CN1316274A - Electrochemical process for modifying surface of biologic metal/Ca-P ceramic material - Google Patents

Electrochemical process for modifying surface of biologic metal/Ca-P ceramic material Download PDF

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CN1316274A
CN1316274A CN 00134910 CN00134910A CN1316274A CN 1316274 A CN1316274 A CN 1316274A CN 00134910 CN00134910 CN 00134910 CN 00134910 A CN00134910 A CN 00134910A CN 1316274 A CN1316274 A CN 1316274A
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metal
ceramic
electrochemical
biologic
electrolyte
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CN1162188C (en
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林昌健
胡浩冰
胡仁
张建民
冷扬
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Xiamen University
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Xiamen University
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Abstract

An electrochemical deposition process for chemically modifying the Ca-P ceramic layer coated on the surface of metal features that said Ca-P ceramic layer is used as cathode, Pt electrode is used as anode, and after the electrolyzing liquid containing Ca(NO3)2 and NH4P2PO4 is added, the electrochemical deposotion is conducted at 30-60 deg.C under action of constant current or voltage. After modification the dispersed hydroxy phosphorite microcrystals with fine structure are generated, which benefits the bone forming induction and has high biocompatibility and bioactivity.

Description

The surface of biologic metal/Ca-P ceramic material electrochemical modification method
The present invention relates to a kind of method of the plasma spraying Ca-P ceramic of metal material surface being carried out the modification processing with electrochemical deposition method.
Biomedical material relates to the raising of human beings'health and quality of life, is the hi tech and new material of a class new development, is developing into a pillar industry of 21 century World Economics.In the Artificial bone material implant into body, must satisfy two primary conditions: (1) embedded material should have excellent biological compatibility and high biological activity; (2) embedded material should have suitable mechanical property and certain chemical stability.
Still a large amount of clinically at present metal alloy compositions that use, as rustless steel, titanium alloy and vitallium etc., though mechanical property is better, its biocompatibility is poor, biological activity is low, can not meet the demands.Hydroxyapatite (Hydroxyapatite, be called for short HA) be a kind of and skeleton chemical constituent and the very close calcium phosphate compound of structure, have excellent biological compatibility and superior biological activity, but its fragility is big, anti-fatigue performance is poor, can't use separately.The metal surface of development in recent years applies the calcium phosphorous compound coating, form Metal Substrate complex biological medical material, metal material good mechanical performance and machinability had both been utilized, overcome the shortcoming of metal material biocompatibility difference again, therefore be subjected to common concern, and in clinical, obtain certain application.The most frequently used technology of metal current surface-coated calcium phosphorous compound coating is a plasma spraying method, because the high temperature (instantaneous temperature can reach 6000~10000 ℃) in spraying process, (hydroxyapatite promptly begins instability at 600~700 ℃ can to cause hydroxyapatite that serious phase transformation and decomposition take place, when being higher than 1330 ℃, can undergo phase transition and decompose), the sample cooling also can cause the be full of cracks of Ca-P ceramic coating.Thereby be difficult to obtain and the hydroxyapatite composition of natural person's bone, the coat of structural similarity.Studies show that the biocompatibility and the biological activity that make hydroxyapatite coating layer with conventional plasma spraying method obviously reduce.
Purpose of the present invention aims to provide a kind of method of the metal/Ca-P ceramic coat with the plasma spraying method preparation being carried out surface modification optimization with electrochemical deposition method, make it to generate hydroxyapatite disperse crystallite, be formed with the activity modifying layer that is beneficial to osteogenic induction with perfect structure on metal/Ca-P ceramic coat surface.
The said method of modifying step of the present invention is as follows:
1, the preparation of electric depositing solution: with Ca (NO 3) 2And NH 4H 2PO 4Solution mixes the back and adds deionized water, is mixed with to contain Ca (NO 3) 20.01~0.15mol/L, NH 4H 2PO 40.01 the electrolyte of~0.05mol/L, regulating electrolyte PH value is 3.8~5.2;
2, electrochemical deposition: make negative electrode with the Ca-P ceramic sample that the clean metal surface plasma spray method of surface clean applies, platinum electrode is an anode, adds electrolyte, heating, carry out constant potential or galvanostatic deposition, its electrochemical deposition condition is constant current 0.1~10mA/cm 2, constant potential-1.20~-2.50V, 30~60 ℃ of temperature, sedimentation time 1~60min;
3, sample post processing, the Ca-P ceramic sample wash behind the electrochemical deposition is clean, place 0.1~0.5mol/L NaOH solution, constant temperature is 30~60 ℃ under water bath condition, handles 24~48h, takes out afterflush, dries naturally.
Adopt electrochemical deposition method to carry out modification and handle, can generate many calcium phosphorous compound crystal grains on the Ca-P ceramic surface on the Ca-P ceramic surface of existing plasma spraying.Amplify to observe through Electronic Speculum, find to form on the Ca-P ceramic surface of plasma spraying preparation behind the surperficial electrochemical modification CaP crystal of perfect structure.The Ca-P ceramic coating surface that applies with plasma spraying technology then is molten condition.Because the interaction between artificial implant and body tissue is always at first by the surface/interface between material and body tissue, so manually implant the surface characteristic that the biological property of hard tissue material is decided by material substantially.The Ca-P ceramic coating surface modifying of Applied Electrochemistry sedimentation article on plasma spraying is optimized, make it to have the calcium phosphorus disperse crystallite of perfect structure or the crystalline substance of receiving in the generation of coat surface, be formed with the active center that is beneficial to induced osteogenesis, thereby can significantly improve the biocompatibility and the biological activity of biologic metal/Ca-P ceramic material.Under identical condition, carry out cell culture experiments in vitro with the titanium-based metal surface with calcium hydroxyapatite coating and the sample after electrochemical deposition method is handled that general plasma spraying method prepares, select fibrocyte for use, condition of culture is 37 ± 1 ℃, PH7.2~7.4, cultivated 10 days, the result shows that two kinds of material cell growth all have good facilitation with growing, and distortion is found in the cell growth.But find calcium hydroxyapatite coating surface at general plasma spraying, the density of the growth of cell is lower, the speed of developmental process is inconsistent, cell distribution is not really even: and the Ca-P ceramic plasma spraying laminar surface after handling through the electrochemical deposition method modification, the density of cell growth obviously increases, and cell distribution is even, and the speed of growth course is fast.After experiment showed, that the Ca-P ceramic coating surface that adopts the preparation of electrochemical deposition method article on plasma spraying process carries out the modification processing, the biological activity of Ca-P ceramic plasma spraying laminar surface obviously improves, and helps the Ca-P ceramic superficial growth of cell in modification.Osteoblastic culture experiment shows that also electrochemical deposition method can obviously improve the biological activity on the plasma-coated surface of Ca-P ceramic.
Fig. 1 is Ca-P ceramic coating surface 500 * SEM pattern of embodiment 1 surface modification post plasma spraying.
Fig. 2 is Ca-P ceramic coating surface 15000 * SEM pattern of embodiment 1 surface modification post plasma spraying.
Fig. 3 is Ca-P ceramic coating surface 500 * SEM pattern of embodiment 2 surface modification post plasmas spraying.
Fig. 4 is Ca-P ceramic coating surface 5000 * SEM pattern of embodiment 2 surface modification post plasmas spraying.
Fig. 5 is Ca-P ceramic coating surface 15000 * SEM pattern of embodiment 3 surface modification post plasmas spraying.
The invention will be further described below in conjunction with embodiment.
Embodiment 1: with Ca (NO 3) 2And NH 4H 2PO 4Solution mixes the back and adds deionized water to 50mL, Ca (NO in the electrolyte 3) 2Concentration is 0.01mol/L, NH 4H 2PO 4Be 0.05mol/L, regulating pH value with weak ammonia is 4.2, to clean up by the titanium-based metal surface-coated Ca-P ceramic sample surfaces of general plasma spraying method preparation, make negative electrode with this sample, with the platinum electrode is anode, in electrolysis bath, add the electrolyte of above-mentioned preparation, be heated with stirring to 60 ℃, in 1.0mA/cm 2Constant current deposit 5min, deposition finishes the back takes out sample and rinses well with deionized water, places 0.1mol/LNaOH solution, constant temperature is handled 24h for 60 ℃ under water bath condition, takes out the back and uses deionized water rinsing, dries naturally.Fig. 1 and Fig. 2 handle 500X and the 15000X shape appearance figure that back Ca-P ceramic coating surface electron microscopic observation arrives for electrochemical modification, can clearly see the CaP crystal situation of perfect structure from Fig. 2.
Embodiment 2: the method with embodiment 1 is identical, changes Ca (NO in the electrolyte 3) 2Concentration is 0.15mol/L, NH 4H 2PO 4Be 0.01mol/L, pH value is 4.2, under the constant potential of-1.8V, and 30 ℃ of deposition 30min.Take out the back and rinse well with deionized water, place 0.5mol/LNaOH solution, constant temperature is handled 48h for 30 ℃ under water bath condition, and taking-up is dried.Coating surface SEM shape appearance figure after modification is handled is seen Fig. 3, Fig. 4.
Embodiment 3: Ca (NO in the electrolyte 3) 2Concentration is 0.045mol/L, NH 4H 2PO 4Be 0.025mol/L, pH value is 5.0, and the electrochemical deposition temperature is 45 ℃, and constant potential-2.5V, sedimentation time are 10min.Fig. 5 is the calcium phosphor coating surface SEM shape appearance figure of electrochemical modification after handling.

Claims (4)

1, surface of biologic metal/Ca-P ceramic material electrochemical modification method is characterized in that its method step is at first preparing electric depositing solution, with Ca (NO 3) 2And NH 4H 2PO 4Solution mixes the back and adds deionized water, is mixed with to contain Ca (NO 3) 20.01~0.15mol/L, NH 4H 2PO 40.01 the electrolyte of~0.05mol/L, electrolyte PH value are 3.8~5.2; Applying the Ca-P ceramic sample with the metal surface then is negative electrode, and platinum electrode is an anode, adds electrolyte, at 30~60 ℃, and constant current 0.1~10mA/cm 2Or constant voltage-1.20~-2.5V, electrochemical deposition 1~60min; Ca-P ceramic sample wash behind the electrochemical deposition is clean, place 0.1~0.5mol/L NaOH solution, constant temperature water bath was handled 24~48 hours for 30~60 ℃, took out flushing, dried naturally.
2, surface of biologic metal/Ca-P ceramic material electrochemical modification method as claimed in claim 1 is characterized in that the pH value of electrolyte is regulated under room temperature by dilute ammonia solution.
3, surface of biologic metal/Ca-P ceramic material electrochemical modification method as claimed in claim 1 is characterized in that said metal is a titanium-based metal.
4, surface of biologic metal/Ca-P ceramic material electrochemical modification method as claimed in claim 1 is characterized in that said rinsing step adopts deionized water rinsing.
CNB001349104A 2000-12-07 2000-12-07 Electrochemical process for modifying surface of biologic metal/Ca-P ceramic material Expired - Fee Related CN1162188C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309875C (en) * 2004-07-30 2007-04-11 哈尔滨工业大学 Process for preparing zirconium oxide coating of titanium alloy surface
CN100383291C (en) * 2005-01-21 2008-04-23 四川大学 Surface activating method of medical metal material
CN100391557C (en) * 2003-12-16 2008-06-04 四川大学 Biological active material for realizing percutaneous device biological sealing and method for making same
CN100439569C (en) * 2004-07-06 2008-12-03 厦门大学 Electrochemical preparing method for nano ordered hydroxy apatite coating
CN101991879A (en) * 2010-11-11 2011-03-30 奇瑞汽车股份有限公司 Preparation method of carbon-carbon composite material/hydroxyapatite/polylactic acid biological material
CN102631705A (en) * 2012-04-27 2012-08-15 中南大学 Lanthanum-doped hydroxyapatite compound coating and preparation method thereof
CN103866368A (en) * 2012-12-12 2014-06-18 北京纳通科技集团有限公司 Calcium and phosphate salt biofilm layer and pulse electrochemistry modification method thereof
WO2017118101A1 (en) * 2016-01-05 2017-07-13 郑州大学 Coating for improving corrosion resistance and biocompatibility of medical magnesium and magnesium alloy and preparation method therefor

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100391557C (en) * 2003-12-16 2008-06-04 四川大学 Biological active material for realizing percutaneous device biological sealing and method for making same
CN100439569C (en) * 2004-07-06 2008-12-03 厦门大学 Electrochemical preparing method for nano ordered hydroxy apatite coating
CN1309875C (en) * 2004-07-30 2007-04-11 哈尔滨工业大学 Process for preparing zirconium oxide coating of titanium alloy surface
CN100383291C (en) * 2005-01-21 2008-04-23 四川大学 Surface activating method of medical metal material
CN101991879A (en) * 2010-11-11 2011-03-30 奇瑞汽车股份有限公司 Preparation method of carbon-carbon composite material/hydroxyapatite/polylactic acid biological material
CN102631705A (en) * 2012-04-27 2012-08-15 中南大学 Lanthanum-doped hydroxyapatite compound coating and preparation method thereof
CN103866368A (en) * 2012-12-12 2014-06-18 北京纳通科技集团有限公司 Calcium and phosphate salt biofilm layer and pulse electrochemistry modification method thereof
CN103866368B (en) * 2012-12-12 2016-04-06 北京纳通科技集团有限公司 Calcium microcosmic salt biological membranous layer and pulse electrochemical method of modifying thereof
WO2017118101A1 (en) * 2016-01-05 2017-07-13 郑州大学 Coating for improving corrosion resistance and biocompatibility of medical magnesium and magnesium alloy and preparation method therefor

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