CN105624753B - A kind of medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique - Google Patents
A kind of medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique Download PDFInfo
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C25D9/00—Electrolytic coating other than with metals
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Abstract
The present invention relates to the surface modification treatment fields of medical material, specifically disclose a kind of medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique.The porous titanium or titanium alloy deposition hydroxyapatite coating layer technical process of the present invention includes pretreatment to porous metal substrate, the preparation of electroplate liquid and electrodeposition process.The preprocessing process of the present invention can carry out effective mechanical grinding and cleaning treatment to porous metals surfaces externally and internally；Electrodeposition process carries out porous metals using rotation electrode electrolysis unit the electrodeposition process of hydroxyapatite, porous metals inner and outer surfaces thickness of diffusion layer can be effectively reduced, can effectively avoid the nonsynchronous problem of porous structure surfaces externally and internally electrodeposition technology in the case where diffusion mixes control condition；The uniform hydroxyapatite deposition layer of porous metals inner and outer surfaces is obtained by adjusting rotating speed.
Description
Technical field
The present invention relates to the surface modification treatment fields of medical material, and in particular to a kind of medical porous titanium or titanium alloy is equal
Even deposition hydroxyapatite coating layer technique.
Background technology
Porous metals are applied to the trend that the treatment Orthopedic Clinicals such as osteonecrosis and bone defect have been current.Clinical test
The result shows that materials microstructure compatibility can be significantly improved only surface is the implantation material of porous form, this main table
It is now porous material and bone tissue, the binding ability of fibr tissue and bond strength is all greatly improved.From biomethanics
Angle sees that the advantage of POROUS TITANIUM or titanium alloy bone implant is fairly obvious：Different holes can be produced by adjusting the thickness of holder
Gap rate, aperture and its porous titanium alloy of distribution comply with the support requirement of carrying bone.And from Biocompatibility angle
Degree, although Titanium and its alloy are the most commonly used metals of clinical application in orthopedic implanting material, with autologous bone and biology
Active artificial bone can not generate synostosis compared to biologically inert is still with bone tissue.Skeletonization after being implanted into due to material
Activity is mainly determined that the titanium or titanium alloy implantation material clinically used also needs further to be surface-treated by its surface nature.
Hydroxyapatite [Ca10(PO4)6(OH)2] (Hydroxyapatite, HA) have and main mine in human body hard tissue
The similar chemical composition of substance apatite and crystal structure, biocompatibility are excellent.Currently, titanium-based HA coating composite materials are general
It is clinical all over being applied to.There are many technology that HA coatings are prepared in fine and close surface of metal titanium, mainly have plasma spraying, laser melting coating,
The methods of ion beam assisted depositing, sol-gel, bionical deposition, electro-deposition.But conventional bunch surface treatment is because of inherently straight
Penetrating property limits, and can not handle porous metals interior surface.The special microcellular structure of porous metals determines that carrying out surface to it changes
The difficulty of property is the processing of the hole being distributed in inside porous alloy and micropore inwall.Therefore POROUS TITANIUM and its alloy are carried out
Surface be modified mainly with chemistry and electrochemical method, both methods be to carry out in the solution, solution can relatively easily into
Enter inside porous metals.
But existing porous metals electrochemical deposition process is the flat metal for amplifying porous metals as surface area,
The design feature for not being directed to porous metals is optimized and is adjusted to original compact metal electrodeposition technology.Practical electrochemistry is heavy
Because of activation polarization, concentration polarization and ohmic polarization lead to be distributed in the Different electrodes thickness inside porous structure during product
Effective overpotential at place is obviously relatively low compared with outmost surface, so as to cause heavy at a distance of the electricity of auxiliary electrode different location in porous structure
Lamination growth course and final surface quality are uneven, this is the electrochemical metal reaction process of any porous structure all without regulation
It keeps away, if if not intervening this non-homogeneous chemistry, electrochemical reaction mechanism work, the table with certain thickness porous metals
Face modification will cause uneven.
Invention content
In view of this, it is necessary to be directed to above-mentioned problem, a kind of medical porous titanium or titanium alloy uniform deposition hydroxyl is provided
Apatite coating technique.
To achieve the above object, the present invention takes technical solution below：
The medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique of the present invention, including：
Step 1：Pretreatment to porous metal substrate
(1) it mechanically polishes：The machine of surfaces externally and internally is carried out to porous metals exemplar using the automatic mode of blast sand with tumbling barrel
Tool is polished, and the irregular flash in porous metals surfaces externally and internally forming process is removed；
(2) oil removing：Then by the porous metals exemplar through mechanical grinding, it is positioned under the conditions of thermokalite degreasing fluid had children outside the state plan
After oil removal treatment, takes out exemplar and rinsed well with deionized water；
(3) acid attack：Pickling processes are finally carried out under ultrasonic wave using pickle liquor, are cleaned and are done with deionized water after processing
Only；Naturally dry, it is spare；
Step 2：The preparation of electroplate liquid
Prepare 2-3 times of solution lower than bath concentration of the routine containing calcium salt, phosphate and supporting electrolyte；
Step 3：Electrodeposition process
, as cathode, using platinum plating titanium plate as anode, will match in step 2 through the pretreated porous metals exemplar of step 1
Electroplate liquid be heated to 60~80 DEG C, in the way of rotation electrode electrolysis unit, in constant current or constant potential under to metal exemplar
Surfaces externally and internally carries out electro-deposition；Exemplar after electro-deposition is taken out, is rinsed well with deionized water, in vacuum drying chamber
It is dry, you can to obtain being formed the porous metals exemplar of uniform hydroxyapatite coating layer in surfaces externally and internally；
The porous metals are POROUS TITANIUM or titanium alloy.
Further, in mechanical polishing process described in step 1：Compressed air pressure is 4-10MPa when sand-blasting machine works；It beats
The Brown Alundum or white fused alumina that selection granularity is 100~No. 280 when mill are sand-blasting abrasive, carry out blasting treatment 1-5min.
Further, described in step 1 when thermokalite oil removal treatment porous metals exemplar, thermokalite temperature is 70-90 DEG C, when processing
Between be 2~10min.
The thermokalite degreasing fluid is by 20~40gL-1NaH2PO2·H2O, 10~20gL-1Anhydrous Na2CO3, 3~
5g·L-1NaOH is dissolved in deionized water and forms.
Further, pickle liquor described in step 1 is with HF and HNO3The mixed liquor being formulated, the mixed liquor include 5
~15mLL-1HF and 10~30mLL-1HNO3。
Further, the pH value of electroplate liquid described in step 2 at room temperature is 4.5~6.0；The pH value of the electroplate liquid uses
0.1~10mLL-1HCl solution, 0.1~10mLL-1HNO3Solution or 0.1~10mLL-1Ammonium hydroxide is adjusted.
Further, the Ca in calcium salt described in step 22+From CaCl2、CaCl2、Ca(NO3)2、Ca(NO3)2·4H2O
At least one of；H in the microcosmic salt2PO4 -、HPO4 2-From NH4H2PO4、NaH2PO4、KH2PO4、(NH4)2HPO4、
Na2HPO4、K2HPO4At least one of；The supporting electrolyte is sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sulfuric acid
At least one of sodium, potassium sulfate.
Further, in the electrodeposition process in the step 3, the electrode rotating speed of rotation electrode electrolysis unit is 10~
1000rpm, current density are 1.0~50.0mAcm-2, sedimentation potential is 1.0~10.0V, and electrodeposition time is 0.5~4h；
Drying temperature is 80~100 DEG C in vacuum drying chamber, and drying time is 1~4h.
A kind of rotation electrode electrolysis unit, including constant temperature water bath, electrolytic cell, as the platinum plating titanium plate of anode, as the moon
The porous metals of pole, electric rotating pole bar；The electrolytic cell is placed in constant temperature water bath；The platinum plating titanium plate is placed in electrolytic cell；
Electric rotating pole bar one end is connected with the porous metals being placed in electrolytic cell, the other end and DC power supply or potentiostat phase
Even；The electric rotating pole bar one end that is connected with porous metals exemplar is designed for external screw thread, and electric rotating pole bar rotating speed is controlled by motor speed
Device controls.
Further, the platinum plating titanium plate is rectangular or annular；The rectangular platinum plating titanium plate quantity is a pair of or more.
Beneficial effects of the present invention are：
(1) dilute concentration electroplate liquid is used：The present invention is less than using the conventional electroplate liquid such as calcium salt, microcosmic salt of dilute concentration, concentration
2-3 times of conventional electroplate liquid ensures that porous metals electrodeposit reaction is to be spread or spread electrochemistry to mix control process.
(2) pretreatment of porous metals exemplar of the invention uses the roller sand blasting unit under automatic mode, using surpassing
Thin Brown Alundum or white fused alumina abrasive material operate under high pressure draught effect, and effective machinery can be carried out to porous metals surfaces externally and internally and is beaten
Mill processing；Chemical disposing oil under Ultrasonic Conditions and pickling can effectively further carry out porous metals surfaces externally and internally
Pretreatment.
(3) present invention carries out porous metals using rotation electrode electrolysis unit the electrodeposition process of hydroxyapatite, has
Electrochemical reaction mass transfer ability is not improved by solution flowing in traditional air stirring, magnetic agitation etc., rotary electrode method relies on
Working electrode high speed rotation makes the solution near porous metal electrode flow " laminar flow " condition of satisfaction, can effectively reduce porous gold
Belong to inner and outer surfaces thickness of diffusion layer, can effectively avoid porous structure surfaces externally and internally electro-deposition work in the case where diffusion mixes control condition
The nonsynchronous problem of skill；The uniform hydroxyapatite deposition layer of porous metals inner and outer surfaces is obtained by adjusting rotating speed.
Description of the drawings
Fig. 1 is the structural schematic diagram of rotation electrode electrolysis unit of the present invention.
Fig. 2 is the vertical view of Fig. 1.
Fig. 3 is the vertical view for increasing a pair of of platinized titanium plate electrode in Fig. 1.
Fig. 4 is the vertical view of the rectangular platinum plating titanium plate in annular platinum plating titanium plate alternate figures 1.
Fig. 5 is that the Potential Distributing under rotation electrode electrolysis unit of the present invention and conventional magnetic stirring compares schematic diagram.
Reference numeral：Constant temperature water bath 1；Electrolytic cell 2；Platinum plating titanium plate 3；Porous metals 4；Electric rotating pole bar 5.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution work further clearly and completely describes.It should be noted that described embodiment is only the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Go out the every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.
Embodiment
The medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique of the present invention, including：
Step 1：Pretreatment to porous metal substrate
(1) it mechanically polishes：Interior appearance is carried out to POROUS TITANIUM or titanium alloy exemplar using the automatic mode of blast sand with tumbling barrel
The mechanical grinding in face, specific operation process are：Under the conditions of sand-blasting machine compressed air pressure is 4-10MPa, it is 100 to select granularity
~No. 280 Brown Alundums or white fused aluminas are sand-blasting abrasive, carry out blasting treatment 1-5min, removal porous structure surfaces externally and internally molding
Irregular flash in the process；
(2) oil removing：Then by POROUS TITANIUM or titanium alloy exemplar through mechanical grinding, it is positioned over 70-90 DEG C of thermokalite degreasing fluid
In had children outside the state plan under the conditions of processing 2~10min after, take out exemplar simultaneously rinsed well with deionized water.The thermokalite degreasing fluid is
By 20~40gL-1NaH2PO2·H2O, 10~20gL-1Anhydrous Na2CO3, 3~5gL-1NaOH is dissolved in deionized water
In form.
(3) acid attack：Pickling processes are finally carried out under ultrasound condition using pickle liquor, are cleaned with deionized water after processing
Totally；Naturally dry, it is spare；The pickle liquor is with HF and HNO3The mixed liquor being formulated, the mixed liquor include 5~
15mL·L-1HF and 10~30mLL-1HNO3.Preferably, the HF mass percentage concentrations for preparing mixed liquor are 48%,
HNO3Mass percentage concentration is 68%.
Step 2：The preparation of electroplate liquid
Prepare 2-3 times of solution lower than bath concentration of the routine containing calcium salt, phosphate and supporting electrolyte；Liquid chamber is electroplated
PH value under temperature is 4.5~6.0；The pH value of electroplate liquid uses 0.1~10mLL-1HCl solution, 0.1~10mLL-1HNO3It is molten
Liquid or 0.1~10mLL-1Ammonium hydroxide is adjusted.
Step 3：Electrodeposition process
Using through the pretreated POROUS TITANIUM of step 1 or titanium alloy exemplar as cathode, will be by step 2 using platinum plating titanium plate as anode
The diluted plating liquor of gained is heated to 60~80 DEG C, using rotation electrode electrolysis unit, using constant current or constant potential
Mode carries out electro-deposition to POROUS TITANIUM or titanium alloy exemplar surfaces externally and internally；In electrodeposition process, electrolysis unit electrode rotating speed is 10
~1000rpm, current density are 1.0~50.0mAcm-2, sedimentation potential is 1.0~10.0V, and sedimentation time is 0.5~4h；
Exemplar after electro-deposition is taken out, is rinsed well with deionized water, dry 1~4h in 80~100 DEG C of vacuum drying chambers,
Hydroxyapatite coating layer is formed in POROUS TITANIUM or titanium alloy exemplar surfaces externally and internally.
Preferably, Ca in calcium salt described in step 22+From CaCl2、CaCl2、Ca(NO3)2、Ca(NO3)2·4H2O
At least one of；H in the microcosmic salt2PO4 -、HPO4 2-From NH4H2PO4、NaH2PO4、KH2PO4、(NH4)2HPO4、
Na2HPO4、K2HPO4At least one of；The supporting electrolyte is sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sulfuric acid
At least one of sodium, potassium sulfate.
Preferably, the porous pure titanium in the present invention is TA1, TA2, TA3, TA4；Porous titanium alloy is Ti-6Al-4V.
Electroplate liquid of the heretofore described routine containing calcium salt, phosphate and supporting electrolyte refer to：Containing Ca2+A concentration of 10.1
~50.0mmolL-1, H2PO4-A concentration of 5.1~30.0mmolL-1, Ca/P molar ratio are 1.6~1.8, supporting electrolyte
A concentration of 0.5~2.0molL-1Electroplate liquid；Such as routine electroplate liquid A is formulated as：Ca(NO3)2(NH4)2HPO4Concentration point
Not Wei 14.01mmol/L and 8.33mmol/L, Ca/P molar ratios 1.67, supporting electrolyte sodium nitrate 1.2mol/L, pH value 5.5；
Conventional electroplate liquid B is formulated as：CaCl2And NH4H2P04Concentration is respectively 21.01mmol/L and 12.50mmol/L, Ca/P molar ratios
1.67, supporting electrolyte sodium chloride 0.8mol/L, pH value 5.0.Liquor is electroplated then than conventional electricity in dilution used in the present invention
Low 2-3 times of the solution of plating solution A or B concentration is as electroplate liquid, to ensure that POROUS TITANIUM or titanium alloy electrodeposit reaction are diffusion or expand
It dissipates electrochemistry and mixes control process.
As shown in Figure 1, be rotation electrode electrolysis unit of the present invention, including constant temperature water bath 1, electrolytic cell 2, as anode
Platinum plating titanium plate 3, the POROUS TITANIUM as cathode or titanium alloy 4, electric rotating pole bar 5；The electrolytic cell 2 is placed in constant temperature water bath 1；
The platinum plating titanium plate 3 is placed in electrolytic cell 2；Described 5 one end of electric rotating pole bar and the POROUS TITANIUM being placed in electrolytic cell 2 or titanium alloy
4 are connected, and the other end is connected with DC power supply or potentiostat；Electric rotating pole bar 5 is connected one with POROUS TITANIUM or titanium alloy exemplar 4
End is designed for external screw thread, and 5 rotating speed of electric rotating pole bar is controlled by motor speed controller.
As in Figure 2-4, it is the vertical view of rotation electrode electrolysis unit of the present invention, preferably, the rotation electrode
Electrolysis unit can select different anode platinum plating titanium plate number and shape according to POROUS TITANIUM or the size of titanium alloy exemplar size；
It is rectangular to electrode platinum plating titanium plate or annular platinum plating titanium plate that exemplar becomes large-sized optional four block length.
As shown in figure 5, being 10mm thickness POROUS TITANIUM exemplar of the present invention, under conventional magnetic stirring and rotation electrode of the present invention is electric
When solving device high speed rotation, Potential Distributing situation of the electrode interior under identical Electrodeposition Conditions：
(a) is using 10 in Fig. 5-3A·cm2The potential profile of magnetic agitation under constant current (b) uses electrode of the present invention
Relative solution does the potential profile of 500rpm rotary speed movements.
As seen from the figure, in conventional magnetic stirring, constant current 10-3A·cm2Under the conditions of, 10mm thickness POROUS TITANIUM sample surfaces and
Bottom potential difference is up to 500mV, and potential difference only has less than 100mV when doing high-speed motion using electrode relative solution of the present invention.
Increase with POROUS TITANIUM exemplar size, the difference of effective overpotential at different-thickness can also increase therewith.According to above-mentioned experiment knot
Fruit can obtain, do effective high-speed motion by electrode relative solution to reduce Potential Distributing unevenness, to improving in POROUS TITANIUM
The uniformity of outer surface electro-deposition is feasible.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique, which is characterized in that including：
Step 1：Pretreatment to porous metal substrate
（1）Mechanical polishing：The machinery for being carried out surfaces externally and internally to porous metals exemplar using the automatic mode of blast sand with tumbling barrel is beaten
Mill removes the irregular flash in porous metals surfaces externally and internally forming process；
（2）Oil removing：Then by the porous metals exemplar through mechanical grinding, it is positioned over thermokalite degreasing fluid and is surpassed
Under the conditions of sound after oil removal treatment, takes out exemplar and rinsed well with deionized water；
（3）Acid etch：Pickling processes are finally carried out under ultrasonic wave using pickle liquor, are spent after processing
Ionized water cleans up；Naturally dry, it is spare；
Step 2：The preparation of electroplate liquid
Prepare 2-3 times of solution lower than bath concentration of the routine containing calcium salt, phosphate and supporting electrolyte；
Step 3：Electrodeposition process
Using through the pretreated porous metals exemplar of step 1 as cathode, using platinum plating titanium plate as anode, electricity that will match in step 2
Plating solution is heated to 60 ~ 80oC, in the way of rotation electrode electrolysis unit, in constant current or constant potential under to table inside and outside metal exemplar
Face carries out electro-deposition；Exemplar after electro-deposition is taken out, is rinsed well with deionized water, it is dry in vacuum drying chamber,
It can be obtained the porous metals exemplar that uniform hydroxyapatite coating layer is formed in surfaces externally and internally；
The porous metals are POROUS TITANIUM or titanium alloy；
In electrodeposition process in the step 3, the electrode rotating speed of rotation electrode electrolysis unit is 10 ~ 1000rpm, current density
For 1.0 ~ 50.0mAcm-2, sedimentation potential is 1.0 ~ 10.0V, and electrodeposition time is 0.5 ~ 4h；Drying temperature in vacuum drying chamber
For 80 ~ 100oC, drying time is 1 ~ 4h.
2. medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique according to claim 1, feature
It is, in mechanical polishing process described in step 1：Compressed air pressure is 4-10MPa when sand-blasting machine works；Granularity is selected when polishing
It is sand-blasting abrasive for 100 ~ No. 280 Brown Alundums or white fused alumina, carries out blasting treatment 1-5min.
3. medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique according to claim 1, feature
It is, described in step 1 when thermokalite oil removal treatment porous metals exemplar, thermokalite temperature is 70-90oC, and processing time is 2 ~ 10min.
4. medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique according to claim 3, feature
It is, the thermokalite degreasing fluid is by 20 ~ 40gL-1NaH2PO2·H2O、10~20g·L-1Anhydrous Na2CO3、3~5g·L- 1NaOH is dissolved in deionized water and forms.
5. medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique according to claim 1, feature
It is, pickle liquor described in step 1 is with HF and HNO3The mixed liquor being formulated, the mixed liquor include 5 ~ 15mLL-1 HF
With 10 ~ 30mLL-1 HNO3。
6. medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique according to claim 1, feature
It is, the pH value of electroplate liquid described in step 2 at room temperature is 4.5 ~ 6.0；The pH value of the electroplate liquid uses 0.1 ~ 10mLL-1HCl
Solution, 0.1 ~ 10mLL-1 HNO3Solution or 0.1 ~ 10mLL-1Ammonium hydroxide is adjusted.
7. medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique according to claim 1, feature
It is, the Ca in calcium salt described in step 22+From CaCl2、CaCl2、Ca(NO3)2、Ca(NO3)2·4H2At least one of O；
H in the phosphate2PO4 -、HPO4 2-From NH4H2PO4、NaH2PO4、KH2PO4、(NH4)2HPO4、Na2HPO4、K2HPO4
At least one of；The supporting electrolyte is in sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium sulphate, potassium sulfate
It is at least one.
8. the medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer work according to claim 1-7 any one
Skill, which is characterized in that the rotation electrode electrolysis unit includes constant temperature water bath, and electrolytic cell is made as the platinum plating titanium plate of anode
For the porous metals of cathode, electric rotating pole bar；The electrolytic cell is placed in constant temperature water bath；The platinum plating titanium plate is placed in electrolytic cell
In；Electric rotating pole bar one end is connected with the porous metals being placed in electrolytic cell, the other end and DC power supply or constant potential
Instrument is connected；The electric rotating pole bar one end that is connected with porous metals exemplar is designed for external screw thread, and electric rotating pole bar rotating speed is by motor speed
Controller controls.
9. medical porous titanium or titanium alloy uniform deposition hydroxyapatite coating layer technique according to claim 1, feature
It is, the platinum plating titanium plate is rectangular or annular；The rectangular platinum plating titanium plate quantity is a pair of or more.
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