CN107233618A - A kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy - Google Patents

A kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy Download PDF

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CN107233618A
CN107233618A CN201710523643.8A CN201710523643A CN107233618A CN 107233618 A CN107233618 A CN 107233618A CN 201710523643 A CN201710523643 A CN 201710523643A CN 107233618 A CN107233618 A CN 107233618A
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nano
zno
titanium alloy
prepared
composite coatings
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吴水林
张演哲
刘想梅
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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
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/06—Coatings containing a mixture of two or more compounds
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention provides a kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, the nano-Ag particles of tool excellent antibacterial are first prepared with chemical reduction method, laser melting and coating technique is recycled to prepare firm Ag/ZnO/HA nano-composite coatings, Ag has excellent antibacterial, ZnO has certain antibiotic property and osteogenic, HA has excellent biocompatibility and osteogenic, each component in coating plays respective function and plays the effect of Synergistic biocidal and bio-compatible, and the titanium alloy of coating has durable antibiotic and good biocompatibility after improvement.

Description

A kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy
Technical field
The present invention relates to material science and technical field of nano material, and in particular to one kind is by laser melting and coating technique in titanium The method that the Ag/ZnO/HA nano-composite coatings with durable antibiotic and good biocompatibility are prepared on alloy.
Background technology
It is a kind of technological means risen the nineties in last century that laser, which is used to prepare alloy and the technology of coating,.Its advantage exists In the higher different types of inorganic metal class material of fusing point firmly can be combined together.By development in recent years, hair Exhibition includes the means such as pulsed laser deposition, laser melting coating, wherein, laser melting coating is with its relatively simple operation and to raw material It is required that relatively low and quite favored.By the electric current to laser device, pulsewidth, the setting of the parameter such as frequency, so as to realize to coating Cladding thickness, bond strength, coating patternsization are more accurately controlled.Because laser corollary equipment can carry out programing operation, Intelligentized level meets quick to material significantly, the dynamics of regulating microstructure.
Because China progressively marches toward the society of aging population, the probability that the elderly fractures is larger, and society plants to bone The demand for entering body material rises year by year.And current many implant materials itself do not possess antibacterial and biocompatibility, cause Postoperative generation bacterium infection, the situation for implant rejection occur happens occasionally.Secondary implantation not only brings economy to patient On burden, and bigger pain can be caused to the body and mind of patient with tormenting.Meanwhile, a large amount of uses of antibiotic can make human body There is drug resistance in the bacterium of infection, can without effective antibiotic when human body can only be treated by antibiotic With.Therefore, by preparing inorganic antibacterial particle as study hotspot in recent years.
The content of the invention
In view of this, the present invention passes through a kind of silver/zinc oxide of laser melting coating/hydroxyapatite (Ag/ZnO/ on titanium alloy HA) nano-composite coating, makes the titanium alloy after improvement have durable antibiotic and good biocompatibility；Preparing Ag/ZnO/ During HA nano-composite coatings, the present invention first prepares the nano-Ag particles of tool excellent antibacterial, then profit with chemical reduction method Firm Ag/ZnO/HA nano-composite coatings are prepared with laser melting and coating technique, Ag has excellent antibacterial, and ZnO has certain There is antibiotic property and osteogenic, HA each component in excellent biocompatibility and osteogenic, coating to play respective function simultaneously Play the effect of Synergistic biocidal and bio-compatible.
First aspect present invention provides a kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, step Suddenly include：
S1, by hydroxyapatite and the AgNO that is dissolved in ammoniacal liquor3After mixing, N is added dropwise into system2H4Make AgNO3In silver Ion is reduced into Nano Silver simple substance；
S2, Zinc oxide nanoparticle is added into step S1 resulting solutions, suction filtration, grinding are then configured to suspension, The suspension is added dropwise on polished titanium alloy material, prefabricated coating sample is formed after drying；
S3, prefabricated coating sample obtained by step S2 is placed on laser melting coating platform, laser is carried out in argon atmosphere and is melted Cover.
Second aspect of the present invention, which is provided, uses the above-mentioned method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy The product prepared.
The beneficial effects of the invention are as follows：
(1) inorganic composite coating can be prepared with simple and quick using laser melting and coating technique；
(2) the problem of only solving biocompatibility compared to general implant, Ag/ZnO/HA coatings have well simultaneously Antibacterial, skeletonization, the combination property such as bio-compatible；
(3) because Ag and ZnO have a fusing point of larger difference, therefore silver and the rate of release of zinc after laser melting coating are not It is synchronous, make coating that there is the lasting sterilizing ability for taking into account shot and long term, and typically carrying medicine or other means can not all have for a long time surely Fixed antibacterial effect；
(4) drug resistance will not be produced compared to using the Ag/ZnO/HA of antibiotic antibacterial, laser melting coating.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the SEM figures of the laser melting coating of uncombined coating in embodiment 1.
Fig. 2 schemes for the SEM in embodiment 2 by laser melting coating Ag/ZnO/HA nano-composite coatings.
Fig. 3 is that the floating coat of embodiment 3 is immersed in zinc ion elution profiles figure in SBF solution.
Fig. 4 is that the floating coat of embodiment 3 is immersed in silver ion elution profiles figure in SBF solution.
Fig. 5 is the SEM figures of the Escherichia coli on Ag/ZnO/HA nano-composite coatings surface in embodiment 4.
Fig. 6 is the SEM figures of the staphylococcus aureus on Ag/ZnO/HA nano-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.
Embodiment
The invention provides a kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, step includes：
S1, by hydroxyapatite and the AgNO that is dissolved in ammoniacal liquor3After mixing, N is added dropwise into system2H4Make AgNO3In silver Ion is reduced into Nano Silver simple substance；
S2, Zinc oxide nanoparticle is added into step S1 resulting solutions, suction filtration, grinding are then configured to suspension, The suspension is added dropwise on polished titanium alloy material, prefabricated coating sample is formed after drying；
S3, prefabricated coating sample obtained by step S2 is placed on laser melting coating platform, laser is carried out in argon atmosphere and is melted Cover.
It is preferred that, the titanium alloy material is Ti6Al4V。
Nano simple substance Argent grain has excellent anti-microbial property, and it can produce active oxygen by Induction of bacterial cytoplasm, make Cell membrane is inside and outside to form oxygen pressure, so that bacteria cell wall, membranolysis apoptosis, while it can allow bacterium to make damage in division Its DNA of evil, so as to influence to divide to reach the effect of antibacterial.Nano ZnO particles are as nanometer simple substance silver, with same Nanometer size effect, can be produced needed for the zinc ion in certain active oxygen antibacterial, simultaneous oxidation zinc is tissue cell growth A kind of element, the growth recovery of bone tissue can be promoted.HA be with a kind of natural bone component especially close material, it has excellent Different bioactivity, biocompatibility promotes Bone Defect Repari, induces the ability of New born formation.Titanium alloy has more classification, Ti6Al4V is as one kind therein, and there is higher intensity to be widely used for it, and be largely used in medical implant. Ti6Al4V has higher fusing point, can be well as the base material of the functional coating of cladding.Each component hair in coating Wave respective function and play the effect of Synergistic biocidal and bio-compatible.
It is preferred that, in step S1, hydroxyapatite is mixed with deionized water, stirred after ultrasound, then with being dissolved in ammoniacal liquor AgNO3Mixing.
It is preferred that, in step S1, N is added dropwise into system2H4When sporting coffee color by white to mixed solution, stop drop Plus N2H4, now AgNO3In silver ion be reduced into Nano Silver simple substance.Intuitively accurately sentenced by the significant change of color Disconnected AgNO3Middle silver ion reduction situation, more easily and effectively, it is easy to operate.
More preferred, the hydroxyapatite, AgNO3、The addition of Zinc oxide nanoparticle is by quality ratio, to make Ag：ZnO：HA=0~10：0~10：90.
Using chemical method by AgNO3Silver ion reduction in solution is into Nano Silver simple substance, and nano-scale is smaller, and (20nm is left It is right), Size Distribution is more uniform.Compared to ultraviolet reduction, N is used in step S1 of the invention2H4Can be by AgNO3Silver in solution Ion Restore All, and ultraviolet reduction can not be quantified, and be difficult the quality of the Nano Silver simple substance of detection reduction, and also ultraviolet reduction is needed Nucleator is added, the nano-Ag particles preparation method that the present invention is used can obtain the nano-Ag particles for having excellent antibacterial.
It is preferred that, in step S2, it is configured to 8~12mg/mL suspension.Further, the dropwise addition is in Ti6Al4V substrates On suspension be 50uL.
It is preferred that, in step S2, with respectively cleaning at least three times of ethanol and deionized water after the suction filtration step, cleaning is finished Afterwards again suction filtration and at 55~65 DEG C dry 0.8~1.2h, be then ground.
More preferred, the suction filtration uses 0.22um miillpore filter.
It is preferred that, in one embodiment of the invention, in step S3, laser cladding process uses model JHM- 1GY-300B laser, the laser melting coating conditional parameter is electric current I=50~300A, pulsewidth W=1~100ms, frequency f =10~50Hz, beam diameter D=0.1~1mm, operating rate V=1~20mm/s.
By to Ti6Al4Ag/ZnO/HA preset coatings on V carry out laser melting coating under given conditions, make Ag/ZnO/HA Nano-composite coating is firmly combined with substrate.Because the fusing point of zinc oxide has 1975 DEG C, far above Nano Silver simple substance 961.78 DEG C fusing point, in the coating formed during cladding, the more bottom for being distributed in coating of Nano Silver simple substance is simultaneously excessively combined with substrate, The most of zinc oxide is distributed in coating surface.Element this distribution in the coating and combination make its rate of release and time Duan Butong, after material is implanted in vivo, the release that early stage relies primarily on Zn-ef ficiency carrys out antibacterial, and is implanted into the later stage, and silver element rises Main antibacterial action.General implant infection can occur in three months after surgery, the Ag/ZnO/HA nanometers of laser melting coating Composite coating effectively solves the permanent sex chromosome mosaicism of sustained anti-microbial.
For the ease of understanding the present invention, below in conjunction with Figure of description and embodiment the present invention is made more comprehensively, it is careful Ground is described, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city Field is commercially available or can prepared by existing method.
Embodiment 1
The present embodiment has directly carried out Laser Cladding Treatment to titanium alloy, and step includes：
(1) step one：By Ti6Al4V is polished polishing with the sand paper of 240 mesh, makes Ti6Al4V obtains one side and minute surface is presented Shape.Then ultrasound is cleaned with ethanol 3 times, is then cleaned and dried with deionized water again.
(2) step 2：Laser cladding process uses model JHM-1GY-300B laser.Open laser two-dimensional Platform sets cladding parameter, and electric current is set into I=100A, pulsewidth W=2ms, frequency f=20Hz, beam diameter D=0.6mm, Sample is positioned on laser melting coating platform by operating rate V=5mm/s., is adjusted platform X-axis and Y-axis by program, is made at sample In the starting point of generating laser.Opening argon bottle makes sample be in argon atmosphere, is separately turned on " driving " in control platform, " program control ", " program " system carries out laser melting coating.
Electronic Speculum detection is scanned to the product that the above method is obtained, obtained SEM is schemed as shown in figure 1, testing result table It is bright：Uncoated Ti6Al4V samples form obvious molten bath crest after laser treatment, and this is that substrate surface is quick by high-energy Melt the effect of cooling.
Embodiment 2
A kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy is present embodiments provided, step includes：
(1) step one：Weigh 135mg hydroxyapatites (HA) and be put into the beaker equipped with 10mL deionized waters, ultrasonic 30min After carry out magnetic agitation.Weigh 11.81mg silver nitrate crystals (AgNO3) be put into another beaker, and add 10mL ammoniacal liquor by its Dissolving, treats AgNO3It is dissolved completely in after ammoniacal liquor and solution is poured slowly into the beaker equipped with HA solution, continues to stir.It is then past Hydrazine hydrate (N is slowly added dropwise in the mixed solution of stirring2H4), when mixed solution sports coffee color by white, stop being added dropwise N2H4, now AgNO3In silver ion be reduced into Nano Silver simple substance.
(2) step 2：7.5mg Zinc oxide nanoparticles (ZnO) are added in above-mentioned coffee-like solution, are entered with organic filter membrane Row suction filtration, and respectively cleaned 3 times with ethanol and deionized water.It is put into after the completion of suction filtration in 60 DEG C of drying boxes and dries 1h, then with grinds Alms bowl is ground, and 10mg/mL suspension is made into, in polished Ti6Al450uL suspension is added dropwise on V, is put into 60 DEG C of drying boxes Dry 1h and form prefabricated coating.
(3) step 3：Laser cladding process uses model JHM-1GY-300B laser.Open laser two-dimensional Platform sets cladding parameter, and electric current is set into I=100A, pulsewidth W=2ms, frequency f=20Hz, beam diameter D=0.6mm, Sample is positioned on laser melting coating platform by operating rate V=5mm/s., is adjusted platform X-axis and Y-axis by program, is made at sample In the starting point of generating laser.Opening argon bottle makes sample be in argon atmosphere, is separately turned on " driving " in control platform, " program control ", " program " system carries out laser melting coating.
Electronic Speculum detection is scanned to the product that the above method is obtained, obtained SEM is schemed as shown in Fig. 2 testing result table It is bright：Ag/ZnO/HA ratios are (7:3:90) coating sample is after Laser Cladding Treatment, and surface forms the spherical knot of micro/nano level Structure, this roughness of coating can change the hydrophobe property of material, bacterial cell adherence situation.Big specific surface area can make bacterium More it is adequately exposed to antimicrobial nano material.
Embodiment 3
A kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy is present embodiments provided, and to the party The titanium alloy for the coating that method is obtained has carried out the test of the release concentration of zinc ion and silver ion, and specific steps include：
(1) step one：Weigh hydroxyapatite (HA) and be put into the beaker equipped with 10mL deionized waters, ultrasonic 30min is laggard Row magnetic agitation.Weigh silver nitrate crystal (AgNO3) be put into another beaker, and add 10mL ammoniacal liquor and dissolved, treat AgNO3 It is dissolved completely in after ammoniacal liquor and solution is poured slowly into the beaker equipped with HA solution, continues to stir.Mixing then toward stirring is molten Hydrazine hydrate (N is slowly added dropwise in liquid2H4), when mixed solution sports coffee color by white, stop that N is added dropwise2H4, now AgNO3In silver ion be reduced into Nano Silver simple substance.
(2) step 2：Zinc oxide nanoparticle (ZnO) is added in above-mentioned coffee-like solution, is taken out with organic filter membrane Filter, and respectively cleaned 3 times with ethanol and deionized water.It is put into after the completion of suction filtration in 60 DEG C of drying boxes and dries 1h, is then ground with mortar Mill, is made into 10mg/mL suspension, in polished Ti6Al450uL suspension is added dropwise on V, is put into 60 DEG C of drying boxes and dries 1h forms prefabricated coating.
(3) step 3：Laser cladding process uses model JHM-1GY-300B laser.Open laser two-dimensional Platform sets cladding parameter, and electric current is set into I=100A, pulsewidth W=2ms, frequency f=20Hz, beam diameter D=0.6mm, Sample is positioned on laser melting coating platform by operating rate V=5mm/s., is adjusted platform X-axis and Y-axis by program, is made at sample In the starting point of generating laser.Opening argon bottle makes sample be in argon atmosphere, is separately turned on " driving " in control platform, " program control ", " program " system carries out laser melting coating.
Using the above method, adjustment Ag/ZnO/HA ratios prepare multigroup titanium alloy with different ratio coating, specifically , Ag/ZnO/HA ratios include several groups as follows, by quality ratio：0:10:90、3:7:90、5:5:90、7:3:90、10:0:90.
(4) coating of the said ratio made is put into the sustained release bottle equipped with 30mLSBF and be sustained, respectively in Isosorbide-5-Nitrae, It is sampled when 7,14,21D, 3mL SBF solution is supplemented while 3mL is taken every time, is tested by atomic absorption spectrophotometer The release concentration of zinc ion and silver ion, is depicted as sustained release figure, respectively as shown in Figure 3, Figure 4 after being calculated.
Testing result shows：Tested and found by atomic absorption spectrophotometer, Zn in sample coatings2+Release preceding four It quickly, behind rate of release it is slower, burst size is also less, and this is due to that ZnO fusing points are high, and thermal conductivity factor is low, laser melt During covering and in substrate and coating the combination of other components not as Ag firmly, antibacterial Zn at this moment2+Play main function.Pass through Ag+Release profiles understand, Isosorbide-5-Nitrae, Ag in 7,14,21D+Sustained release, can play lasting antibacterial action.Because Ag's is molten Point is relatively low, and thermal conductivity factor is high, melts and is excessively combined with substrate and other components at first during progress laser melting coating.
Embodiment 4
Present embodiments provide a kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, and by the party The titanium alloy for the coating that method is obtained is acted on Escherichia coli and cultivated, and specific steps include：
(1) step one：Weigh 135mg hydroxyapatites (HA) and be put into the beaker equipped with 10mL deionized waters, ultrasonic 30min After carry out magnetic agitation.Weigh 11.81mg silver nitrate crystals (AgNO3) be put into another beaker, and add 10mL ammoniacal liquor by its Dissolving, treats AgNO3It is dissolved completely in after ammoniacal liquor and solution is poured slowly into the beaker equipped with HA solution, continues to stir.It is then past Hydrazine hydrate (N is slowly added dropwise in the mixed solution of stirring2H4), when mixed solution sports coffee color by white, stop being added dropwise N2H4, now AgNO3In silver ion be reduced into Nano Silver simple substance.
(2) step 2：7.5mg Zinc oxide nanoparticles (ZnO) are added in above-mentioned coffee-like solution, are entered with organic filter membrane Row suction filtration, and respectively cleaned 3 times with ethanol and deionized water.It is put into after the completion of suction filtration in 60 DEG C of drying boxes and dries 1h, then with grinds Alms bowl is ground, and 10mg/mL suspension is made into, in polished Ti6Al450uL suspension is added dropwise on V, is put into 60 DEG C of drying boxes Dry 1h and form prefabricated coating.
(3) step 3：Laser cladding process uses model JHM-1GY-300B laser.Open laser two-dimensional Platform sets cladding parameter, and electric current is set into I=100A, pulsewidth W=2ms, frequency f=20Hz, beam diameter D=0.6mm, Sample is positioned on laser melting coating platform by operating rate V=5mm/s., is adjusted platform X-axis and Y-axis by program, is made at sample In the starting point of generating laser.Opening argon bottle makes sample be in argon atmosphere, is separately turned on " driving " in control platform, " program control ", " program " system carries out laser melting coating.
(4) sample obtained by step (3) is put into 48 orifice plates, it is 10 that 400uL concentration is added into hole7CFU/mL large intestine Bacillus bacterium solution makes it there not to be sample surfaces, and and then orifice plate is placed in incubator and cultivates 12h.By the Ti6Al4V samples after culture On bacterium be fixed dehydration, the pattern of bacterium is observed after drying under a scanning electron microscope, as shown in Figure 5.
Testing result shows：The shrinkage of Bacillus coli cells wall is damaged more serious, it was demonstrated that sterilization of the coating to Escherichia coli Mechanism is to act on cell membrane to make its apoptosis.
Embodiment 5
Present embodiments provide a kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, and by the party The titanium alloy for the coating that method is obtained is acted on staphylococcus aureus and cultivated, and specific steps include：
(1) step one：Weigh 135mg hydroxyapatites (HA) and be put into the beaker equipped with 10mL deionized waters, ultrasonic 30min After carry out magnetic agitation.Weigh 11.81mg silver nitrate crystals (AgNO3) be put into another beaker, and add 10mL ammoniacal liquor by its Dissolving, treats AgNO3It is dissolved completely in after ammoniacal liquor and solution is poured slowly into the beaker equipped with HA solution, continues to stir.It is then past Hydrazine hydrate (N is slowly added dropwise in the mixed solution of stirring2H4), when mixed solution sports coffee color by white, stop being added dropwise N2H4, now AgNO3In silver ion be reduced into Nano Silver simple substance.
(2) step 2：7.5mg Zinc oxide nanoparticles (ZnO) are added in above-mentioned coffee-like solution, are entered with organic filter membrane Row suction filtration, and respectively cleaned 3 times with ethanol and deionized water.It is put into after the completion of suction filtration in 60 DEG C of drying boxes and dries 1h, then with grinds Alms bowl is ground, and 10mg/mL suspension is made into, in polished Ti6Al450uL suspension is added dropwise on V, is put into 60 DEG C of drying boxes Dry 1h and form prefabricated coating.
(3) step 3：Laser cladding process uses model JHM-1GY-300B laser.Open laser two-dimensional Platform sets cladding parameter, and electric current is set into I=100A, pulsewidth W=2ms, frequency f=20Hz, beam diameter D=0.6mm, Sample is positioned on laser melting coating platform by operating rate V=5mm/s., is adjusted platform X-axis and Y-axis by program, is made at sample In the starting point of generating laser.Opening argon bottle makes sample be in argon atmosphere, is separately turned on " driving " in control platform, " program control ", " program " system carries out laser melting coating.
(4) sample obtained by step (3) is put into 48 orifice plates, it is 10 that 400uL concentration is added into hole7CFU/mL's is golden yellow Color staphylococcus bacterium solution makes it there not to be sample surfaces, and and then orifice plate is placed in incubator and cultivates 12h.After culture Dehydration is fixed in bacterium on Ti6Al4V samples, observes the pattern of bacterium, such as accompanying drawing after drying under a scanning electron microscope Shown in 6.
Testing result shows：Damaged, cytoplasm outflow occurs for staphylococcus aureus part cell membrane, illustrates coating to gold The sterilization mechanism of staphylococcus aureus is to act on cell membrane to make its apoptosis.But because aureus cell wall is thicker, All bacteria cell walls can not be allowed to rupture.
Embodiment 6
Present embodiments provide a kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, and by the party The titanium alloy for the coating that method is obtained carries out alkaline phosphatase activities (ALP) test, and specific steps include：
(1) step one：Weigh hydroxyapatite (HA) and be put into the beaker equipped with 10mL deionized waters, ultrasonic 30min is laggard Row magnetic agitation.Weigh silver nitrate crystal (AgNO3) be put into another beaker, and add 10mL ammoniacal liquor and dissolved, treat AgNO3 It is dissolved completely in after ammoniacal liquor and solution is poured slowly into the beaker equipped with HA solution, continues to stir.Mixing then toward stirring is molten Hydrazine hydrate (N is slowly added dropwise in liquid2H4), when mixed solution sports coffee color by white, stop that N is added dropwise2H4, now AgNO3In silver ion be reduced into Nano Silver simple substance.
(2) step 2：Zinc oxide nanoparticle (ZnO) is added in above-mentioned coffee-like solution, is taken out with organic filter membrane Filter, and respectively cleaned 3 times with ethanol and deionized water.It is put into after the completion of suction filtration in 60 DEG C of drying boxes and dries 1h, is then ground with mortar Mill, is made into 10mg/mL suspension, in polished Ti6Al450uL suspension is added dropwise on V, is put into 60 DEG C of drying boxes and dries 1h forms prefabricated coating.
(3) step 3：Laser cladding process uses model JHM-1GY-300B laser.Open laser two-dimensional Platform sets cladding parameter, and electric current is set into I=100A, pulsewidth W=2ms, frequency f=20Hz, beam diameter D=0.6mm, Sample is positioned on laser melting coating platform by operating rate V=5mm/s., is adjusted platform X-axis and Y-axis by program, is made at sample In the starting point of generating laser.Opening argon bottle makes sample be in argon atmosphere, is separately turned on " driving " in control platform, " program control ", " program " system carries out laser melting coating.
Using the above method, adjustment Ag/ZnO/HA ratios prepare multigroup titanium alloy with different ratio coating, specifically , Ag/ZnO/HA ratios include several groups as follows, by quality ratio：0:10:90、3:7:90、5:5:90、7:3:90、10:0:90.
(4) coating sample of the said ratio made is put into 96 orifice plates, is 10 with 150uL concentration5Cell/mL's MC3T3E1 cells, which are added in orifice plate, cultivates 3,7,14D, and the alkaline phosphatase activities of cell on sample is detected with AKP kits, Testing result is as shown in Figure 7.
Testing result shows：The MC3T3E1 Cellular alkaline phosphatases activity of coating sample is to gradually rise at 3,7D, Especially Ag/ZnO/HA ratios are (7:3:90) sample is upgraded to highest in 7D, and in 14D, coating sample ALP values have all declined.Say Bright early stage is conducive to cell to breed, and the later stage starts differentiation.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.

Claims (10)

1. a kind of method that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that step includes：
S1, by hydroxyapatite and the AgNO that is dissolved in ammoniacal liquor3After mixing, N is added dropwise into system2H4Make AgNO3In silver ion It is reduced into Nano Silver simple substance；
S2, Zinc oxide nanoparticle is added into step S1 resulting solutions, suction filtration, grinding are then configured to suspension, in polishing The suspension is added dropwise on good titanium alloy material, prefabricated coating sample is formed after drying；
S3, prefabricated coating sample obtained by step S2 is placed on laser melting coating platform, laser melting coating is carried out in argon atmosphere.
2. the method as claimed in claim 1 that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that： In step S1, hydroxyapatite is mixed with deionized water, stirred after ultrasound, then with the AgNO that is dissolved in ammoniacal liquor3Mixing.
3. the method as claimed in claim 1 that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that： In step S1, N is added dropwise into system2H4When sporting coffee color by white to mixed solution, stop that N is added dropwise2H4, now AgNO3 In silver ion be reduced into Nano Silver simple substance.
4. as described in any one of claims 1 to 3 claim Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy Method, it is characterised in that：The hydroxyapatite, AgNO3、The addition of Zinc oxide nanoparticle is by quality ratio, to make Ag： ZnO：HA=0~10：0~10：90.
5. the method as claimed in claim 1 that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that： In step S2,8~12mg/mL suspension is configured to.
6. the method as claimed in claim 1 that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that： In step S2, with respectively cleaning at least three times of ethanol and deionized water after the suction filtration step, cleaning finish after again suction filtration and in 0.8~1.2h is dried at 55~65 DEG C, is then ground.
7. the method as claimed in claim 1 that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that： In step S2, the suction filtration uses 0.22um miillpore filter.
8. the method as claimed in claim 1 that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that： In step S3, the laser melting coating conditional parameter be electric current I=50~300A, pulsewidth W=1~100ms, frequency f=10~ 50Hz, beam diameter D=0.1~1mm, operating rate V=1~20mm/s.
9. the method as claimed in claim 1 that Ag/ZnO/HA nano-composite coatings are prepared on titanium alloy, it is characterised in that： The titanium alloy material is Ti6Al4V。
10. use and prepare the production that the method for Ag/ZnO/HA nano-composite coatings is prepared on the titanium alloy described in claim 1 Product.
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CN109023343A (en) * 2018-07-07 2018-12-18 中国矿业大学 A kind of processing method of medical titanium alloy antibacterial surface biological coating
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