CN110152056A - A method of functional ionic is rapidly introduced into titanium alloy surface - Google Patents
A method of functional ionic is rapidly introduced into titanium alloy surface Download PDFInfo
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- A61L2430/00—Materials or treatment for tissue regeneration
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Abstract
A method of it being rapidly introduced into functional ionic in titanium alloy surface, belongs to the surface-functionalized modification treatment technology field of titanium alloy medical embedded material.First using TC4 as electrolytic anode, electrolytic cell forms volcano shape porous coating in TC4 sample surfaces as electrolysis cathode, by the agglomeration of plasma high-temperature high pressure moment；Then functional ionic is introduced into the coating using hydro-thermal reaction method, while improves the hydrophily on surface.Multiple functions ion is evenly distributed in titanium alloy surface, is conducive to the adherency and the proliferative capacity that increase osteoblast.This method both can be convenient efficiently in titanium alloy surface prepares coating, the ingredient of the adjusting solution in subsequent water-heat process can be passed through again, functional ionic Cu, Zn, Mg, Ce, Sr etc. are introduced into coating surface, the performances such as antibacterial or the skeletonization of biomedical metallic material are improved, the fields such as modification have a good application prospect on the surface of medical embedded material.
Description
Technical field
The invention belongs to the surface-functionalized modification treatment technology fields of titanium alloy medical embedded material, and in particular to one kind is adopted
With differential arc oxidation and hydro-thermal reaction method in the simple and quick method for introducing one or more functional ionics of titanium alloy surface, to mention
The bioactivity of titanium master alloy, it is with important application prospects in fields such as biomedicines.
Background technique
Substitute material for human hard tissues, such as joint prosthesis and tooth-implanting are the important components of biomaterial, oneself
One of hot spot as biomaterial research.At present in Artificial Intervention material, using it is most be titanium and its alloy material.With it
Its material is compared, and titanium alloy has many advantages, such as that nonmagnetic, light, good toughness, mechanical property and bio-compatible performance are good.But titanium and
The elasticity modulus of its alloy itself is much higher than nature bone tissue, and the corrosion resisting property in body fluid is not high, and bioactivity is undesirable, cannot
Induce hydroxyapatite deposition.It, both can be with by preparing the ceramic coating of multiple functions modification by ion-doping in titanium alloy surface
The good mechanical performance of titanium alloy is kept to assign its good bioactivity again.Therefore, for titanium and its alloy as biology doctor
The shortcoming existing for metal material carries out surface to it and is modified, and it is particularly important for promoting its performance.
On medical titanium alloy surface there are many ways to prepares coating: plating, plasma spraying, ion implanting, colloidal sol are solidifying
Glue method, vapor deposition etc..But there is apparent defect in these methods, if sol-gal process preparation temperature is low, cause amorphous phase
Excessively, coating binding force is loosely；Plasma spraying causes thermal stress to remain because cooling rate is too fast under high temperature, coating and matrix
Bond strength is low, expensive, and can not prepare uniform coating in the complex-shaped product surface such as dental implant.Therefore, change
Into coating production, the binding force of coating and matrix is improved, makes coating stable for extended periods of time and release function ion in vivo
It is urgent problem.
Bioactive ions (Sr, Mg, Cu, Ca, Zn etc.) are the important microelements of human body.Such as strontium ion can enhance bone
Matter intensity and improvement bone metabolism, promote the Proliferation, Differentiation of osteoblast；Magnesium ion can promote marrow stromal cell differentiation and
Calcium deposition, magnesium deficiency will lead to osteoporosis；Copper ion is a kind of putative antibacterial ion, has been widely used in bone remoulding
During；Calcium ion is all indispensable ion of body items physiological activity, is the important substance that bone is constituted；Zinc ion
All metabolic processes have almost been participated in human body.Zinc also has catalysis and adjustment effect simultaneously, facilitates cell Proliferation point
Change and related enzyme system plays its function, accelerates the formation and calcification of bone tissue, to reduce healing time.
Proposed adoption differential arc oxidization technique of the present invention carries out bioactivation processing to titanium alloy, is rich in titanium alloy surface preparation
The bioactivity, porous film layer of calcium phosphorus, hydro-thermal process is then carried out to it makes the amorphous state calcium phosphorous compound in film layer be converted into hydroxyl
Base apatite, while increasing matrix surface bioactivity, and because introducing the function such as Sr, Mg, Cu, Ca, Zn in oxidation film layer
Can ion and make it have the performances such as good antibacterial, cell proliferation and differentiation, Integrated implant, protein adsorption.
Summary of the invention
The present invention provides a kind of simple and quick on medical titanium alloy surface by differential arc oxidation and hydro-thermal reaction Synergistic method
The method for introducing one or more functional ionics.Used technical solution is the present invention to solve above-mentioned technical problem: first
It is used as electrolytic anode with Ti6Al4V (TC4 is shaped using DiMetal-280 laser 3D printing machine), electrolytic cell is as electrolysis yin
Pole forms volcano shape porous coating in TC4 sample surfaces by the agglomeration of plasma high-temperature high pressure moment；Then it utilizes
Functional ionic is introduced into the coating by hydro-thermal reaction method, while improving the hydrophily on surface.It is prepared by this method a variety of
Functional ionic is evenly distributed in titanium alloy surface, is conducive to the adherency and the proliferative capacity that increase osteoblast.
This method not only can be convenient efficiently in titanium alloy surface prepares coating, but also can be by subsequent water-heat process
Functional ionic Cu, Zn, Mg, Ce, Sr etc. are introduced into coating surface, improve bio-medical metal material by the middle ingredient for adjusting solution
The performances such as the antibacterial of material or skeletonization, on the surface of medical embedded material, the fields such as modification have a good application prospect.
A kind of method being rapidly introduced into functional ionic in titanium alloy surface of the present invention, its step are as follows:
(1) preparation of differential arc oxidation coating: the TC4 sample of 10~20mm of diameter, 1.5~3.0mm of thickness are punched, aperture
It for 1.5~3.0mm, then is successively polished with 400,1200,2000 mesh carborundum papers, removes the oxidation film of TC4 sample surfaces；So
Successively it is cleaned by ultrasonic respectively 10~20 minutes with ethyl alcohol, deionized water afterwards, pre-treatment is completed after drying；
(2) the TC4 sample after pre-treatment is immersed in the micro-arc oxidation electrolyte of electrolytic cell as electrolytic anode, is electrolysed
For slot as electrolysis cathode, micro-arc oxidation electrolyte is the deionized water solution of phosphate and calcium salt, phosphatic concentration is 4.5~
6.4g/L, the concentration of calcium salt are 8~40g/L, and electrolyte temperature is 10~25 DEG C；Apply square pulse on TC4 sample and carries out 2
Oxidation in~8 minutes, to form ceramic membrane in TC4 sample surfaces；The direct impulse voltage of square pulse is 250~400V,
Negative-going pulse voltage is 30~80V, and direct impulse voltage is identical with the frequency of negative-going pulse voltage, is 200~1000Hz, duty
Than being 12~35%；Successively it is cleaned by ultrasonic with ethyl alcohol, distilled water after finally the TC4 sample after differential arc oxidation is taken out and uses nitrogen
Drying, so that bioactivity calcium phosphate ceramic coating be prepared on the surface TC4；
(3) preparation of titanium alloy surface functional ionic doping coating: 2~10g functional ionic salt and 2~5g boric acid are added
Into 100mL water, pH to 7~10 is adjusted with alkaline solution；Then the solution is transferred in reaction kettle, step (2) is obtained
TC4 sample be immersed in the solution, then reaction kettle is heated into 2~10h at 130~200 DEG C；It is naturally cooled to reaction kettle
TC4 sample is taken out after room temperature, and TC4 sample is 20~40 minutes ultrasonic in deionized water, rinsed with deionized water, finally existed
It is dried in vacuo 1.5~3h under the conditions of 50~80 DEG C, is applied so that the calcium phosphate ceramic containing functional ionic be prepared on the surface TC4
Layer.
Phosphate described in above-mentioned steps is sodium β-glycerophosphate, diammonium hydrogen phosphate, phosphoric acid dihydro amine, one in ammonium phosphate
Kind is several；Calcium salt is one or more of calcium gluconate, calcium acetate, calcium nitrate, calcium chloride；Functional ionic salt is grape
One of saccharic acid copper, zinc gluconate, calcium gluconate, cerous nitrate, magnesium nitrate, strontium nitrate, calcium hydroxide, strontium hydroxide or
It is several；Alkaline solution is ammonium hydroxide or 1M sodium hydroxide solution.
As the preferred embodiment of the present invention, the temperature of electrolyte described in step (1) is 10~15 DEG C, oxidization time
It is 2~6 minutes.
First passage differential arc oxidation of the present invention and hydro-thermal reaction method prepare the phosphoric acid of functional ionic doping in titanium alloy surface
Calcium ceramic coating, has the advantage that
1. the introducing method of functional ionic is simple and quick, applied widely, it is suitably adapted for the introducing of different kinds of ions, ion is equal
It is even to be distributed in titanium alloy surface.
2. hydro-thermal process is conducive to improve the hydrophily of coating and adherency, the Proliferation, Differentiation of osteoblast.Pass through analogue body
Liquid immersion test verifies this coating with good bioactivity.
3. it is simple production process, high-efficient, at low cost, it is convenient for large-scale preparation.
Detailed description of the invention
Fig. 1: for the SEM picture of raw material titanium alloy TC 4 described in the embodiment of the present invention 1；
Fig. 2: there is the SEM picture of calcium phosphate ceramic coating for the growth of the surface TC4 described in the embodiment of the present invention 1；
Fig. 3: the SEM after having the TC4 hydrothermal treatment of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 1
Picture；
Fig. 4: for the XRD diagram piece of raw material titanium alloy TC 4 described in the embodiment of the present invention 1；
Fig. 5: there is the XRD diagram piece of calcium phosphate ceramic coating for the growth of the surface TC4 described in the embodiment of the present invention 1；
Fig. 6: the XRD after having the TC4 hydrothermal treatment of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 1
Picture；
Fig. 7: for the water contact angle picture of raw material titanium alloy TC 4 described in the embodiment of the present invention 1；
Fig. 8: there is the water contact angle picture of calcium phosphate ceramic coating for the growth of the surface TC4 described in the embodiment of the present invention 1；
Fig. 9: the water after having the TC4 hydrothermal treatment of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 1
Contact angle picture；
Figure 10: there is the TC4 hydrothermal treatment rear surface of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 1
The distribution map of zinc ion；
Figure 11: there is the TC4 hydrothermal treatment rear surface of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 1
EDS energy spectrum diagram；
Figure 12: there is the TC4 hydrothermal treatment rear surface of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 2
EDS energy spectrum diagram；
Figure 13: there is the TC4 hydrothermal treatment rear surface of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 3
EDS energy spectrum diagram；
Figure 14: there is the TC4 hydrothermal treatment rear surface of calcium phosphate ceramic coating for the growth of surface described in the embodiment of the present invention 4
EDS energy spectrum diagram.
As shown in Figure 1, 2, 3, raw material titanium alloy TC 4 surface relative smooth, and there are a large amount of fire through differential arc oxidation rear surface
Mountain shape micropore, and be made of inner compact layer layer and outer layer weaker zone；After being strengthened by further hydro-thermal process, obtain containing zinc
There is small gully shape pattern in the ceramic coating surface of ion, is conducive to the adherency of cell.
As shown in Figure 4,5, 6, comparison XRD diagram piece obviously finds that the diffraction maximum of zinc occurs, and shows there is zinc really in the coating
The presence of ion.
As shown in Fig. 7,8,9, the water contact angle of titanium alloy TC 4 is 64.3 degree, shows certain hydrophobicity；And through differential of the arc oxygen
Its water contact angle is 36.3 degree after change, and increased hydrophilicity for opposite titanium alloy, bioactivity improves；At hydro-thermal
Its contact angle is reduced to 11.6 degree after reason, and hydrophilicity is obviously improved, and is conducive to the adherency of osteoblast.
As shown in Figure 10,11, coating surface constituent content analysis directly demonstrates this method and can be realized in titanium alloy table
The zinc ion of face Load Balanced distribution, the mass percent of zinc ion are 1.53%.
As shown in figure 12, coating surface constituent content analysis directly demonstrate this method can be realized it is negative in titanium alloy surface
The zinc ion of load, the mass percent of zinc ion are 5.63%.
As shown in figure 13, coating surface constituent content analysis directly demonstrate this method can be realized it is negative in titanium alloy surface
Antibacterial copper ion is carried, the mass percent of copper ion is 3.42%.
As shown in figure 14, coating surface constituent content analysis directly demonstrate this method can be realized it is same in titanium alloy surface
When load magnesium and zinc ion, mass percent be respectively 1.87% and 0.26%.
Specific embodiment
Below by embodiment, the present invention will be further described, and embodiments of the present invention are not limited thereto, cannot
It is interpreted as limiting the scope of the invention.
Embodiment 1:
TC4 sample (diameter 12mm, thickness 2mm) is punched into (aperture 2mm), then successively with 400,1200,2000 mesh carbon
The polishing of SiClx sand paper, it is ensured that surface non-scale, it is smooth.Then successively it is cleaned by ultrasonic respectively 10 minutes with ethyl alcohol, deionized water,
Pre-treatment is completed after drying.The TC4 sample that pre-treatment is completed is immersed in micro-arc oxidation electrolyte as electrolytic anode, is electrolysed
For slot as electrolysis cathode, electrolyte is sodium β-glycerophosphate 6.12g, calcium acetate 35.2g and 1.0L deionized water.Control electrolyte
Temperature is 12 DEG C, and applying square pulse on TC4 sample makes electrolytic anode and electrolyte solution interact to form ceramic membrane, side
The direct impulse voltage 350V of shape pulse, the negative-going pulse voltage 50V of square pulse.Direct impulse voltage and negative-going pulse voltage
Frequency is 500Hz, duty ratio 20%, and oxidization time 3 minutes.Finally ethyl alcohol, distilled water is successively used to be cleaned by ultrasonic in TC4 sample
And with being dried with nitrogen, so that bioactivity calcium phosphate ceramic coating be prepared on the surface TC4.
2.85g zinc gluconate and 3.09g boric acid are added in 100mL water, adjusted with ammonium hydroxide (mass fraction 28%)
PH value of solution is to 8.The solution is transferred in reaction kettle, and the TC4 after differential arc oxidation is immersed in the solution, then reaction kettle is existed
5h is heated at 180 DEG C.TC4 is taken out after reaction kettle cooled to room temperature, and TC4 is 30 minutes ultrasonic in deionized water,
It is rinsed with deionized water, 2h is finally dried in vacuum drying oven under the conditions of 60 DEG C, to be prepared on the surface TC4 containing zinc ion
Calcium phosphate ceramic coating.
Embodiment 2:
TC4 sample (diameter 12mm, thickness 2mm) is punched into (aperture 2mm), then successively with 400,1200,2000 mesh carbon
The polishing of SiClx sand paper, it is ensured that surface non-scale, it is smooth.Then successively it is cleaned by ultrasonic respectively 10 minutes with ethyl alcohol, deionized water,
Pre-treatment is completed after drying.The TC4 sample that pre-treatment is completed is immersed in micro-arc oxidation electrolyte as electrolytic anode, is electrolysed
For slot as electrolysis cathode, electrolyte is sodium β-glycerophosphate 4.5g, calcium gluconate 40g and 1.0L deionized water.Control electrolysis
Liquid temperature is 12 DEG C, and applying square pulse on TC4 sample makes electrolytic anode and electrolyte solution interact to form ceramic membrane,
The direct impulse voltage 250V of square pulse, the negative-going pulse voltage 30V of square pulse；Direct impulse voltage and negative-going pulse electricity
The frequency of pressure is 800Hz, duty ratio 25%, and oxidization time 5 minutes.The TC4 after oxidation is successively finally used into ethyl alcohol, distilled water
It is cleaned by ultrasonic and uses and be dried with nitrogen, so that bioactivity calcium phosphate ceramic coating is prepared on the surface TC4.
2g zinc acetate and 2g boric acid are added in 100mL water, adjust pH value of solution to 10 with 1M sodium hydroxide solution.It will system
Standby solution is transferred in reaction kettle, and the TC4 after differential arc oxidation is immersed in the solution, then reaction kettle is added at 200 DEG C
Hot 2h.TC4 is taken out after reaction kettle cooled to room temperature, and TC4 is 30 minutes ultrasonic in deionized water, use deionized water
It rinses, finally dries 2h in vacuum drying oven under the conditions of 60 DEG C, so that the pottery of the calcium phosphate containing zinc ion be prepared on the surface TC4
Porcelain coating.
Embodiment 3:
10g copper gluconate and 5g boric acid are added in 100mL water, adjust pH value of solution with ammonium hydroxide (mass fraction 28%)
To 7.The solution of preparation is transferred in reaction kettle, and the TC4 after differential arc oxidation in embodiment 1 is immersed in solution, then will be anti-
It answers kettle to heat 10h at 130 DEG C, TC4 is taken out after reaction system cooled to room temperature, and TC4 is surpassed in deionized water
It sound 20 minutes, is rinsed with deionized water, finally the dry 3h in 50 DEG C of vacuum drying ovens, so that cupric be prepared on the surface TC4
The calcium phosphate ceramic coating of ion.
Embodiment 4:
By 2.84g zinc gluconate, 3.21g magnesium nitrate and 3.09g boric acid are added in 100mL water, with ammonium hydroxide (quality point
Number 28%) pH value of solution is adjusted to 8.The solution of preparation is transferred in reaction kettle, and by the TC4 after differential arc oxidation in embodiment 1
It immerses in the solution, then reaction kettle is heated into 8h at 180 DEG C, TC4 is taken out after reaction kettle cooled to room temperature, and will
TC4 is 40 minutes ultrasonic in deionized water, is rinsed with deionized water, the dry 1.5h in 80 DEG C of vacuum drying ovens, thus in TC4 table
Face is prepared while the calcium phosphate ceramic coating containing zinc and magnesium ion.
Claims (6)
1. a kind of method for being rapidly introduced into functional ionic in titanium alloy surface, its step are as follows:
(1) preparation of differential arc oxidation coating: the TC4 sample of 10~20mm of diameter, 1.5~3.0mm of thickness are punched, aperture is
1.5~3.0mm, then successively polished with 400,1200,2000 mesh carborundum papers, remove the oxidation film of TC4 sample surfaces；Then
Successively it is cleaned by ultrasonic respectively 10~20 minutes with ethyl alcohol, deionized water, pre-treatment is completed after drying；
(2) the TC4 sample after pre-treatment is immersed in the micro-arc oxidation electrolyte of electrolytic cell as electrolytic anode, electrolytic cell is made
For electrolysis cathode, micro-arc oxidation electrolyte is the deionized water solution of phosphate and calcium salt, phosphatic concentration is 4.5~
6.4g/L, the concentration of calcium salt are 8~40g/L, and electrolyte temperature is 10~25 DEG C；Apply square pulse on TC4 sample and carries out 2
Oxidation in~8 minutes, to form ceramic membrane in TC4 sample surfaces；The direct impulse voltage of square pulse is 250~400 V,
Negative-going pulse voltage is 30~80 V, and direct impulse voltage is identical with the frequency of negative-going pulse voltage, is 200~1000 Hz, accounts for
Sky is than being 12~35%；Successively it is cleaned by ultrasonic with ethyl alcohol, distilled water after finally the TC4 sample after differential arc oxidation is taken out and uses nitrogen
Air-blowing is dry, so that bioactivity calcium phosphate ceramic coating be prepared on the surface TC4；
(3) preparation of titanium alloy surface functional ionic doping coating: 2~10g functional ionic salt and 2~5g boric acid are added to
In 100mL water, pH to 7~10 is adjusted with alkaline solution；Then the solution is transferred in reaction kettle, step (2) is obtained
TC4 sample is immersed in the solution, then reaction kettle is heated 2~10h at 130~200 DEG C；Room is naturally cooled to reaction kettle
TC4 sample is taken out after temperature, and TC4 sample is 20~40 minutes ultrasonic in deionized water, rinsed with deionized water, finally 50
1.5~3h is dried in vacuo under the conditions of~80 DEG C, so that the calcium phosphate ceramic coating containing functional ionic be prepared on the surface TC4.
2. a kind of method for being rapidly introduced into functional ionic in titanium alloy surface as described in claim 1, it is characterised in that: phosphoric acid
Salt is one or more of sodium β-glycerophosphate, diammonium hydrogen phosphate, phosphoric acid dihydro amine, ammonium phosphate.
3. a kind of method for being rapidly introduced into functional ionic in titanium alloy surface as described in claim 1, it is characterised in that: calcium salt
For one or more of calcium gluconate, calcium acetate, calcium nitrate, calcium chloride.
4. a kind of method for being rapidly introduced into functional ionic in titanium alloy surface as described in claim 1, it is characterised in that: function
Ion salt is copper gluconate, zinc gluconate, calcium gluconate, cerous nitrate, magnesium nitrate, strontium nitrate, calcium hydroxide, hydroxide
One or more of strontium.
5. a kind of method for being rapidly introduced into functional ionic in titanium alloy surface as described in claim 1, it is characterised in that: alkalinity
Solution is ammonium hydroxide or 1 M sodium hydroxide solution.
6. a kind of method for being rapidly introduced into functional ionic in titanium alloy surface as described in claim 1, it is characterised in that: step
(1) temperature of electrolyte described in is 10~15 DEG C, and oxidization time is 2~6 minutes.
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