CN100572612C - Nanometer hydroxyapatite/carbon nanotube preparation method of composite coating - Google Patents
Nanometer hydroxyapatite/carbon nanotube preparation method of composite coating Download PDFInfo
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- CN100572612C CN100572612C CNB2005101183570A CN200510118357A CN100572612C CN 100572612 C CN100572612 C CN 100572612C CN B2005101183570 A CNB2005101183570 A CN B2005101183570A CN 200510118357 A CN200510118357 A CN 200510118357A CN 100572612 C CN100572612 C CN 100572612C
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Abstract
Nanometer hydroxyapatite/carbon nanotube preparation method of composite coating, relate to a kind of nanometer hydroxyapatite/carbon nanotube compound coating, especially relate to a kind of method that adopts electrophoretic deposition to prepare novel carbon nanotube/nano carboxy apatite composite coating, a kind of method that adopts electrophoretic deposition to prepare nanometer hydroxyapatite/carbon nanotube compound coating is provided.Substrate pretreatment, preparation of nano level HA and CNTs electrophoretic deposition suspension leave standstill electrophoretic deposition suspension, and is ultrasonic, centrifugal, pours out the upper strata suspension liquid; Electrophoretic deposition is handled, and sintering under argon gas atmosphere promptly gets target product.Adopt nano level HA and CNTs, can reduce sintering temperature significantly, can obtain the compound coating of the good and compact structure of bonding force, can avoid causing the destruction of HA coating, keep its good biological property because of high temperature sintering.Increase substantially the bonding force between biological composite coating and the medical metal material, be expected to use as human body heavy burden position implant.
Description
Technical field
The present invention relates to a kind of nanometer hydroxyapatite/carbon nanotube compound coating, especially relate to a kind of method that adopts electrophoretic deposition to prepare novel carbon nanotube/nano carboxy apatite composite coating, prepared thus compound coating has the good mechanical performance, is expected to become a kind of biomedical material of novelty.
Background technology
Since the seventies in 20th century, (Hydroxyapatite is called for short HA to hydroxyapatite, and chemical formula is Ca
10(PO
4)
6(OH)
2) preparation of bio-ceramic coating causes research workers' such as vast chemistry, materialogy, biology, clinical medicine very big interest.HA has excellent biological compatibility and biological activity, is the main inorganic moiety of human body hard tissue (bone and tooth), can form with tissue at short notice behind the implant into body and combine closely.But the fragility of Ha is big, intensity is low, folding strength and fracture toughness property index all are lower than artificial dense bone, thereby has limited its application at human body heavy burden position.In order to improve its mechanical property, developed multiple medical metal/biological ceramic composite material.Titanium makes titanium/HA coating both have the mechanical property of titanium because of its good physical properties is widely used, and has biological property (Magnus Gottlander, Carina B.Johansson .J.Biomaterials 18 (1997) 551-557I of HA again; ZHITOMIRSKY, L.GAL-OR.J.MATERIALS SCIENCE 8 (1997) 213-219).Reported the method for a lot of HA of preparation coatings at present, as plasma spraying method, electrodip process, sol-gel method, detonation flame spraying method and biomimetic method etc.But above-mentioned the whole bag of tricks all has drawback and deficiency, and particularly the high temperature technology of preparing can cause the decomposition of HA coating and the destruction of crystalline phase, also may cause crackle, causes degradation problem under the bonding force.The preparation condition gentleness of electrophoretic deposition technique is not subjected to restriction (O.S.Yildirim, B.Aksakal, the H.Celik..J.Medical Engineering﹠amp of body material shape; Physics27 (2005) 221-228), the pattern of coating, controllable thickness (the controllable thickness scope is from 1 μ m to 500 μ m), make the coating densification by aftertreatment-low-temperature sintering method again, further improve the bonding force of coating and matrix, therefore it has become one of research focus (M.We J.Maretials Science:Materials in medicine16 (2005) 319-324:R.wang, Y.X.K.J.BiomedicalMaterials Research 1 (2003) 270-275 in this field in recent years; Cong Wang, J.Ma, Wen Cheng, Ruifang Zhang.J.Materials Letters57 (2002) 99-105).Titanium or titanium alloy has been widely used in preparing the matrix of composite biological material, but because the thermal expansivity (14.0 * 10 of matrix titanium
-6/ k) and the thermal expansivity (8.4 * 10 of HA
-6/ K) difference is bigger, can produce bigger stretching unrelieved stress in the process of sintering cooling, causes the bonding force of the two to descend.In order to solve this important techniques problem, people are devoted to develop various compound coatings and gradient cladding (J.Ma
A*, C.Wang
*, K W.Peng
b.J.Biomaterials, 24 (2003) 3505-3510:Hae-Won Kim, Young-Hag Koh .J.Biomaterials 25 (2004) 2533-2538; Kim HW Noh YJ .J.Am Ceram Soc, in press. Chen Xiao is bright, and Jiao Yuheng is permitted to pass ripple .J., Materials science and engineering, 2002,20 (4); Jiao Yuheng, Chen Xiaoming, Xu Chuanbo, He Jianhua .J. functional materials, 20041 (35); M.Wei, A.J.Ruys, M V.Swain, S.H.Kim.J.Maretials Science:Materials in medicine, 10 (1999) 401-409; Yun-Mo Sung
*And Yeong-Keun.Shin.J.Crystal Growth﹠amp; Design5 (2005) 29).Carbon nanotube (Carbon nanotube, be called for short CNTs) be the special type material of finding in 1991 of a kind of structure, have excellent mechanical property and electric property, especially has high intensity and toughness, and HA itself has excellent biological compatibility and biological activity, though the existing at present report (Gong Huajun that adopts blending method to prepare HA/CNTs block matrix material, Yang Xiaoping, Chen Guoqiang ..J. polymer journal, 2 (2005), and utilize Laser Surface Treatment to apply the HA/CNTs compound coating in the metallic surface, but because pyroprocess causes HA to be decomposed into CaO and TCP in a large number, influence the biological activity (Yao Chen, Cuihua Gan.J.Applied Physics Letters86 (2005)) of material.So far the relevant report that does not still have the preparation HA/CNTs compound coating of mild conditions.Metal titanium has with the human body bone and has close Young's modulus, consider if can develop electrophoretic deposition under the mild conditions, make the compound coating of HA/CNTs at the titanium substrate surface, advantage in conjunction with Ti/HA/CNTs three, must obtain to have the complex biological material of good mechanical property and biological property, and be expected to satisfy the requirement of using at human body heavy burden position as high-performance implant as a kind of novelty.
The specific surface area of CNTs is huge, has bigger length-to-diameter ratio, and specific surface energy is high, and CNTs is easy to reunite in solution.Discover that adding tensio-active agent or prolongation ultrasonic time can make CNTs good dispersion (M.S.P.Shaffer, X.Fan andA.H.Windle
*.J.Carbon36 (1998) 1603-1612; Jiang Linqin, high Lian .J. Journal of Inorganic Materials 18 (2003); Hu Jie opens the .J. of word army electron microscopic journal 22 (2003); Zheng becomes Pei, Yang Sheng woods .J. functional polymer journal 17 (2004); Brian J.Landi, Herbert J.Ruf, J.Phys.Chem.B (108) 200417089-17095).The dispersion liquid of CNTs can be with negative electricity or positive electricity (LipingZhao, LIan Gao under ultrasound condition when adding negatively charged ion or cats product
*.J.Carbon42 (2004) 423-460), pass through electrophoretic deposition, it can be deposited to negative electrode or anode surface, evenly distributed to obtain CNTs, has the stable electricity and the coating of mechanical property (Jun Cheol Bae, Young JoonYoon, Se-Jong Lee.J.Physica B 323 (2002) 168-170; Chunsheng Du, D.Heldebrant, NingPan
*.J.Materials Science Letters21 (2002) 565-568; Bo Gao, Guozhen Z.Yue, Qi Qiu, Yuan ChengJ.Advanced materials 13 (2001)).The pure HA of electrophoretic deposition then is subjected to solution, current potential, the influence of coagulation time (MWei, A.J.Ruys, B.K.Milthorpe, C.C.Soeeell..J.Bimedical Materials Research 45 (1999) 11-19; M.C.Kuo, S.K.Yen Materials Science and Engineering C 20 (2002) 153-160).
Summary of the invention
The objective of the invention is to provides a kind of method that adopts electrophoretic deposition to prepare nanometer hydroxyapatite/carbon nanotube compound coating at the problem that differs the bonding force weakening that causes greatly between HA coating and the bio-medical metal titanium owing to thermal expansivity.
Concrete steps of the present invention are:
1) substrate pretreatment;
2) preparation comprises the electrophoretic deposition suspension of HA and CNTs, and the total concn of electrophoretic deposition suspension is 0.001～0.015g/ml, calculates by mass percentage, and the content of CNTs accounts for 10%～50% of total electrophoretic deposition suspension, is preferably 20%～30%, uses HNO
3Regulate its pH value 4～5, said HA and CNTs are nano level;
3) the electrophoresis system is a non-aqueous system, and dispersion agent is a straight alcohol;
4) it is ultrasonic, centrifugal electrophoretic deposition suspension to be left standstill stable back, pours out the upper strata suspension liquid, preferably standby after the supersound process;
5) electrophoretic deposition is handled, and voltage is 10～50V, and the electrophoretic deposition time is 10～90s, preferably constant voltage;
6) at 600～900 ℃, sintering under best 700 ℃ of argon gas atmosphere promptly gets target product.
Said substrate is selected from metals such as titanium, titanium alloy, stainless steel, and its size is generally unrestricted, can select according to actual needs.Said substrate pretreatment can adopt behind the mechanical sanding and polishing in surface, use at least a ultrasonic cleaning in water, acetone, ethanol etc. successively, at 120～160 ℃, best 140 ℃ in the alkaline solution of 8～12mol/L etching standby, said alkali can be selected from least a among NaOH, the KOH etc., and its time of said etching is 1～10h; Use a kind of cleaning in ionized water, the pure water etc. after the cooling again, and at 3%～8% NaHCO
3Soak 1～10h in the solution.
Said electrophoretic deposition suspension leaves standstill ultrasonic 1～5h after best a day, and with the centrifugal 1～5min of 1000～3000r/min, pours out the upper strata suspension liquid and to standby behind the ultrasonic 0.1～5h of this suspension liquid.
Its temperature control time of said sintering is 1～2h.The argon stream amount is controlled at 4000～6000ml/h, is preferably 5100ml/h.
The present invention adopts the control electrophoretic deposition condition of optimization, can make CNTs uniform distribution in the HA coating, and CNTs is cross-linked the effect of playing support in coating, improves the toughness of coating, strengthens the bonding force of coating and substrate.The present invention only needs to add several concentrated nitric acids adjusting pH values in the alcohol dispersant of HA/CNTs be 4-5, need not to add tensio-active agent and promptly record its Zeta potential for just, HA/CNTs can be deposited to cathode surface under the deposition condition.Because the present invention adopts nano level HA and CNTs, thereby can reduce sintering temperature (in the existing technology, the HA sintering temperature is generally 1200 ℃) significantly.Sample after the sintering is tested its bonding strength through the bonding stretching experiment, experiment shows, because the present invention is with sample sintering under lower temperature and argon gas atmosphere, under this condition, can obtain the compound coating of the good and compact structure of bonding force, and can avoid causing the destruction of HA coating because of high temperature sintering, keep its good biological property.The bonding stretching experiment is binding agent to be clipped in (stressed area is about 1cm between coating and the uncoated titanium plate
2), then sample is clamped, be incubated 1.5h down at 163 ± 1 ℃, make the binding agent melting and solidification.Stretching experiment (model is WDW-100) on the extensive experimentation machine carries out, and draw speed is 1mm/min.Simultaneously, because compound coating at metal titanium surface deposition HA/CNTs, handle by follow-up sintering, increase substantially the bonding force between biological composite coating and the medical metal material, therefore, be expected to reach the requirement of using as human body heavy burden position implant by the resulting nanometer hydroxyapatite of the present invention/carbon nanotube composite coating material.
Description of drawings
Fig. 1 is the SEM shape appearance figure before and after the HA/CNTs compound coating sintering of the different CNTs content of electrophoretic deposition preparation.In Fig. 1, figure a is before 20% sintering of CNTs content position, and figure b is after 20% sintering of CNTs content position, and figure c is before 30% sintering of CNTs content position, and figure d is after 30% sintering of CNTs content position, and figure e is before the pure HA sintering, and figure f is, after the pure HA sintering.As seen from Figure 1, the content of CNTs increases along with the increase of CNTs per-cent in the coating, and the HA that electrophoresis obtains still is rhabdolith, and crystalline structure is intact, and the CNTs pattern does not change, and keeps reasonable tubular structure.And CNTs and HA are evenly distributed, and coating is finer and close after the sintering, and the content of CNTs does not change, and CNTs is cross-linked between HA and is equivalent to action of steel bars in the Steel Concrete, can significantly improve the mechanical property of coating.Experiment finds, when content is lower than when being 10%, because of CNTs content is low excessively, can not reach the purpose of improving the coating mechanical property; And content surpasses at 50% o'clock, because of CNTs content is too high, may influence the biology performance of HA/CNTs.
Fig. 2 is the XRD figure spectrum of 20% o'clock HA/CNTs compound coating sintering front and back for CNTs content.In Fig. 2, it is 20% o'clock forward and backward XRD figure spectrum of sintering that curve a, b are respectively CNTs content.The XRD test result shows that the coating that deposits to the titanium surface is still pure HA crystal, and finds that the spectrum peak after the sintering is more sharp-pointed, illustrates at suitable sintering temperature, can make the crystal formation of HA perfect more.The peak of CNTs is the peak of graphite among the curve a, is the peak of graphite (002) crystal face near 2 θ angles are 26 °, and the peak of graphite among the curve b (002) crystal face still exists, and the peak does not change a lot by force, and the sintering not obviously minimizing of content of CNTs afterwards is described.
Fig. 3 is the XRD figure spectrum of 30% o'clock HA/CNTs compound coating sintering front and back for CNTs content.In Fig. 3, it is XRD figure spectrum before and after 30% o'clock sintering that curve c, d are respectively CNTs content, and the increase of CNTs content does not as can be known have influence on the deposition of HA, XRD spectrum peak after sintering variation tendency and CNTs content be 20% o'clock similar.
Embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1: base material is the pure titaniums of commodity, and sample size is 10mm * 20mm * 3mm, with sand paper machinery sanding and polishing, and adopts water, acetone, ethanol ultrasonic cleaning, immerses in the NaOH solution of 10mol/l in 140 ℃ of thermal treatment 6h again.Use washed with de-ionized water after cooling, be placed on 5% NaHCO
3Soak 1～10h in the solution, make its surface keep neutral.Configuration CNTs content is 20% the total concn electrophoretic deposition solution for (comprising HA and CNTs) 0.005g/ml, drips several dense HNO
3, regulate its pH value between 4～5, record its Zeta potential under this condition for just, the particle positively charged is described.Solution coagulation one angel's system after preparing reaches stable, ultrasonic 3h, larger particles is fallen in centrifugation, after ultrasonic again 0.5h standby.The circular stainless steel coil that with the external diameter is 50cm is the anode counter electrode, and the pure titanium of commodity is a negative electrode.Electrophoretic deposition adopts constant voltage mode in this experiment, and applied voltage is 30V, and the electrophoretic deposition time is 60s, can obtain uniform grey coating, its thickness in time prolongation and thickening (is seen Fig. 1 a).
HA can adopt synthetic being about of obtaining of hydro-thermal to be 30nm, the wide rhabdolith that is about 20nm.CNTs is a multi-walled pipes, uses before at dense HNO
3In under 125 ℃ of heating keep to reflux, boil 1～5h, to reach the purifying purpose.
Embodiment 2: electrophoretic deposition condition and electrode pre-treatment are with embodiment 1.Obtain sample airing in air, the following 700 ℃ of sintering of argon shield, and under this temperature temperature control 2h, reduce to room temperature then.The grey coating (seeing Fig. 1 b) of evenly not had be full of cracks.Mechanical test results is listed in table 1, and coating-titanium substrate caking power is 34.94MP.Table 1 is that the bonding force size of the compound coating of different content CNTs correspondence compares.By table 1 result as can be known, add that the bonding force of compound coating and metal base has increased significantly behind the CNTs, CNTs content be 20% and the bonding force size differences of 30% o'clock compound coating and substrate little.
Embodiment 3: the electrophoretic deposition condition wherein is adjusted into CNTs content 30% and obtains uniform black coating (seeing Fig. 1 c) at last with embodiment 1.Sample is airing in air, and in 700 ℃ of sintering, and temperature control 2h under this temperature is cooled to room temperature under the argon shield.The black coating (seeing Fig. 1 d) that is not evenly had be full of cracks.Mechanical test results is listed in table 1, and coating-titanium substrate caking power is 35.44MP.
Embodiment 4: the processing of base material with embodiment 1, is disposed pure HA suspension with the electrophoretic deposition condition, and concentration is 0.03-0.005g/ml, drips several dense HNO
3, regulate its pH value between 4-5, be that the circular stainless steel coil of 50cm is the anode counter electrode with the external diameter, the constant voltage mode electrophoretic deposition adopts 30V voltage, and the electrophoretic deposition time is 60s, obtains surface white coating (seeing Fig. 1 e) uniformly.With sample under argon gas atmosphere in 700 ℃ of sintering, temperature control 2h is cooled to room temperature.The white coating (seeing Fig. 1 f) that is not evenly had be full of cracks.Mechanical test results is listed in table 1, and coating-titanium substrate caking power is 20.62MP.
Embodiment 5: similar to Example 1, its difference is the austenitic stainless steel (316L) after base material adopts sanding and polishing, and sample size is 10mm * 20mm * 3mm, with sand paper machinery sanding and polishing.Containing the 1mol/lH of 3%NaCl
2SO
4Control current potential 1.2V (SCE) anodic polarization 2min under the room temperature makes surface roughening in the solution.Take out electrolyzer, clean with pure water, drying, standby.Configuration CNTs content is 20% the total concn electrophoretic deposition solution for (comprising HA and CNTs) 0.005g/ml, drips several dense HNO
3, regulate its pH value between 4～5.Adopt constant voltage mode to carry out electrophoretic deposition, applied voltage is 30V, and the electrophoretic deposition time is 60s, can obtain uniform grey coating, its thickness in time prolongation and thickening (is seen Fig. 1 a).
Claims (10)
1, nanometer hydroxyapatite/carbon nanotube preparation method of composite coating is characterized in that its concrete steps are:
1) substrate pretreatment;
2) preparation comprises the electrophoretic deposition suspension of HA and CNTs, and the total concn of electrophoretic deposition suspension is 0.001～0.015g/ml, calculates by mass percentage, and the content of CNTs accounts for 10%～50% of total electrophoretic deposition suspension, uses HNO
3Regulate its pH value 4～5, said HA and CNTs are nano level;
3) the electrophoresis system is a non-aqueous system, and dispersion agent is a straight alcohol;
4) it is ultrasonic, centrifugal electrophoretic deposition suspension to be left standstill stable back, pours out the upper strata suspension liquid;
5) electrophoretic deposition is handled, and voltage is 10～50V, and the electrophoretic deposition time is 10～90s;
6) at 600～900 ℃, sintering under the argon gas atmosphere promptly gets target product.
2, nanometer hydroxyapatite as claimed in claim 1/carbon nanotube preparation method of composite coating is characterized in that said substrate is selected from titanium, titanium alloy, stainless steel metal.
3, nanometer hydroxyapatite as claimed in claim 1 or 2/carbon nanotube preparation method of composite coating, it is characterized in that said substrate pretreatment adopts behind the mechanical sanding and polishing in surface, use at least a ultrasonic cleaning in water, acetone, the ethanol successively, at 120～160 ℃, etching is standby in the alkaline solution of 8～12mol/L, said alkali is selected from least a among NaOH, the KOH, and its time of said etching is 1～10h.
4, nanometer hydroxyapatite as claimed in claim 1 or 2/carbon nanotube preparation method of composite coating is used a kind of cleaning in ionized water, the pure water again after it is characterized in that cooling off, and at 3%～8% NaHCO
3Soak 1～10h in the solution.
5, nanometer hydroxyapatite as claimed in claim 1/carbon nanotube preparation method of composite coating, it is characterized in that said electrophoretic deposition suspension leaves standstill ultrasonic 1～5h after 1 day, and with the centrifugal 1～5min of 1000～3000r/min, pour out the upper strata suspension liquid and to standby behind the ultrasonic 0.1～5h of this suspension liquid.
6, nanometer hydroxyapatite as claimed in claim 1/carbon nanotube preparation method of composite coating is characterized in that calculating by mass percentage, and the content of CNTs accounts for 20%～30% of total electrophoretic deposition suspension.
7, nanometer hydroxyapatite as claimed in claim 1/carbon nanotube preparation method of composite coating is characterized in that said electrophoretic deposition suspension leaves standstill ultrasonic 1～5h after 1 day, and with the centrifugal 1～5min of 1000～3000r/min, the ultrasonic 0.1～5h of suspension liquid.
8,, it is characterized in that the voltage that electrophoretic deposition is handled is constant voltage as claim 1 or 7 described nanometer hydroxyapatite/carbon nanotube preparation method of composite coating.
9, nanometer hydroxyapatite as claimed in claim 1/carbon nanotube preparation method of composite coating is characterized in that its temperature control time of said sintering is 1～2h, and the argon stream amount is controlled at 4000～6000ml/h.
10, as claim 1 or 9 described nanometer hydroxyapatite/carbon nanotube preparation method of composite coating, it is characterized in that said sintering temperature is 700 ℃, the argon stream amount is controlled to be 5100ml/h.
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| CN101949046B (en) * | 2010-09-20 | 2012-07-04 | 上海师范大学 | Preparation method of carbonate hydroxyapatite/carbon nano tube composite coating material |
| CN105963780A (en) * | 2016-04-29 | 2016-09-28 | 太原理工大学 | Titanium dioxide nanotube/hydroxyapatite composite coating used for medical porous titanium and preparation method of titanium dioxide nanotube/hydroxyapatite composite coating |
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| DE19601153A1 (en) * | 1996-01-15 | 1997-07-17 | Kunze Egon Prof Dr Rer Nat Hab | Application of bioactive phosphate layers, e.g. hydroxy apatite ceramic, onto titanium alloy artificial hip joint shafts |
| JP2001020093A (en) * | 1999-07-09 | 2001-01-23 | Matsushita Electric Ind Co Ltd | Electrophoresis device, electron releasing element and image display device produced by utilizing the same as well as their production |
| CN1312402A (en) * | 2001-01-09 | 2001-09-12 | 武汉理工大学 | Technological process of electrophoretic coprecipitation-sintering to prepare gradient metal/biological glass ceramic coating |
| US6616497B1 (en) * | 1999-08-12 | 2003-09-09 | Samsung Sdi Co., Ltd. | Method of manufacturing carbon nanotube field emitter by electrophoretic deposition |
| CN1440948A (en) * | 2003-04-02 | 2003-09-10 | 山东大学 | Composite hydroxyapatite/carbon nanotube material and its prepn process |
| CN1587442A (en) * | 2004-07-06 | 2005-03-02 | 厦门大学 | Electrochemical preparing method for nano ordered hydroxy apatite coating |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19601153A1 (en) * | 1996-01-15 | 1997-07-17 | Kunze Egon Prof Dr Rer Nat Hab | Application of bioactive phosphate layers, e.g. hydroxy apatite ceramic, onto titanium alloy artificial hip joint shafts |
| JP2001020093A (en) * | 1999-07-09 | 2001-01-23 | Matsushita Electric Ind Co Ltd | Electrophoresis device, electron releasing element and image display device produced by utilizing the same as well as their production |
| US6616497B1 (en) * | 1999-08-12 | 2003-09-09 | Samsung Sdi Co., Ltd. | Method of manufacturing carbon nanotube field emitter by electrophoretic deposition |
| CN1312402A (en) * | 2001-01-09 | 2001-09-12 | 武汉理工大学 | Technological process of electrophoretic coprecipitation-sintering to prepare gradient metal/biological glass ceramic coating |
| CN1440948A (en) * | 2003-04-02 | 2003-09-10 | 山东大学 | Composite hydroxyapatite/carbon nanotube material and its prepn process |
| CN1587442A (en) * | 2004-07-06 | 2005-03-02 | 厦门大学 | Electrochemical preparing method for nano ordered hydroxy apatite coating |
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