CN106676604A - Preparation method and application of bacteriostatic bio-active ceramic membrane for porous titanium or titanium alloy surface of lattice structure - Google Patents
Preparation method and application of bacteriostatic bio-active ceramic membrane for porous titanium or titanium alloy surface of lattice structure Download PDFInfo
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Abstract
The invention discloses a preparation method and application of bacteriostatic bio-active ceramic membrane for a porous titanium or titanium alloy surface of a lattice structure and belongs to the technical field of metal surface treatment. The preparation method of the bacteriostatic bio-active ceramic membrane for the porous titanium or titanium alloy surface of the lattice structure comprises the steps of chemical polishing, preparation of a prefabricated oxide film at a direct-current voltage and preparation of the bacteriostatic bio-active ceramic membrane at a bidirectional square-wave pulse voltage. Chemical polishing is conducted through a chemical acid pickling method. Preparation of the prefabricated oxide film is conducted through a low-voltage direct-current anodic oxidation method. Preparation of the bacteriostatic bio-active functional ceramic layer is prepared through a micro-arc oxidation preparation method. The ceramic layer obtained by the adoption of the preparation method is firmly combined with a matrix, the surface of the ceramic layer is provided with a micron-level microcellular structure, and the ceramic layer can greatly improve the bacteriostatic performance and biological activity of the porous titanium or titanium alloy surface. When an interbody fusion cage for the orthopedics field and an implant for the dentistry field are manufactured based on the preparation method of the bacteriostatic bio-active ceramic membrane for the porous titanium or titanium alloy surface of the lattice structure, the synosteosis time of the implant is shortened, and the bacteriostatic performance of the implant is improved.
Description
Technical field
The present invention relates to field of metal surface treatment technology, and in particular to a kind of titanium with lattice structure porous or
The preparation method and applications of the antibacterial bioactive ceramicses film of titanium alloy surface.
Background technology
Discussion of the medical circle for porous metal material in field of orthopaedics application in recent years day by day increases, and the whole world is each big
Orthopaedics implant manufacturer also attempts one after another releasing the implantation produce with similarity surface function using various techniques
Product, imply that similar products will face the rapid growth phase.Metal polyporous material refers to the gold with a large amount of hole groups
Category material, metal polyporous material generally has excellent physical characteristics and good mechanical performance, its density is little,
Specific surface area is big, has great application space in aviation, electronic applications, while in medical material and bioid
Field is also concerned more and more and uses.People adopt different preparation methoies to obtain porous metals,
Such as powder metallurgy spraying, microballon microparticles sinter, metal fabric structures etc., but they still have some to limit to
Property, such as relatively low porosity, relatively high elastic modelling quantity and relatively low coefficient of friction.
Electron beam melting rapid shaping technique (electron beam melting rapid prototyping, EBM RP), letter
Claim EBM RP technologies, be a kind of direct manufacturing technology of novel metal part developed in recent years, be by height
Can electron beam selectively fusing metal powder, and by fused deposition layer by layer, until producing required gold
The process of category part.EBM RP technologies can simple and direct, quick, accurately complete extremely complex form parts
Manufacture, particularly can mold with complex three-dimensional connection pore structure, be orthopaedics implant induction bone
Cell grows into the structural condition of offer, therefore, there is unique advantage in terms of orthopaedics implant, become satisfaction
The important channel of property demand.
However, its surface of pure titanium or titanium alloy with lattice structure porous prepared using EBM RP methods
It is biologically inert.Inducibility is lacked to bone, it is a kind of mechanical bond to cause with osseous tissue, meanwhile,
Its surface does not possess biocidal property yet, therefore, improve with the synosteosis of lattice structure porous titanium alloy and antibacterial
Property has great significance.
Differential arc oxidization technique is that for setting up on the basis of anodic oxidation in recent years is former in non-ferrous metal surface
The new technique of position growth ceramic membrane, at work using high voltage, period there occurs heat chemistry, plasma
Various reactions such as chemistry and electrochemistry, it forms inner compact layer, the stable TiO of outer layer porous2Active ceramic
Layer, hence it is evident that improve the biological activity that titanium is implanted into material, improve its wear resistance and corrosion resistance.Ceramic coating formed by micro-arc oxidation be
Surface of metal titanium growth in situ, with metallurgical binding, thus shows very high bond strength and (is close to
30Mp), far above the bond strength (about 10Mp) of coating prepared by clinical conventional plasma spraying method.
Simultaneously electrolyte ion not only take part in the physical-chemical reaction of differential arc oxidation in micro-arc oxidation process, also by height
Temperature has been diffused in oxide-film.Therefore, by controlling differential arc oxidation electrical quantity and adjustment bath composition, can be with
The convenient chemical composition for changing oxide layer, adjusts micro structure, chemical composition and the crystal phase structure of ceramic membrane.
Recent domestic research finds, adds made by the compositions such as Ca, P, Si, Mg in electrolyte
TiO2Coating, can promote the combination of implantation body and bone.And zinc is the important trace element of human body, joined in body
One of trace element most with physiological function.This element at aspects such as DNA synthesis, protein metabolisms all
Play a significant role, while contributing to cell proliferation and differentiation and relevant enzyme system plays its functional activity, accelerate bone
Formation and calcification, so as to promote union of fracture.Research finds that zinc has dual function to skeletonization, to skeletonization
The propagation of cell has special direct stimulation, there is certain inhibitory action to osteoclast.It is both bone formation
Potential activator, be again effective inhibitor of bone resorption.Meanwhile, zinc also has good antibiotic property, can have
Effect suppresses growing for pathogenic bacterium.
Additionally, early in 1893, find in the famous botanist's vital QI flowing in the body against the natural law of Switzerland, mixed with trace copper water have it is frightened
The bactericidal action of people, also referred to as oligodynamic action：As long as can just kill microorganism and algae in water using micro copper
Class aquatile.As long as being found that millesimal copper ion can just kill the effect of blue or green algae in vital QI flowing in the body against the natural law.In metal
In the middle of ion, particularly silver, hydrargyrum, copper this three oligodynamic action it is most strong, these muriatic 2～5 × 10-6
Mole liquid of concentration, in the state of 37 DEG C, typhoid fever pathogenic bacteria can be just killed through 24 hours, show micro copper
Metal ion just has extremely strong sterilizing power.The bactericidal action of copper just by medical institutions is paid attention to and is answered for a long time
With it can be conducive to the hygiene of holding appliance, there is many copper and pyrite utensil on the medical apparatus and instruments of hospital
The example for using, it is such as clinically widely used to press tongue bars, contraceptive device, catheter, disinfection basin.Base
In this, we are using differential arc oxidation differential arc oxidization technique in pure titanium or titanium alloy its table with lattice structure porous
Face is prepared containing Zn or the antibacterial bioactive ceramic coating of copper, promotes the Integrated implant of implantation body using the coating, in advance
Inflammation around anti-implant, can improve the success rate at a specified future date of implant.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of titanium with lattice structure porous or
The preparation method and applications of the antibacterial bioactive ceramicses film of titanium alloy surface.The porous life prepared using the method
Thing active ceramic film is not only firmly combined with matrix, and, the ceramic membrane has higher wearability and protective
Can, in addition, by introducing antibacterial element zinc or copper, the ceramic membrane shows obvious bacteria resistance function, so as to
Realize the multifunctionality of imbedded body in porous titanium.
For achieving the above object, the technical solution adopted in the present invention is as follows：
A kind of preparation method of the titanium with lattice structure porous or the antibacterial bioactive ceramicses film of titanium alloy surface,
The method is comprised the following steps：
(1) chemical polishing：Titanium with lattice structure porous or titanium alloy are carried out in pickle chemical throwing
Light；The pickle is the mixed aqueous solution of organic acid, corrosion inhibiter and mineral acid, wherein：The mineral acid is
One or two in Fluohydric acid. and nitric acid, the organic acid is citric acid, tartaric acid, malic acid or oxalic acid；
The corrosion inhibiter is o- nitrophenols, o-nitroaniline, p- dinitrophenol, p- nitro saliva quinoline or bitterness
Acid etc..
(2) preparation of prefabricated anode oxide-film：In the first electrolyte and under the conditions of DC voltage, lead to
Cross DC anodizing method carries out prefabricated anode in the POROUS TITANIUM or titanium alloy surface Jing after step (1) process
The preparation of oxide-film；By weight percentage, the first electrolyte composition is as follows：
In the prefabricated anode oxide-film preparation process, 5～30 DEG C of electrolyte temperature, electric source modes are direct current,
The whole voltage of oxidation is 50～150V, oxidization time 3～10 minutes, 0.2～5A/dm of electric current density2, acquisition
Prefabricated anode oxide thickness is 1～3 μm.
The carbonate is sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate；The acylate is Fructus Mali pumilae
Sour sodium, potassium malate, sodium tartrate, Soluble tartar., sodium citrate, potassium citrate, Disodium oxalate., oxalic acid
Potassium, sodium succinate or Potassium Suceinate etc.；The pH adjusting agent be acetic acid, oxalic acid, tartaric acid, citric acid or
Person's phosphoric acid.
(3) preparation of antibacterial porous ceramic film：In the second electrolyte and in bi-directional square wave pulse voltage bar
Under part, antibacterial porous ceramic film is carried out in POROUS TITANIUM or titanium alloy surface by bidirectional pulse differential arc oxidation method
Prepare；By weight percentage, the second electrolyte composition is as follows：
In the antibacterial porous ceramic film preparation process, 5～30 DEG C of electrolyte temperature, electric source modes are bidirectional square
Wave impulse, the whole voltage of forward direction oxidation is 350～450V, and the whole voltage of negative sense oxidation is 50～150V；Oxidization time
10～40 minutes, 2～20A/dm of electric current density2, 200～1000Hz of frequency；The antibacterial porous ceramic film for obtaining
Thickness is 5～30 μm, and porosity is 20～60%, and surface has micron-sized microcellular structure, and micro-pore diameter is
0.5～5 μm.
In step (3), the calcium salt is one or more in calcium acetate, calcium oxide and dalcium biphosphate；
The phosphate is disodium-hydrogen, potassium phosphate,monobasic, Polymeric sodium metaphosphate., potassium metaphosphate, polyphosphate sodium, poly- phosphorus
One or more in sour potassium, sodium glycerophosphate and potassium glycerinophosphate；The zinc salt is zinc acetate or zinc nitrate；
The mantoquita is Schweinfurt green or copper nitrate etc.；The pH adjusting agent is acetic acid, oxalic acid, tartaric acid, citric acid
Or phosphoric acid；The chelating agent is EDTA, EDETATE SODIUM salt, EGTA, ethylenediamine tetrapropionic acid, sulfo group water
Poplar acid or thiourea etc.；The surfactant is stearic acid, dodecylbenzene sodium sulfonate, sodium lauryl sulphate
Or sodium laurylsulfate etc..
In step (3), in the antibacterial porous ceramic film preparation process, solution is carried out using refrigeration system
Cooling, controls solution temperature for 5～30 DEG C, to maintain the speed of growth and surface matter of antibacterial porous ceramic film
Amount.
Titanium with lattice structure porous of the present invention or titanium alloy are using electron beam melting rapid metallic prototyping technique
(Electron Beam Melting, abbreviation EBM technologies) is prepared, and its porosity is 40～90%；Can press
Chinese patent application (application number：201210514088.X, denomination of invention：One kind prepares high fatigue property porous
The method of Ti-6Al-4V block materials) it is prepared.
The inventive method is put on into the tooth implant or Invasive lumbar fusion device of machined molding so as to which surface produces
One layer of antibacterial bioactive ceramicses film；Shorten the implant and synosteosis time, and improve its biocidal property.
Compared with prior art, the present invention has following significant advantage：
1st, the present invention prepares antibacterial multiporous biological and lives in the titanium with lattice structure porous or titanium alloy surface first
Property ceramic membrane.Because porous material has complex structure, the characteristics of surface area is big, using conventional differential arc oxidation
Or anodised method (Fig. 2), show following shortcoming：(1) electric current density is big, to equipment
Power requirement is higher；(2) solution quick heating, matrix surface is difficult film forming；(3) coating growth is uneven,
Part film layer is soluble；(4) coating growth speed is low, and thinner thickness causes low production efficiency；Cause
This, is the preparation for realizing the titanium or titanium alloy porous surface ceramic coating formed by micro-arc oxidation with lattice structure porous, must
The course of processing of traditional differential arc oxidation, including bath composition, electrical quantity, solution temperature, pH value must be changed
And the course of processing etc..Because the precondition of differential arc oxidation plasma discharge is, matrix surface generates one layer absolutely
The non-porous passivating film of edge, the passivating film requires that fine and close and thickness is uniform, and conventional technique is using under action of low-voltage pulse voltage
Direct formation of film at surface, but it is undesirable for the titanium or titanium alloy film-formation result with lattice structure porous, and the present invention is attempted
Under the conditions of direct current low current density, in the alkaline solution system of low temperature, one layer of uniform anodic oxygen is generated
Change film, then, in the electrolyte of acid partial neutral bacteriostatic agent, using high current density, make POROUS TITANIUM and
Titanium alloy surface is rapidly achieved and breaks up voltage, and realizes plasma discharge, then, maintains certain electric current density straight
Terminate to reaction.Conventional differential arc oxidation method is this method solved, is closed in the titanium with lattice structure porous and titanium
It is relatively thin that gold surface is difficult film forming, film layer, the shortcomings of non-porous or uneven hole.
2nd, the ceramic film thickness using the method preparation is uniform, and the speed of growth is very fast, due to using low temperature bar
Part, it is ensured that the production of the technique continuous-stable.The ceramic membrane is well combined with matrix, not only with good hard
Degree and corrosion resistance, and with higher biological activity and biocidal property.
3rd, the bioactive ceramicses film main component for preparing in differential arc oxidation system of the present invention is with high chemistry
The anatase of stability and the titanium dioxide of rutile；Or the Zinc Oxide copper oxide with obvious bacteriostasis；
And with higher degradation capability and induce the calcium monohydrogenphosphate that hydroxyapatite deposition acts on.
4th, form micro- etc. in the porous pure titanium with lattice structure porous or titanium alloy surface using the inventive method
Gas ions, by controlling technological parameter in the antibacterial bioactive ceramicses film of its Surface Creation.Performance test shows this
The controlled porosity of ceramic membrane is made as 30%～60%, and surface has micron-sized microcellular structure, and (micro-pore diameter is
0.5～5 μm), the corrosion current density of ceramic layer is 6.0E-8～1.0E-6A/cm in biosimulation solution2；
Jing cytologys detect, with matrix phase ratio, its surface alkalinty phosphatase assay improves 1～3 times, Bone Gla protein point
Secrete detection and improve 1～3 times；Cell propagation detection improves 2～5 times；Total protein content improves 1～5 times, and does not contain
The porous ceramic film of zinc or copper is compared, and bacteria resistance function improves 1～3 times.
5th, using the titanium or titanium alloy implant with lattice structure porous of the inventive method manufacture through animal
Experiment test, its synosteosis time is 10～15 days.
Description of the drawings：
Fig. 1 is the titanium or titanium alloy matrix with lattice structure porous.
Fig. 2 is ceramic membrane scanning electron microscope (SEM) photograph prepared by conventional micro-arc oxidation.
Fig. 3 is the scanning electron microscope (SEM) photograph of sample after prefabricated anode oxidation of the present invention.
Fig. 4 is the scanning electron microscope (SEM) photograph of sample after pulse differential arc oxidation of the present invention；In figure：2000 times of (a)；
500 times of (b).
Fig. 5 is the XRD figure of sample after pulse differential arc oxidation of the present invention.
Fig. 6 is the XPS figures of sample after pulse differential arc oxidation of the present invention；In figure：A () is containing zinc (in figure
" (a) ") and without the full analysis of spectrums of zinc () micro-arc oxidation films surface XPS in figure " (b) "；B () is the differential of the arc containing zinc
The full analysis of spectrums of oxide-film surface C a2p XPS；C () is the full spectrums point of the surface of micro-arc oxidation films containing zinc Zn2p XPS
Analysis.
Specific embodiment：
Below in conjunction with the accompanying drawings and embodiment is described further to the present invention.
In following examples, using the Ti-6Al-4V porous titanium alloys with lattice structure porous as matrix material
Material, its pattern is as shown in figure 1, its preparation process is according to disclosed in Chinese patent application 201210514088.X
Technical scheme is carried out, as prepared in this application porous Ti-6Al-V block materials, many with lattice structure
The Ti-6Al-4V titanium alloys in hole have unit grid structure, and its unit grid structure is square or rhombus 12
Face body, porosity is 40-90%, and aperture is adjustable in 300-5000 μ ms.The fatigue of the porous material is strong
Up to 0.3-0.7, elastic modelling quantity scope is 0.1-20GPa to degree/yield strength ratio.According to actual needs, the porous
The profile of material, porosity and pore size are fully controllable.
Embodiment 1
1. material prepares：Adopt electron beam melting rapid metallic prototyping technique to prepare porosity and there is lattice structure for 50%
The Ti-6Al-4V titanium alloys of porous.
2. chemical pickling：Pickle is constituted：40% (volumetric concentration) HF 1ml/L, 70% (volumetric concentration)
HNO34ml/L, tartaric acid 3g/L, slow releasing agent is o- nitrophenols, and remaining is water.Temperature：Room temperature, is processed
10 seconds time, cleaned 1～2 minute with tap water immediately after taking-up, then deionized water cleans 1～2 point
Clock.
3. prefabricated anode oxidation film preparation：Electrolyte is constituted：Concentration is the sodium carbonate of 10g/L, and concentration is 3g/L
Disodium oxalate., concentration for 0.5g/L sodium hydroxide, remaining is water.
In oxide-film preparation process, 20 DEG C of electrolyte temperature is maintained using refrigeration, electric source modes are direct current, it is permanent
Electric current 1A/dm2, the whole voltage of oxidation is 80V, and oxidization time is 3 minutes, and the present embodiment obtains non-porous passivating film
Thickness is about 2 μm (Fig. 3).
4. bi-directional square wave pulse differential arc oxidation film preparation：Electrolyte is constituted：Concentration is the sodium dihydrogen phosphate of 5g/L,
Concentration is the calcium acetate of 10g/L, and concentration is 0.5g/L acetic acid, and concentration is 0.5g/L zinc nitrates, and concentration is 0.5g/L
EDTA, concentration be 0.5g/L dodecyl sodium sulfates, remaining is water.
During antibacterial bioactive ceramicses film preparation, by 20 DEG C of circulating cooling water management electrolyte temperature,
Electric source modes be positive and negative bi-directional square wave pulse, electric current density 5A/dm2, the whole voltage of forward direction oxidation is 350V, is born
To the whole voltage 50V of oxidation；Oxidization time is 10 minutes, and frequency is 600Hz, and dutycycle is 0.5：0.3, obtain
The antibacterial bioactive ceramicses film thickness for obtaining is 10 μm, and porosity is 40%, and surface has micron-sized micropore
Structure (micro-pore diameter is 0.5～5 μm) is (Fig. 4).Preparation in the present embodiment differential arc oxidation system is biological living
Property ceramic membrane main component be the anatase with high chemical stability and rutile titanium dioxide (figure
5) Zinc Oxide or copper oxide (Fig. 6 (a) and Fig. 6 (c)), with obvious bacteriostasis, and tool
There is higher degradation capability and induce the calcium monohydrogenphosphate (see Fig. 6 (b)) of hydroxyapatite deposition effect.
After drying, obtain multiporous biological in the Ti-6Al-4V titanium alloy surfaces with lattice structure porous and live
Property ceramic membrane.The correlated performance data of the present embodiment is as follows：
The corrosion current density of ceramic layer is 3.96E-7A/cm in biosimulation solution2；
Jing cytologys detect, with matrix phase ratio, its surface alkalinty phosphatase assay improves 1 times, bone calcium
Element secretion detection improves 2 times；Cell propagation detection improves 1 times；Total protein content improves 2 times, and without zinc
Or the porous ceramic film of copper is compared, bacteria resistance function improves 2 times.
Using this method in the porous life prepared with lattice structure porous Ti-6Al-4V titanium alloy implant surfaces
Thing active ceramic film animal experiments prove that its synosteosis time is 15 days.
Embodiment 2
1. material prepares：Adopt electron beam melting rapid metallic prototyping technique to prepare porosity and there is lattice structure for 70%
The Ti-6Al-4V titanium alloys of porous.
2. chemical pickling：Pickle is constituted：40% (volumetric concentration) HF 2ml/L, 70% (volumetric concentration)
HNO36ml/L, oxalic acid 1g/L, slow releasing agent is p- dinitrophenol, and remaining is water.Temperature：Room temperature, is processed
10 seconds time, cleaned 1～2 minute with tap water immediately after taking-up, then deionized water cleans 1～2 point
Clock.
3. prefabricated anode oxidation film preparation：Electrolyte is constituted：Concentration is the sodium bicarbonate of 20g/L, and concentration is
The sodium citrate of 3g/L, concentration is the oxalic acid of 0.5g/L, and remaining is water.
In oxide-film preparation process, 15 DEG C of electrolyte temperature is maintained using recirculated water, electric source modes are direct current,
Constant current 1.5A/dm2, the whole voltage of oxidation is 100V, and oxidization time is 3 minutes, and the present embodiment obtains non-porous
Passivation film thickness is about 2 μm.
4. prepared by positive square-wave pulse micro-arc oxidation films：Electrolyte is constituted：Concentration for 10g/L calcium acetate, concentration
For the sodium glycerophosphate of 5g/L, concentration is 0.3g/L zinc acetates, and concentration is 0.5g/L acetic acid, and concentration is 0.5g/L
EDTA, concentration for 0.2g/L sodium laurylsulfate, remaining is water.
During antibacterial bioactive ceramicses film preparation, by 15 DEG C of circulating cooling water management electrolyte temperature,
Electric source modes be positive and negative bi-directional square wave pulse, electric current density 10A/dm2, the whole voltage of forward direction oxidation is 380V, is born
It is 80V to the whole voltage of oxidation, oxidization time is 15 minutes, and frequency is 600Hz, and dutycycle is 0.6：0.2,
The antibacterial bioactive ceramicses film thickness for obtaining is 12 μm, and porosity is 50%, and surface has micron-sized micro-
Pore structure (micro-pore diameter is 0.5～5 μm), in the present embodiment differential arc oxidation system bioactive ceramicses are prepared
Film main component is the titanium dioxide of the anatase with high chemical stability and rutile, with substantially antibacterial
The Zinc Oxide or copper oxide of effect, and with higher degradation capability and induce hydroxyapatite deposition to act on
Calcium monohydrogenphosphate.
After drying, obtain multiporous biological in the Ti-6Al-4V titanium alloy surfaces with lattice structure porous and live
Property ceramic membrane.The correlated performance data of the present embodiment is as follows：
The corrosion current density of ceramic layer is 6.89E-7A/cm in biosimulation solution2；
Jing cytologys detect, with matrix phase ratio, its surface alkalinty phosphatase assay improves 1.5 times, bone
Calcium element secretion detection improves 1 times；Cell propagation detection improves 2 times；Total protein content improves 2 times.
The porous prepared in the Ti-6Al-4V titanium alloys implant surfaces with lattice structure porous using this method
Bioactive ceramicses film animal experiments prove that its synosteosis time is 15 days.
Porous ceramic film without zinc or copper is compared, and bacteria resistance function improves 2 times.
Embodiment 3
1. material prepares：Successively forming technique (AM-EBM) prepares porosity for 60% tool to adopt electron-beam melting
There is the beta-titanium alloy of dot matrix structural porous.
2. chemical pickling：Pickle is constituted：40% (volumetric concentration) HF 2ml/L, 70% (volumetric concentration)
HNO36ml/L, tartaric acid 5g/L, slow releasing agent is picric acid, and remaining is water.Temperature：Room temperature, process time
10 seconds, cleaned 1～2 minute with tap water immediately after taking-up, then deionized water is cleaned 1～2 minute.
3. prefabricated anode oxidation film preparation：Electrolyte is constituted：Concentration is the sodium bicarbonate of 20g/L, and concentration is
The Disodium oxalate. of 2g/L, concentration is the tartaric acid of 1g/L, and remaining is water.
In oxide-film preparation process, 15 DEG C of electrolyte temperature is maintained using recirculated water, electric source modes are direct current,
Constant current 1A/dm2, the whole voltage of oxidation is 80V, and oxidization time is 5 minutes, and the present embodiment obtains non-porous passivation
Film thickness is about 1 μm.
4. prepared by positive square-wave pulse micro-arc oxidation films：Electrolyte is constituted：Concentration is the calcium acetate of 10g/L, 5g/l's
Calcium oxide, concentration is the sodium dihydrogen phosphate of 10g/L, and concentration is 3g/L Schweinfurt greens, and concentration is 1g/L acetic acid, dense
The EDETATE SODIUM for 0.5g/L is spent, remaining is water.
In oxide-film preparation process, by 20 DEG C of circulating cooling water management electrolyte temperature, electric source modes are for just
Negative bi-directional square wave pulse, electric current density 15A/dm2, the whole voltage of forward direction oxidation is 400V；The whole voltage of negative sense oxidation
For 100V, oxidization time is 15 minutes, and frequency is 800Hz, and dutycycle is 0.5：0.3, the oxidation of acquisition
Film thickness is 15 μm, and porosity is 60%, and surface has micron-sized microcellular structure, and (micro-pore diameter is
0.5～5 μm), surface has micron-sized microcellular structure (micro-pore diameter is 0.5～5 μm), the present embodiment differential of the arc
The bioactive ceramicses film main component for preparing in oxidation system is the anatase with high chemical stability and gold
The titanium dioxide of red stone, the Zinc Oxide with obvious bacteriostasis or copper oxide, and with higher degraded
Ability and induce hydroxyapatite deposition act on calcium monohydrogenphosphate.
After drying, on the beta-titanium alloy surface with lattice structure porous multiporous biological active ceramic is obtained
Film.The correlated performance data of the present embodiment is as follows：
The corrosion current density of ceramic layer is 7.64E-8A/cm in biosimulation solution2；
Jing cytologys detect, with matrix phase ratio, its surface alkalinty phosphatase assay improves 1.5 times, bone
Calcium element secretion detection improves 2 times；Cell propagation detection improves 2 times；Total protein content improves 1 times；With do not contain
The porous ceramic film of zinc or copper is compared, and bacteria resistance function improves 2 times.
The multiporous biological activity prepared in the beta-titanium alloy implant surfaces with lattice structure porous using this method
Ceramic membrane animal experiments prove that its synosteosis time is 10 days.
Claims (9)
1. the preparation side of a kind of titanium with lattice structure porous or the antibacterial bioactive ceramicses film of titanium alloy surface
Method, it is characterised in that：The method is comprised the following steps：
(1) chemical polishing：Titanium with lattice structure porous or titanium alloy are carried out in pickle chemical throwing
Light；
(2) preparation of prefabricated anode oxide-film：In the first electrolyte and under the conditions of DC voltage, lead to
Cross DC anodizing method carries out prefabricated anode in the POROUS TITANIUM or titanium alloy surface Jing after step (1) process
The preparation of oxide-film；By weight percentage, the first electrolyte composition is as follows：
(3) preparation of antibacterial porous ceramic film：In the second electrolyte and in bi-directional square wave pulse voltage bar
Under part, antibacterial porous ceramic film is carried out in POROUS TITANIUM or titanium alloy surface by bidirectional pulse differential arc oxidation method
Prepare；By weight percentage, the second electrolyte composition is as follows：
2. the titanium with lattice structure porous according to claim 1 or titanium alloy surface are antibacterial biological living
The preparation method of property ceramic membrane, it is characterised in that：The titanium with lattice structure porous or titanium alloy have single
First network, its unit grid structure is square or granatohedron, and porosity is 40-90%, hole
Footpath is 300-5000 μm；It is to be prepared using electron beam melting rapid metallic prototyping technique.
3. the titanium with lattice structure porous according to claim 1 or titanium alloy surface are antibacterial biological living
The preparation method of property ceramic membrane, it is characterised in that：In step (1), the pickle is organic acid, inhibition
Agent and the mixed aqueous solution of mineral acid, wherein：The mineral acid is one or two in Fluohydric acid. and nitric acid,
The organic acid is citric acid, tartaric acid, malic acid or oxalic acid；The corrosion inhibiter is o- nitrophenols, o-
Nitroaniline, p- dinitrophenol, p- nitro saliva quinoline or picric acid etc..
4. the titanium with lattice structure porous according to claim 1 or titanium alloy surface are antibacterial biological living
The preparation method of property ceramic membrane, it is characterised in that：In step (2), the prefabricated anode aoxidizes film preparation
Cheng Zhong, 5～30 DEG C of electrolyte temperature, electric source modes are direct current, and the whole voltage of oxidation is 50～150V, during oxidation
Between 3～10 minutes, 0.2～5A/dm of electric current density2, the prefabricated anode oxide thickness of acquisition is 1～3 μm.
5. the titanium with lattice structure porous according to claim 1 or 4 or the antibacterial life of titanium alloy surface
The preparation method of thing active ceramic film, it is characterised in that：In step (2), the carbonate be sodium carbonate,
Potassium carbonate, sodium bicarbonate or potassium bicarbonate；The acylate is natrium malicum, potassium malate, tartaric acid
Sodium, Soluble tartar., sodium citrate, potassium citrate, Disodium oxalate., potassium oxalate, sodium succinate or Potassium Suceinate
Deng；The pH adjusting agent is acetic acid, oxalic acid, tartaric acid, citric acid or phosphoric acid.
6. the titanium with lattice structure porous according to claim 1 or titanium alloy surface are antibacterial biological living
The preparation method of property ceramic membrane, it is characterised in that：In step (3), the antibacterial porous ceramicss film preparation
Cheng Zhong, 5～30 DEG C of electrolyte temperature, electric source modes are bi-directional square wave pulse, and the whole voltage of forward direction oxidation is
350～450V, the whole voltage of negative sense oxidation is 50～150V；Oxidization time 10～40 minutes, electric current density 2～
20A/dm2, 200～1000Hz of frequency；The antibacterial porous ceramicss film thickness for obtaining is 5～30 μm, and porosity is
20～60%, surface has micron-sized microcellular structure, and micro-pore diameter is 0.5～5 μm.
7. the titanium with lattice structure porous according to claim 1 or 6 or the antibacterial life of titanium alloy surface
The preparation method of thing active ceramic film, it is characterised in that：In step (3), the calcium salt is calcium acetate, oxygen
Change one or more in calcium and dalcium biphosphate；The phosphate is disodium-hydrogen, potassium phosphate,monobasic, partially
One kind in sodium phosphate, potassium metaphosphate, polyphosphate sodium, PA 800K, sodium glycerophosphate and potassium glycerinophosphate or
It is several；The zinc salt is zinc acetate or zinc nitrate；The mantoquita is Schweinfurt green or copper nitrate etc.；The pH is adjusted
Section agent is acetic acid, oxalic acid, tartaric acid, citric acid or phosphoric acid；The chelating agent is EDTA, EDETATE SODIUM
Salt, EGTA, ethylenediamine tetrapropionic acid, sulfosalicylic acid or thiourea etc.；The surfactant be stearic acid,
Dodecylbenzene sodium sulfonate, sodium lauryl sulphate or sodium laurylsulfate etc..
8. the titanium with lattice structure porous according to claim 1 or 6 or the antibacterial life of titanium alloy surface
The preparation method of thing active ceramic film, it is characterised in that：In step (3), the antibacterial porous ceramic film system
During standby, solution is cooled down using refrigeration system, control solution temperature for 5～30 DEG C, to maintain suppression
The speed of growth and surface quality of bacterium porous ceramic film.
9. the titanium with lattice structure porous according to claim 1 or titanium alloy surface are antibacterial biological living
The application of the preparation method of property ceramic membrane, it is characterised in that：The method is put on into the Dental implantion of machined molding
Body or Invasive lumbar fusion device so as to which surface produces one layer of antibacterial bioactive ceramicses film；Shorten the implant and bone
Binding time, and improve its biocidal property.
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