CN104911671B - A kind of preparation method of titanium alloy surface combined oxidation bioceramic film - Google Patents
A kind of preparation method of titanium alloy surface combined oxidation bioceramic film Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of titanium alloy surface combined oxidation bioceramic film, belongs to the technical field of surface of orthopaedics metal material.The method of the invention prepares interior solid layer by anodizing, directly prepare porous surface bioceramic film layer on the basis of anode oxidation membrane by micro-arc oxidation again, finally aoxidized for a long time in the case of low-voltage or low current on the basis of differential arc oxidation film layer using anodizing, so that the binder course of film layer is thicker, hole on compacted zone is less, hole in rough layer is interconnected, and the present invention prepares combined oxidation bioceramic film inner layer for binder course, compact structure；Intermediate layer is compacted zone, close structure, the said minuscule hole for having many even aperture distributions；Outer layer is porosity and looseness layer, and rough surface is porous, with good hydrophily；Make up anode oxidation membrane thin, the low feature of hardness；Next solves the single shortcoming of differential arc oxidation film layer color.
Description
Technical field
The present invention relates to a kind of preparation method of titanium alloy surface combined oxidation bioceramic film, belong to orthopaedics metal material
Technical field of surface.
Background technology
After bone substitution material implants, preferable combination is that bone substitution material is asked with bone bonding pattern with bone tissue
With reference to, make between implant and bone continuity functionally to be presented by the continuity of interfacial structure, and interface bond strength
It can reach even more than bone itself, the implant bond strength of itself.Bone bonding process includes mechanical interlock and acted on and chemical bond
Cooperation is used, and only the material with bioactivity could form this bone bonding.Due to the structure and property of medical metal material
Differed greatly with bone tissue, it is impossible to occur chemical key with bone tissue and combined.In addition, titanium differs outstanding with bone tissue modulus of elasticity
Very, the adverse consequences such as stress concentration and bone information are also easy to produce after implanting.Thus find that modulus of elasticity is low (avoids material in body
Interior fracture), to bone tissue " stress shielding is small ", more matched with skeleton mechanical compatibility, good biocompatibility and energy
The titanium alloy material being bonded with bon e formation bone turns into the emphasis of medical titanium alloy developing material.
In order to assign the bioactivity that medical titanium is good, activation process need to be carried out to medical titanium surface.The activation of medical titanium
Method substantially has plasma spray method, anodizing, colloidal sol gel methods, spatial induction mineralising method and micro-arc oxidation etc..
The oxidation film layer that medical titanium and titanium alloy anode oxidation are obtained is bright in colour, and can form knot with Titanium base surface
Structure is fine and close, one layer of strong hydrophobic silica film layer of adhesion, can not only improve the wearability and corrosion resistance of material, and can
Digestion of metallic ion is largely solved the problems, such as, cytotoxicity is reduced, greatly improves the biocompatibility of implant.Separately
Outside, the oxide-film of different colours is also used as a kind of means that different implantation pieces are distinguished.Meanwhile, with plastic surgery dummy
Gradually increase in clinical application, the requirement of people has been not limited only to the recovery of its basic function, the also day of the requirement to aesthetic property
Benefit is improved, such as, and the chromatic beauty of artificial tooth can give visual sense of beauty enjoyment.One kind side that anode oxidation process is modified as surface
Method, its technique is simple, opens the new way of a strip material feature and aesthetic property harmony.
But single conventional anodization technology can only prepare the titanium dioxide existed with amorphous form in titanium alloy surface
Film, although oxide-film various colors, but film layer is often too thin, and the hardness of anode oxide film is general between 300-500HV, anode
The maximum gauge of oxide-film is only 3 ~ 10 μm, and wearability is poor.And film surface is also easy to produce sharp side defect, and anodic oxidation is suitable
It is narrower with scope.
Differential arc oxidization technique can be directly formed in one layer of hydrophilic film, film layer due to part on titanium or titanium alloy surface
There is rutile TiO in the influence of high temperature2With Detitanium-ore-type TiO2Phase structure.Due to there is the high-temperature-phase of titanium dioxide in film layer
Rutile TiO2Presence, the hardness of micro-arc oxidation films can reach more than 600HV, can reach 2500HV, thickness side
Face, differential arc oxidation can obtain the uniform oxidation film layer of surfaces externally and internally, and its maximum gauge can reach 200-300 μm.And can
To adjust electrolyte prescription, by using the electrolyte rich in Ca, P so that the film layer that differential arc oxidation is obtained, which exists, has biology
The hydroxyapatite phase of activity, allows titanium or titanium alloy to be easier to be combined with matrix in implanting tissue, prevents " foreign material repulsion " existing
The generation of elephant.But differential arc oxidation film layer short texture, the amorphous film layer structure formed without anodic oxidation is fine and close, film layer and base
Adhesion is obtained between body not strong.
To sum up, combined oxidation technology, is the fine and close oxygen obtained first in the pre- anodized in titanium or titanium alloy surface
Change film, then on this basis, the method for preparing the ceramic film of one layer of porosity and looseness on surface again using micro-arc oxidation, most
The method for carrying out an anodic oxidation again afterwards（That is AO+MAO+AO）.Ceramic film prepared by this method has three layers of gradient-structure, interior
Layer is fine and close, and there is one layer of small aperture layer in outer layer rough porous, the intermediate layer between outer layer and internal layer.This ceramic film for having gradient can
Stop that free metal ion is separated out into body fluid with effective, so as to cause the infection of body tissue.The membrane structure is fine and close,
Adhesion is good, there is important Research Significance and DEVELOPMENT PROSPECT.
The content of the invention
The technical problem to be solved in the present invention is that anode oxidation membrane is thin, the low shortcoming of hardness；And differential arc oxidation film layer
Binder course hole, when in treated medical titanium alloy implanting tissue, parent metal ion can be free from these holes
Out, so as to cause tissue infection, it is unfavorable for the shortcoming of wound healing.
It is an object of the invention to provide a kind of preparation method of titanium alloy surface combined oxidation bioceramic film, using many
It is in stepped bioceramic film layer to repeat to close mode of oxidizing and prepare, i.e., prepare interior solid layer by anodizing, then lead to
Cross micro-arc oxidation and porous surface bioceramic film layer is directly prepared on the basis of anode oxidation membrane, finally using anodic oxidation
Method is aoxidized for a long time on the basis of differential arc oxidation film layer in the case of low-voltage or low current so that the binder course of film layer
Thicker, the hole on compacted zone is less, and the hole in rough layer is interconnected, and specifically includes following steps：
（1）Titanium alloy is polished, it is oil removing, cleaning, standby after natural drying；
（2）By step（1）The sample handled well is hung in the electrolytic solution as anode, and stainless steel electrolytic groove is negative electrode, is entered
It is standby after row anodic oxidation, cleaning, drying；Wherein, electrolyte is one kind of phosphoric acid and sulfuric acid.
（3）The electrolyte in electrolytic cell is changed, by step（2）The sample of middle process anodic oxidation pretreatment is suspended on again
As anode in electrolyte, stainless steel carries out differential arc oxidation as negative electrode, standby after cleaning, drying；Wherein described electrolyte is
Calcium acetate, one or two kinds of materials of potassium phosphate are mixed in any proportion；
（4）The electrolyte in electrolytic cell is changed, by step（3）In the obtained sample of anodic oxidation be suspended on electrolysis again
As anode in liquid, stainless steel carries out anodic oxidation as negative electrode, wherein, electrolyte is sodium oxalate, nine water sodium metasilicate, di(2-ethylhexyl)phosphate
One or more in hydrogen sodium, sodium hydroxide are mixed to get in any proportion.
（5）By step（4）In the obtained sample of anodic oxidation with after deionized water cleaning, drying in titanium alloy surface just
Obtain combined oxidation bioceramic film.
Step of the present invention（2）The concentration of phosphoric acid is 15 ~ 50g/L in described electrolyte, and the concentration of sulfuric acid is 300 ~ 390g/
L。
Step of the present invention（2）With（4）In described electrolytic process, electrolytic parameter is set as：Forward voltage is 10 ~ 120V,
Positive dutycycle is 10 ~ 60%, and frequency is 100 ~ 800Hz, and positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 100min.
Step of the present invention（3）Described in the formula of electrolyte be：Acetic acid calcium concentration is 15 ~ 40g/L, the concentration of potassium phosphate is
10~30g/L。
Step of the present invention（3）Described in the parameter that is electrolysed be：220 ~ 600V of forward voltage, positive dutycycle is 10% ~ 60%,
Frequency is 100Hz ~ 800Hz, and positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 30min.
Step of the present invention（4）Described in the formula of electrolyte be：The concentration of sodium oxalate is 10 ~ 25g/L, nine water sodium metasilicate 10
~ 15g/L, the concentration of sodium dihydrogen phosphate are that 10 ~ 15g/L, the concentration of sodium hydroxide are 1 ~ 7g/L.
Ceramic film prepared by the method for the invention has three layers of gradient-structure, inner compact layer, outer layer rough porous, outer layer
There is one layer of small aperture layer in intermediate layer between internal layer；This ceramic film for having gradient can effectively stop free metal from
Son is separated out into body fluid, so as to cause the infection of body tissue；The anode oxidation process finally carried out is additionally, since, the process
The film surface of preparation can be by controlling the electrolyte prescription color different with power parameter presentation, therefore, different colours
Oxide-film is also used as a kind of means that different implantation pieces are distinguished, as plastic surgery dummy gradually increases in clinical application
Many, the requirement of people has been not limited only to the recovery of its basic function, and the requirement to aesthetic property is also increasingly improved, therefore present invention system
Standby film layer can also meet the requirement of popular aesthetic property.
Beneficial effects of the present invention：
（1）Due to the anode oxidation process finally carried out, film surface prepared by the process can be by controlling electrolyte
The formula color different with power parameter presentation, therefore, the oxide-film of different colours are also used as what different implantation pieces were distinguished
A kind of means, as plastic surgery dummy gradually increases in clinical application, the requirement of people has been not limited only to its basic training
The recovery of energy, the requirement to aesthetic property is also increasingly improved, therefore film layer prepared by the present invention can also meet wanting for popular aesthetic property
Ask.
（2）The controllability of the present invention is high, is conducive to control, and cost is low, and application is wider, can produce in batches.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is the SEM spectrum for the combined oxidation bioceramic film that embodiment 1 is prepared；
Fig. 3 is the XRD spectrum for the combined oxidation bioceramic film that embodiment 1 is prepared；
Fig. 4 is the SEM spectrum for the combined oxidation bioceramic film that embodiment 2 is prepared；
Fig. 5 is the XRD spectrum for the combined oxidation bioceramic film that embodiment 2 is prepared；
Fig. 6 is the SEM spectrum for the combined oxidation bioceramic film that embodiment 3 is prepared；
Fig. 7 is the XRD spectrum for the combined oxidation bioceramic film that embodiment 4 is prepared.
Embodiment
The present invention is described further with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited to institute
State content.
Embodiment 1
The present embodiment methods described is used for the bioceramic film layer for preparing step type, as shown in figure 1, specifically including following step
Suddenly：
（1）Pretreatment:Titanium alloy TC 4 is cut into cylindrical titanium, punched in the top of sample, table is carried out to titanium alloy
Then face grinding process carries out oil removing, alkali cleaning and deionization washing, natural drying again to specimen surface no marking；
（2）Anodic oxidation：Hung the sample pre-processed as anode in the electrolytic solution, stainless steel electrolytic groove is the moon
Pole, is carried out standby after anodic oxidation, cleaning, drying；Power parameter is set as：Forward voltage is 10V, and positive dutycycle is 10%,
Frequency is 100Hz, and positive negative pulse stuffing number is 1, and oxidization time is 10；Electrolyte prescription is：Phosphoric acid concentration is 15g/L.
（3）Differential arc oxidation：The electrolyte in electrolytic cell is changed, electrolyte prescription is：Acetic acid calcium concentration is 15g/L, phosphoric acid
The concentration of potassium is 10g/L；Will（2）Step hangs on phase again through cylindrical titanium of the anodized with dense oxidation film
With as anode, stainless steel electrolytic groove is negative electrode in electrolyte, then differential arc oxidation is carried out, power supply used is the pulse power, power supply
Parameter setting is：Forward voltage 220V, positive dutycycle is 10%, and frequency is 100Hz, and positive negative pulse stuffing number is 1, and oxidization time is
10min。
（4）Anodic oxidation：Will（3）The sample handled in step through differential arc oxidation carries out anodic oxidation again, changes electricity
Liquid is solved, electrolyte prescription is：The concentration of sodium oxalate is that 10g/L, nine water sodium metasilicate 10g/L, the concentration of sodium dihydrogen phosphate are 10g/
L, the concentration of sodium hydroxide are 1g/L.Power parameter is set as：Forward voltage is 10V, and positive dutycycle is 10%, and frequency is
100Hz, positive negative pulse stuffing number is 1, and oxidization time is 10min.
（5）The sample of MULTIPLE COMPOSITE oxidation processes is just obtained into film layer structure with deionized water cleaning, drying in step type
Bioceramic film layer, with good hydrophily.
（6）As shown in Figure 2,3, detected through XRD and SEM, combined oxidation film layer obtained by the embodiment by interior solid layer and
Outside weaker zone is constituted, and has fraction of said minuscule hole to be connected between the hole and hole of weaker zone, and microhardness is reachable
394Hv, thicknesses of layers contains more Anatase up to 80 μm；Lilac is presented in film layer.
Embodiment 2
The present embodiment methods described is used for the bioceramic film layer for preparing step type, as shown in figure 1, specifically including following step
Suddenly：
（1）Pretreatment:Titanium alloy TC 4 is cut into cylindrical titanium, punched in the top of sample, table is carried out to titanium alloy
Face grinding process, without obvious cut, then carries out oil removing, alkali cleaning and deionization washing, natural drying again to specimen surface；`
（2）Anodic oxidation：Hung the sample pre-processed as anode in the electrolytic solution, stainless steel electrolytic groove is the moon
Pole, carries out anodic oxidation；Power parameter is set as：Forward voltage is 60V, and positive dutycycle is 30%, and frequency is 500Hz, positive and negative
Umber of pulse is 3, and oxidization time is 50min；Electrolyte prescription is：Sulfuric acid concentration is 300g/L.
（3）Differential arc oxidation：The electrolyte in electrolytic cell is changed, electrolyte prescription is：Acetic acid calcium concentration is 30g/L, phosphoric acid
The concentration of potassium is 15g/L.Will（2）Step pre-processes the cylindrical titanium with dense oxidation film through anodic oxidation and hung on again
As anode in identical electrolyte, stainless steel electrolytic groove is negative electrode, then carries out differential arc oxidation, and power supply used is the pulse power, electricity
Source parameter setting is：Forward voltage 400V, positive dutycycle is 30%, and frequency is 500Hz, and positive negative pulse stuffing number is 3, oxidization time
For 20min.
（4）Anodic oxidation：Will（3）The sample handled in step through differential arc oxidation carries out anodic oxidation again, changes electricity
Liquid is solved, electrolyte prescription is：The concentration of sodium oxalate is that 15g/L, nine water sodium metasilicate 12g/L, the concentration of sodium dihydrogen phosphate are 12g/
L, the concentration of sodium hydroxide are 2g/L；Power parameter is set as：Forward voltage is 60V, and positive dutycycle is 30%, and frequency is
500Hz, positive negative pulse stuffing number is 3, and oxidization time is 50min.
（5）The sample of MULTIPLE COMPOSITE oxidation processes is just obtained into film layer structure with deionized water cleaning, drying in step type
Bioceramic film layer, with good hydrophily.
（6）Combined oxidation film layer obtained by the embodiment as shown in Figure 4,5, detects through XRD and SEM, film layer interior solid layer
And outside weaker zone is constituted, the said minuscule hole for having many between the hole and hole of weaker zone is connected, in three-dimensional communication structure, and
Microhardness is up to 450Hv, and thicknesses of layers contains Rutile Type and Anatase up to 100 μm in film layer, film layer presents light greenish blue
Color.
Embodiment 3
The present embodiment methods described is used for the bioceramic film layer for preparing step type, as shown in figure 1, specifically including following step
Suddenly：
（1）Pretreatment:Titanium alloy TC 4 is cut into cylindrical titanium, punched in the top of sample, table is carried out to titanium alloy
Face grinding process, without obvious cut, then carries out oil removing, alkali cleaning and deionization washing, natural drying again to specimen surface；`
（2）Anodic oxidation：Hung the sample pre-processed as anode in the electrolytic solution, stainless steel electrolytic groove is the moon
Pole, carries out anodic oxidation；Power parameter is set as：Forward voltage is 120V, and positive dutycycle is 60%, and frequency is 800Hz, just
Negative pulse number is 6, and oxidization time is 100min；Electrolyte prescription is：The concentration of phosphoric acid is 50g/L.
（3）Differential arc oxidation：The electrolyte in electrolytic cell is changed, electrolyte prescription is：Acetic acid calcium concentration is 40g/L, phosphoric acid
The concentration of potassium is 30g/L.Will（2）Step hangs on phase again through cylindrical titanium of the anodized with dense oxidation film
With as anode, stainless steel electrolytic groove is negative electrode in electrolyte, then differential arc oxidation is carried out, power supply used is the pulse power, power supply
Parameter setting is：Forward voltage 425V, positive dutycycle is 60%, and frequency is 800Hz, and positive negative pulse stuffing number is 6, and oxidization time is
30min。
（4）Anodic oxidation：Will（3）The sample handled in step through differential arc oxidation carries out anodic oxidation again, changes electricity
Liquid is solved, electrolyte prescription is：The concentration of sodium oxalate is that 25g/L, nine water sodium metasilicate 15g/L, the concentration of sodium dihydrogen phosphate are 15g/
L, the concentration of sodium hydroxide are 7g/L；Power parameter is set as：Forward voltage is 120V, and positive dutycycle is 60%, and frequency is
800Hz, positive negative pulse stuffing number is 6, and oxidization time is 100min.
（5）The sample of MULTIPLE COMPOSITE oxidation processes is just obtained into film layer structure with deionized water cleaning, drying in step type
Bioceramic film layer, with good hydrophily.
（6）Combined oxidation film layer obtained by the embodiment as shown in Figure 6,7, is detected through XRD and SEM, in combined oxidation film layer
Portion's compacted zone and outside weaker zone are constituted, and have the hole phase of the even size distribution of many between the hole and hole of weaker zone
Even, in three-dimensional communication structure, and microhardness is up to 475Hv, and thicknesses of layers contains a large amount of rutile up to 120 μm in film layer
Darkcyan is presented in phase and a small amount of Anatase, film layer.
Claims (3)
1. a kind of preparation method of titanium alloy surface combined oxidation bioceramic film, it is characterised in that specifically include following steps：
（1）Titanium alloy is polished, it is oil removing, cleaning, standby after natural drying；
（2）By step（1）The sample handled well is hung in the electrolytic solution as anode, and stainless steel electrolytic groove is negative electrode, carries out sun
Pole is aoxidized, standby after cleaning, drying；Wherein, electrolyte is one kind of phosphoric acid or sulfuric acid；
（3）The electrolyte in electrolytic cell is changed, by step（2）The sample of middle process anodic oxidation pretreatment is suspended on electrolysis again
As anode in liquid, stainless steel carries out differential arc oxidation as negative electrode, standby after cleaning, drying；Wherein described electrolyte is acetic acid
Calcium, potassium phosphate are mixed to get；
（4）The electrolyte in electrolytic cell is changed, by step（3）In the obtained sample of differential arc oxidation hang again in the electrolytic solution
As anode, stainless steel carries out anodic oxidation as negative electrode, wherein electrolyte be sodium oxalate, nine water sodium metasilicate, sodium dihydrogen phosphate,
Sodium hydroxide is mixed to get；
（5）By step（4）In the obtained sample of anodic oxidation with just being obtained in titanium alloy surface after deionized water cleaning, drying
Combined oxidation bioceramic film；
Step（2）The concentration of phosphoric acid is 15 ~ 50g/L in described electrolyte or the concentration of sulfuric acid is 300 ~ 390g/L；
Step（3）Described in the formula of electrolyte be：Acetic acid calcium concentration is that 15 ~ 40g/L, the concentration of potassium phosphate are 10 ~ 30g/L；
Step（4）The concentration of described electrolyte mesoxalic acid sodium is 10 ~ 25g/L, nine 10 ~ 15g/L of water sodium metasilicate, sodium dihydrogen phosphate
Concentration be that 10 ~ 15g/L, the concentration of sodium hydroxide are 1 ~ 7g/L.
2. the preparation method of titanium alloy surface combined oxidation bioceramic film according to claim 1, it is characterised in that：Step
Suddenly（2）With（4）In described electrolytic process, electrolytic parameter is set as：Forward voltage be 10 ~ 120V, positive dutycycle be 10 ~
60%, frequency is 100 ~ 800Hz, and positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 100min.
3. the preparation method of titanium alloy surface combined oxidation bioceramic film according to claim 1, it is characterised in that：Step
Suddenly（3）Described in the parameter that is electrolysed be：220 ~ 600V of forward voltage, positive dutycycle be 10% ~ 60%, frequency be 100Hz ~
800Hz, positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 30min.
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| CN106676604B (en) * | 2015-11-05 | 2018-07-20 | 中国科学院金属研究所 | Preparation method and applications with the porous titanium of lattice structure or the antibacterial bioactive ceramics film of titanium alloy surface |
| CN106676605B (en) * | 2015-11-05 | 2018-07-13 | 中国科学院金属研究所 | Preparation method and applications with the porous pure titanium of lattice structure or titanium alloy surface multiporous biological active ceramic film |
| CN106725928A (en) * | 2016-12-12 | 2017-05-31 | 同济大学 | A kind of dental implant abutment and preparation method thereof |
| CN112301399A (en) * | 2020-07-20 | 2021-02-02 | 江苏燕园精英医疗科技有限公司 | Surface treatment method for dental implant |
| CN114540911B (en) * | 2020-11-25 | 2023-11-14 | 比亚迪股份有限公司 | Metal part and preparation method thereof |
| CN112779583B (en) * | 2020-12-26 | 2023-07-07 | 常州市钛宇新材料科技有限公司 | Titanium alloy surface treatment method combining color and thick film |
| CN113089047A (en) * | 2021-04-12 | 2021-07-09 | 四川九洲电器集团有限责任公司 | Aluminum alloy component and preparation method and application thereof |
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