6 is the SEM figures of the staphylococcus aureus on Lys/CS/Ag/HAp composite coatings surface in embodiment 5.
Fig. 7 is alkaline phosphatase activities (ALP) test chart of Ag/ZnO/HA nano-composite coatings in embodiment 6.
Specific embodiment
The present invention provides a kind of preparation method in composite coating of the surface of metal titanium with synergetic antibacterial effect, steps Including：
S1, alkali heat-treatment is carried out to titanium sheet；
It is prepared by S2, chitosan/silver/carboxy apatite composite coating：Weigh AgNO3, chitosan, hydroxyapatite is dissolved in second As electrochemical deposition liquid in acid solution, the titanium sheet after alkali heat is put into electrochemical deposition liquid and carries out electrochemical deposition, in titanium Prepare chitosan/silver/carboxy apatite composite coating in piece surface；
It is prepared by S3, lysozyme/chitosan/silver/carboxy apatite composite coating：It is revolved after lysozyme is dissolved in acetic acid solution Being coated in surface obtained by step S2 and preparing has in the titanium sheet of chitosan/silver/carboxy apatite composite coating, is prepared in titanium sheet Lysozyme/chitosan/silver/carboxy apatite composite coating.
By CS/Ag/HAp composite coatings prepared by electrochemical deposition with the long-acting of slow release antibacterial material Ag and CS Antibiotic property, CS and the HAp and Lys of spin coating that electro-deposition is got on can effectively control the rate of release of silver ion, make silver ion Slow release plays the role of long-term antibacterial.And the calcium P elements discharged in HAp can facilitate bone, and bone tissue is accelerated to restore. Being prepared into Lys/CS/Ag/HAp composite coatings by spin coating means on the CS/Ag/HAp composite coatings of electrochemical deposition can be quick Lys is discharged, reaches efficient antibacterial effect early period, Lys has high efficiency for dissolution of bacteria cell wall, and Lys is easily It is obtained from egg white, it is cheap.Therefore, Lys/CS/Ag/HAp is prepared using the method that electrochemical deposition and spin coating combine Composite coating can play the role of excellent shot and long term antibiotic property, while can also take into account biocompatibility, promote tissue skeletonization, accelerate Knitting.
Preferably, in step S2, AgNO in the electrochemical deposition liquid3A concentration of 0.1~50mg/mL, chitosan A concentration of 0.1~50mg/mL, a concentration of 0.1~50mg/mL of hydroxyapatite；In step S3, the lysozyme is dissolved in second For the final concentration of lysozyme is made to reach 0.1~50mg/mL in acid solution.
More preferred, the additive amount of the lysozyme is titanium sheet addition 20~50uL lysozyme second per a diameter of 6mm Acid solution.
Preferably, step S2, in S3, the acetic acid solution is the acetic acid aqueous solution of quality of acetic acid a concentration of 1%.
Preferably, the condition of electrochemical deposition is described in step S2：0.1~10mA/cm of constant current2, titanium sheet and platinum electrode Between operating distance for 2~5cm, electrodeposition time is 0.1~30 minute.The electrodeposition temperature is 48~52 DEG C.In spy Under the conditions of fixed electrochemical deposition, HAp/CS/Ag is securely uniformly deposited on to titanium surface, plays long-term slow release antibacterial The effect of matter.
Preferably, in step S3, the condition of the spin coating is：Spin coating 2000~5000r/min of rotating speed, spin-coating time 10~ 60s.Spin coating Lys can easily and fast, uniformly be prepared it on coating before, and play the role of quick sterilization and the former Form the Continuous sterilization advantage of long short-acting combination.
Preferably, in step S1, the alkali heat-treatment is the KOH solution using 3.8~4.2mol/L at 78~82 DEG C 80~100 minutes alkali heat-treatments are carried out to titanium plate surface.
Second aspect of the present invention is provided using the above-mentioned composite coating in surface of metal titanium with synergetic antibacterial effect The product that preparation method is prepared.
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and embodiment more comprehensively, it is careful Ground describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1：
The processing method to coating titanium substrate is present embodiments provided, step includes：
(1) step 1：Ti is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror-like be presented.Then second is used Alcohol cleaning ultrasound 3 times, is then cleaned and is dried with deionized water again；
(2) step 2：90 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 80 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
Electronic Speculum detection is scanned to the titanium sheet that the above method is handled, obtained SEM figures are as shown in Figure 1, detection knot Fruit shows：Titanium sheet is after polishing, alkali heat-treatment, and surface can form the structure of even porous, and such an arrangement provides big ratios Surface area is conducive to the adherency and combination of coating.
Embodiment 2：
The method that electrochemical deposition CS/Ag/HAp composite coatings are carried out to coated titanium substrate surface is present embodiments provided, Step includes：
(1) step 1：Ti is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror-like be presented.Then second is used Alcohol cleaning ultrasound 3 times, is then cleaned and is dried with deionized water again；
(2) step 2：90 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 80 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：200mL electrochemical deposition liquids are prepared, using the acetic acid (Ac) of 1% mass concentration as solvent, are claimed Take the AgNO of 630mg3, the HAp of the CS of 400mg, 400mg, which are dissolved in 1%Ac, is used as solute.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 3mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 10 minutes time, operating distance 2cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
Electronic Speculum detection is scanned to the titanium sheet that the above method is handled, obtained SEM figures are as shown in Fig. 2, detection knot Fruit shows：Gill shape structure is presented in the CS/Ag/HAp composite coatings that the titanium plate surface of alkali heat deposits to adsorb in titanium sheet, coating With titanium sheet substrate good combination.
Embodiment 3：
The method to CS/Ag/HAp composite coatings surface spin coating Lys is present embodiments provided, step includes：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：90 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 80 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, weigh The AgNO of 630mg3, the HAp of the CS of 400mg, 400mg, which are dissolved in 1%Ac, is used as solute.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 3mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 10 minutes time, operating distance 2cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
(5) step 5：The Lys solution of 20mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 50uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
Electronic Speculum detection is scanned to the titanium sheet that the above method is handled, obtained SEM figures are as shown in figure 3, detection knot Fruit shows：After the titanium sheet of alkali heat prepares Lys/CS/Ag/HAp composite coatings by the method for electrochemical deposition and spin coating, sample Membranaceous coating is presented in product surface, and the gap uniformity of the porous and electrochemical deposition of alkali heat is covered.
Embodiment 4：
The method to CS/Ag/HAp composite coatings surface spin coating Lys is present embodiments provided, and will be made from this method Lys/CS/Ag/HAp composite coatings are immersed in test silver ion elution profiles figure, step in SBF solution and include：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：90 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 80 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, weigh The AgNO of 630mg3, the HAp of the CS of 400mg, 400mg, which are dissolved in 1%Ac, is used as solute.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 3mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 10 minutes time, operating distance 2cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
(5) step 5：The Lys solution of 20mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 50uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
(6) step 6：The titanium sheet for being formed with Lys/CS/Ag/HAp composite coatings is put into the PBS equipped with 10mL, Mei Gehuan It releases and places a piece of in bottle, 14 identical sustained release samples and number are set altogether 1 to 14 day, meanwhile, sustained release bottle is put into 37 DEG C of perseverance Incubator is sustained, and the sustained release sample 3mL of reference numeral is taken to carry out ICP test silver ion release concentrations daily, draws release profiles.
Silver ion sustained release figure in the Lys/CS/Ag/HAp composite coatings obtained to above-mentioned test method is as shown in figure 4, inspection Survey the result shows that：CS and the HAp and Lys of spin coating that electro-deposition is got on can effectively control the rate of release of silver ion, make silver Ion slow release plays the role of long-term antibacterial.
Embodiment 5：
Present embodiments provide the method for preparing Lys/CS/Ag/HAp composite coatings, and by Lys/CS/ made from this method Ag/HAp composite coatings carry out Escherichia coli antibiotic property test, and carry out SEM scannings to Escherichia coli, and step includes：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：90 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 80 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, weigh The AgNO of 630mg3, the HAp of the CS of 400mg, 400mg, which are dissolved in 1%Ac, is used as solute.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 3mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 10 minutes time, operating distance 2cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
(5) step 5：The Lys solution of 20mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 50uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
(6) step 6：Sample obtained by step (5) is put into 48 orifice plates, 400uL a concentration of 10 is added in into hole7CFU/ The Escherichia coli bacteria liquid of mL makes it not have sample surfaces, and and then orifice plate is placed in incubator and cultivates 12h.By the Ti after culture Dehydration is fixed in bacterium on sample, observes the pattern of bacterium after dry under a scanning electron microscope, as shown in Figure 5.
Testing result shows：Bacillus coli cells wall shrinkage breakage is more serious, it was demonstrated that sterilization of the coating to Escherichia coli Mechanism is to act on cell wall to make its apoptosis.
Embodiment 6：
Present embodiments provide the method for preparing Lys/CS/Ag/HAp composite coatings, and by Lys/CS/ made from this method Ag/HAp composite coatings carry out staphylococcus aureus antibiotic property test, and carry out SEM scannings, step packet to Escherichia coli It includes：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：90 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 80 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, weigh The AgNO of 630mg3, the HAp of the CS of 400mg, 400mg, which are dissolved in 1%Ac, is used as solute.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 3mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 10 minutes time, operating distance 2cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
(5) step 5：The Lys solution of 20mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 50uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
(6) step 6：Sample obtained by step (5) is put into 48 orifice plates, 400uL a concentration of 10 is added in into hole7CFU/ The staphylococcus aureus bacterium solution of mL makes it there not to be sample surfaces, and and then orifice plate is placed in incubator and cultivates 12h.It will culture Dehydration is fixed in the bacterium on Ti samples afterwards, the pattern of bacterium is observed after dry under a scanning electron microscope, such as attached drawing 6 It is shown.
Testing result shows：Breakage occurs for staphylococcus aureus part cell wall, and cytoplasm outflow illustrates coating to gold The sterilization mechanism of staphylococcus aureus is that cell wall cracking makes its apoptosis.
Embodiment 7：
The method for preparing Lys/CS/Ag/HAp composite coatings is present embodiments provided, and painting is carried by what this method obtained The sample of layer carries out alkaline phosphatase activities (ALP) and tests, and specific steps include：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：90 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 80 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, claim respectively The AgNO of the 630mg taken3, the HAp of the CS of 400mg, 400mg is configured to HAp, CS/HAp, CS/Ag/HAp electrochemical deposition liquids.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 3mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 10 minutes time, operating distance 2cm.With this parameter HAp, the compound painting of CS/HAp, CS/Ag/HAp are prepared in titanium plate surface Layer；
(5) step 5：The Lys solution of 20mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 50uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
(6) step 6：The above-mentioned sample made is put into 96 orifice plates, with 150uL a concentration of 105Cells/mL's MC3T3E1 cells, which are added in orifice plate, cultivates 3,7,14D, and the alkaline phosphatase activities of cell on sample are detected with AKP kits, Testing result is as shown in Figure 7.
Testing result shows：Compared to pure titanium, the sample of coating significantly has higher alkaline phosphatase activities, wherein HAp has most strong ALP activity 3,7,14day, and the ALP values of other samples are slightly below HAp samples, illustrate in sample coatings It is that HAp components play biocompatibility and osteogenic.
Embodiment 8：
The method for preparing Lys/CS/Ag/HAp composite coatings is present embodiments provided, specific steps include：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：80 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 82 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, weigh The AgNO of 2000mg3, the HAp of the CS of 3000mg, 3000mg is configured to CS/Ag/HAp electrochemical deposition liquids.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 1mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 20 minutes time, operating distance 4cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
(5) step 5：The Lys solution of 5mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 50uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
The titanium sheet with Lys/CS/Ag/HAp composite coatings prepared by the above process has good Synergistic antimicrobial Effect, property and 3 products obtained therefrom of embodiment are basically identical.
Embodiment 9：
The method for preparing Lys/CS/Ag/HAp composite coatings is present embodiments provided, specific steps include：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：80 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 82 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, weigh The AgNO of 100mg3, the HAp of the CS of 200mg, 200mg is configured to CS/Ag/HAp electrochemical deposition liquids.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 0.5mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, sink 30 minutes time of product, operating distance 2cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
(5) step 5：The Lys solution of 30mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 20uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
The titanium sheet with Lys/CS/Ag/HAp composite coatings prepared by the above process has good Synergistic antimicrobial Effect, property and 3 products obtained therefrom of embodiment are basically identical.
Embodiment 10：
The method for preparing Lys/CS/Ag/HAp composite coatings is present embodiments provided, specific steps include：
(1) step 1：The titanium sheet of a diameter of 6mm is polished polishing with the sand paper of 240 mesh, makes the one side of Ti that mirror be presented Planar.Then it cleans ultrasound 3 times with ethyl alcohol, is then cleaned and dried with deionized water again；
(2) step 2：80 minutes alkali heat-treatments, alkali are carried out to titanium plate surface at 82 DEG C using the KOH solution of 4mol/L It is rinsed 3 times with deionized water after heat treatment, and dry.
(3) step 3：Prepare 200mL electrochemical deposition liquids, using 1% concentration acetic acid (Ac) as solvent, weigh The AgNO of 6000mg3, the HAp of the CS of 4000mg, 4000mg is configured to CS/Ag/HAp electrochemical deposition liquids.
(4) step 4：Using electrochemical workstation, the titanium sheet after alkali heat is put into a chemical sinking effusion and carries out electrochemistry Deposition.The parameter of electrochemical deposition, constant current density 8mA/cm are set on electrochemical workstation2, 50 DEG C of depositing temperature, deposition 3 minutes time, operating distance 3cm.With this parameter CS/Ag/HAp composite coatings are prepared in titanium plate surface；
(5) step 5：The Lys solution of 1mg/mL is configured to the acetic acid (Ac) of 1% concentration, the parameter of sol evenning machine is set, 700 revs/min of low speed, 10 seconds time；5000 revs/min at a high speed, 30 seconds time.CS/Ag/HAp samples are positioned over sol evenning machine On, the Lys solution that 50uL is added dropwise carries out spin coating.Lys/CS/Ag/HAp composite coatings are prepared in spin coating 3 times in this way.
The titanium sheet with Lys/CS/Ag/HAp composite coatings prepared by the above process has good Synergistic antimicrobial Effect, property and 3 products obtained therefrom of embodiment are basically identical.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (9)

  1. A kind of 1. preparation method in composite coating of the surface of metal titanium with synergetic antibacterial effect, which is characterized in that step packet It includes：
    S1, alkali heat-treatment is carried out to titanium sheet；
    It is prepared by S2, chitosan/silver/carboxy apatite composite coating：Weigh AgNO3, chitosan, it is molten that hydroxyapatite is dissolved in acetic acid As electrochemical deposition liquid in liquid, the titanium sheet after alkali heat is put into electrochemical deposition liquid and carries out electrochemical deposition, in titanium sheet table Prepare chitosan/silver/carboxy apatite composite coating in face；
    It is prepared by S3, lysozyme/chitosan/silver/carboxy apatite composite coating：It is spin-coated on after lysozyme is dissolved in acetic acid solution Surface prepares and has in the titanium sheet of chitosan/silver/carboxy apatite composite coating obtained by step S2, and bacteriolyze is prepared in titanium sheet Enzyme/chitosan/silver/carboxy apatite composite coating.
  2. 2. there is the preparation method of the composite coating of synergetic antibacterial effect in surface of metal titanium as described in claim 1, it is special Sign is：In step S2, AgNO in the electrochemical deposition liquid3A concentration of 0.1~50mg/mL, a concentration of the 0.1 of chitosan ~50mg/mL, a concentration of 0.1~50mg/mL of hydroxyapatite；In step S3, the lysozyme is dissolved in acetic acid solution Final concentration to make lysozyme reaches 0.1~50mg/mL.
  3. 3. there is the preparation method of the composite coating of synergetic antibacterial effect in surface of metal titanium as claimed in claim 2, it is special Sign is：The additive amount of the lysozyme is that the titanium sheet per a diameter of 6mm adds 20~50uL lysozyme acetic acid solutions.
  4. 4. the compound painting in surface of metal titanium with synergetic antibacterial effect as described in any one of claims 1 to 3 claim The preparation method of layer, it is characterised in that：Step S2, in S3, the acetic acid solution is water-soluble for the acetic acid of quality of acetic acid a concentration of 1% Liquid.
  5. 5. there is the preparation method of the composite coating of synergetic antibacterial effect in surface of metal titanium as described in claim 1, it is special Sign is：The condition of electrochemical deposition is described in step S2：0.1~10mA/cm of constant current2, the work between titanium sheet and platinum electrode Make distance as 2~5cm, a length of 0.1~30 minute during electrochemical deposition.
  6. 6. there is the preparation method of the composite coating of synergetic antibacterial effect in surface of metal titanium as claimed in claim 5, it is special Sign is：The electrochemical deposition temperature is 48~52 DEG C.
  7. 7. there is the preparation method of the composite coating of synergetic antibacterial effect in surface of metal titanium as described in claim 1, it is special Sign is：In step S3, the condition of the spin coating is：Spin coating 700~5000r/min of rotating speed, 10~60s of spin-coating time.
  8. 8. there is the preparation method of the composite coating of synergetic antibacterial effect in surface of metal titanium as described in claim 1, it is special Sign is：In step S1, the alkali heat-treatment be using 3.8~4.2mol/L KOH solution at 78~82 DEG C to titanium sheet table Face carries out 80~100 minutes alkali heat-treatments.
  9. 9. it is prepared using the preparation method described in claim 1 in composite coating of the surface of metal titanium with synergetic antibacterial effect Obtained product.
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