CN101709496A - Micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating - Google Patents
Micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coatingDownload PDFInfo
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Abstract
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Translated fromChinese技术领域technical field
本发明属于生物医用材料制备领域，涉及材料表面涂覆技术，具体涉及一种镁基生物活性涂层的微弧氧化-电沉积制备方法。The invention belongs to the field of preparation of biomedical materials, and relates to material surface coating technology, in particular to a micro-arc oxidation-electrodeposition preparation method of a magnesium-based bioactive coating.
背景技术Background technique
硬组织植入材料是生物材料的重要组成部分，因为其应用面广、需求量大，已经成为各国科技工作者开发研究的热点；生物医用金属材料，具有优良的生物力学性能、加工性能和可靠性，是临床应用最广泛的承力植入材料，目前已经用于临床的人体硬组织修补用金属材料包括医用不锈钢、钴合金、钛合金和形状记忆合金等。不过随着时间的推移，金属内固定物应用范围的扩大，其自身的缺点也逐渐暴露，应力遮挡、电解腐蚀、材料断裂、二次手术取出及患者精神负担增加等等，因此可降解吸收的生物材料的研究成为当前生物材料领域的国际研究前沿和热点。Hard tissue implant materials are an important part of biomaterials. Because of their wide application and large demand, they have become a hot spot for research and development by scientific and technological workers in various countries; biomedical metal materials have excellent biomechanical properties, processing properties and reliability. It is the most widely used load-bearing implant material in clinical practice. The metal materials used in human hard tissue repair include medical stainless steel, cobalt alloy, titanium alloy and shape memory alloy. However, with the passage of time, the scope of application of metal internal fixation has expanded, and its own shortcomings have gradually been exposed, such as stress shielding, electrolytic corrosion, material fracture, secondary surgical removal, and increased mental burden on patients, etc. The study of biomaterials has become an international research frontier and hotspot in the field of biomaterials.
由于镁不仅具有良好的力学性能，而且对人体无毒，通过腐蚀可在体内逐步降解，因而镁及其合金作为一种极有发展潜力的可降解植入生物材料日益受到人们的青睐。Since magnesium not only has good mechanical properties, but also is non-toxic to the human body, and can be gradually degraded in the body through corrosion, magnesium and its alloys are increasingly favored as a biodegradable biomaterial with great development potential.
镁及其合金作为生物医用材料主要有以下几个方面的优点：(1)具有优异的生物力学相容性。镁与镁合金的密度为1.7g/cm3在所有结构材料中密度最小，与人体的密质骨密度(1.75g/cm3)极为接近，远低于Ti-6Al-4V的密度(4.47g/cm3)，符合理想接骨板的要求；镁及镁合金有高的比强度和比刚度。镁及其合金的杨氏模量约为45GPa，更接近人骨的弹性模量(20GPa)，可以在骨折愈合初期提供稳定的力学环境，逐渐降低应力遮挡作用，使骨折部位承受逐渐增大乃至生理水平的应力刺激，从而加速愈合，防止局部骨质疏松和再骨折。(2)具有优良的生物学特性。镁离子可以促进钙的沉积，镁可以用于增强骨的传导性，减少骨骼过早老化、骨质疏松、软组织钙化等。(3)具有可吸收降解特性。镁具有很低的标准电极电位，因而镁及其合金在人体液作用下会被逐渐降解，生成的镁离子可被周围肌体组织吸收或通过体液排出体外，故植入后不必取出，避免二次手术对患者的身体痛苦和经济负担。Magnesium and its alloys have the following advantages as biomedical materials: (1) Excellent biomechanical compatibility. The density of magnesium and magnesium alloy is 1.7g/cm3 , which is the smallest density among all structural materials, which is very close to the compact bone density of human body (1.75g/cm3 ), far lower than the density of Ti-6Al-4V (4.47g /cm3 ), meeting the requirements of an ideal bone plate; magnesium and magnesium alloys have high specific strength and specific stiffness. The Young's modulus of magnesium and its alloys is about 45GPa, which is closer to the elastic modulus of human bone (20GPa). It can provide a stable mechanical environment in the early stage of fracture healing, gradually reduce the stress shielding effect, and make the fracture site bear gradually increased and even physiological Horizontal stress stimulation, thereby accelerating healing and preventing localized osteoporosis and refracture. (2) It has excellent biological characteristics. Magnesium ions can promote calcium deposition, and magnesium can be used to enhance bone conductivity, reduce premature bone aging, osteoporosis, soft tissue calcification, etc. (3) It has absorbable and degradable properties. Magnesium has a very low standard electrode potential, so magnesium and its alloys will be gradually degraded under the action of human body fluids, and the generated magnesium ions can be absorbed by surrounding body tissues or excreted through body fluids, so there is no need to take them out after implantation to avoid secondary Physical pain and financial burden of surgery on patients.
任伊宾等、宋光铃等分别研究了纯镁在生理盐水、人工体液中的腐蚀行为，Witte等探讨了镁合金在动物体内的腐蚀行为，认为有望将其发展成为新型生物医用可降解植入材料。但是镁及合金的耐腐蚀性较差，特别是在pH值低于11.5、Cl-存在的生理环境中腐蚀速率更快，人体内的pH值约为7.4，在手术后的人体代谢吸收过程中可能会引起人体内二级酸液过多症，使体内环境的pH值低于7.4，所以镁合金作为植入材料在体内会加速腐蚀。虽然镁是人体的常量元素，但吸收过量镁离子对人体也是有害的。另一方面，可降解生物材料要求材料降解速率与组织新生或者愈合速度之间匹配，骨组织的修复一般需要12～18周，而镁合金因为腐蚀过快导致提前失去应有的承载力，同时，腐蚀过快会导致在植入部位的皮下组织中的大量氢气来不及扩散吸收，从而产生炎症、坏死等现象。Ren Yibin et al., Song Guangling et al. studied the corrosion behavior of pure magnesium in normal saline and artificial body fluids. Witte et al. discussed the corrosion behavior of magnesium alloys in animals, and believed that it is expected to develop into a new type of biomedical degradable implant material. . However, the corrosion resistance of magnesium and alloys is poor, especially in the physiological environment where the pH value is lower than 11.5 and Cl- exists, the corrosion rate is faster. The pH value in the human body is about 7.4. It may cause secondary hyperacidity in the human body, making the pH value of the internal environment lower than 7.4, so magnesium alloys as implant materials will accelerate corrosion in the body. Although magnesium is a constant element for the human body, excessive absorption of magnesium ions is also harmful to the human body. On the other hand, degradable biomaterials require the matching between the material degradation rate and the tissue regeneration or healing rate, and the repair of bone tissue generally takes 12 to 18 weeks, while the magnesium alloy loses its due bearing capacity early due to excessive corrosion, and at the same time , Excessive corrosion will cause a large amount of hydrogen in the subcutaneous tissue at the implantation site to have no time to diffuse and absorb, resulting in inflammation, necrosis and other phenomena.
镁合金能否成为可降解的硬组织植入材料，材料的安全性和降解速率的控制是两个基本条件。一方面要考察镁基材料在生理环境下的降解腐蚀对宿主生理各方面以及对成骨的影响，另一方面就是通过合金化和表面改性提高镁的耐腐蚀性，使其降解速率与骨组织愈合的速度相适应，同时通过表面改性提高植入材料的生物相容性。Whether magnesium alloy can become a degradable hard tissue implant material, the safety of the material and the control of the degradation rate are two basic conditions. On the one hand, it is necessary to investigate the degradation and corrosion of magnesium-based materials in the physiological environment, and the impact on the physiological aspects of the host and on osteogenesis; The speed of tissue healing is adapted while improving the biocompatibility of the implant material through surface modification.
生物医用材料有各自的特点，在临床应用时各具优势，而以结合不同材料优点所设计和构造的复合材料体系是生物医用复合材料研发的一个重点和热点。从20世纪80年代开始，在医用金属基底表面构造磷酸钙盐生物涂层材料逐渐引起各国学者的重视。这主要是基于两个方面的原因：首先，磷酸钙盐，如羟基磷灰石(HA，分子式Ca10(PO4)6(OH)2)、磷酸八钙(OCP)、磷酸三钙(Ca3(PO4)2)、酸式磷酸钙(CaHPO4·2H2O)等，它们与人和动物骨组织的无机成分相似，或能转变为骨组织的无机成分，所以当作为硬组织植入体的表层与周围机体组织相接触时，不会像金属植入体那样有致毒(引起炎症、刺激、过敏等)和导致突变的危险，而且还能诱导附近骨组织的生长，形成牢固的骨键合，表现出优异的生物活性；其次，单纯的磷酸钙盐晶体脆性大、抗折强度低，不宜用于承载硬组织的修复与取代，而金属材料(如钛、钛合金、不锈钢等)则可以弥补磷酸钙盐植入体机械强度不足的缺陷。故磷酸钙盐/金属生物复合体系结合了磷酸钙盐生物活性好和金属机械强度高的优点，是用于人和动物硬组织损伤后修复或取代的一类理想材料。Biomedical materials have their own characteristics and have their own advantages in clinical application. The composite material system designed and constructed by combining the advantages of different materials is a focus and hot spot in the research and development of biomedical composite materials. Since the 1980s, the construction of calcium phosphate biocoating materials on the surface of medical metal substrates has gradually attracted the attention of scholars from all over the world. This is mainly based on two reasons: First, calcium phosphate salts, such as hydroxyapatite (HA, molecular formula Ca10 (PO4 )6 (OH)2 ), octacalcium phosphate (OCP), tricalcium phosphate (Ca3 (PO4 )2 ), acid calcium phosphate (CaHPO4 ·2H2 O), etc., which are similar to the inorganic components of human and animal bone tissue, or can be transformed into inorganic components of bone tissue, so they should be used as hard tissue implants When the surface layer of the implant is in contact with the surrounding body tissue, it will not be toxic (cause inflammation, irritation, allergy, etc.) and cause mutations like metal implants, and it can also induce the growth of nearby bone tissue to form a firm Osteobonding, showing excellent biological activity; secondly, pure calcium phosphate crystals are brittle and have low flexural strength, so they are not suitable for the repair and replacement of bearing hard tissues, while metal materials (such as titanium, titanium alloys, stainless steel, etc.) ) can make up for the insufficient mechanical strength of the calcium phosphate implant. Therefore, the calcium phosphate/metal biocomposite system combines the advantages of good biological activity of calcium phosphate and high mechanical strength of metal, and is an ideal material for repairing or replacing hard tissues of humans and animals after injury.
目前有直接通过等离子喷涂(中国申请号：03117835.9、200510021026.5、200710064147.7)，电化学沉积法(中国申请号：200410071505.3、200810049023.6)在镁合金表面制备羟基磷灰石等生物涂层。但是等离子喷涂是线性过程，难以在形状复杂和表面粗糙基体上获得厚度均匀的涂层，同时由于热膨胀系数差异，喷涂后冷却过程中的HA涂层会因应力集中产生裂纹，另外喷涂过程温度过高易使HA分解导致HA结晶度低。恒流电沉积得到的HA涂层与基体镁合金的结合强度较低，在植入的过程中易于脱落。其他的单一工艺都分别存在相容性和力学稳定性的问题；由于一些极端处理条件使得生物涂层不均匀或发生分解，涂层与基体力学性能不匹配，如热膨胀系数、杨氏模量差别过大，易造成应力集中；涂层与基底之间结合强度不够，致使涂层剥落，涂层不能有效发挥紧密结合基底与新生组织的功能。因此研发具有良好生物活性的抗剥离、腐蚀防护能力的新型生物涂层材料体系和制备新方法将很有必要。At present, biological coatings such as hydroxyapatite are directly prepared on the surface of magnesium alloys by plasma spraying (Chinese application numbers: 03117835.9, 200510021026.5, 200710064147.7), electrochemical deposition (Chinese application numbers: 200410071505.3, 200810049023.6). However, plasma spraying is a linear process, and it is difficult to obtain a coating with a uniform thickness on a substrate with a complex shape and a rough surface. At the same time, due to the difference in thermal expansion coefficient, the HA coating in the cooling process after spraying will produce cracks due to stress concentration. In addition, the temperature of the spraying process is too high. High is easy to decompose HA, resulting in low crystallinity of HA. The bonding strength between the HA coating obtained by constant current electrodeposition and the matrix magnesium alloy is low, and it is easy to fall off during the implantation process. Other single processes have problems of compatibility and mechanical stability; due to some extreme processing conditions, the biological coating is uneven or decomposed, and the mechanical properties of the coating and the substrate do not match, such as the difference in thermal expansion coefficient and Young's modulus If it is too large, it will easily cause stress concentration; if the bonding strength between the coating and the substrate is not enough, the coating will peel off, and the coating will not be able to effectively perform the function of tightly bonding the substrate and the new tissue. Therefore, it will be necessary to develop new biological coating material systems and new preparation methods with good biological activity, anti-stripping and corrosion protection capabilities.
目前已经有人通过微弧氧化和水热处理在钛合金的表面制备HA生物涂层，而在镁合金表面通过微弧氧化结合电沉积法制备钙磷盐生物活性涂层还未经报道。At present, some people have prepared HA biological coatings on the surface of titanium alloys by micro-arc oxidation and hydrothermal treatment, but it has not been reported to prepare calcium-phosphorus salt bioactive coatings on the surface of magnesium alloys by micro-arc oxidation combined with electrodeposition.
发明内容Contents of the invention
本发明的目的旨在针对单一制备工艺的不足，提供一种镁基生物活性涂层的微弧氧化-电沉积制备方法。The purpose of the present invention is to provide a micro-arc oxidation-electrodeposition preparation method for a magnesium-based bioactive coating to address the shortcomings of a single preparation process.
本发明的目的是通过以下技术方案来实现的：The purpose of the present invention is achieved through the following technical solutions:
一种镁基生物活性涂层的微弧氧化-电沉积制备方法，包括以下步骤：A micro-arc oxidation-electrodeposition preparation method for a magnesium-based bioactive coating, comprising the following steps:
(1)预处理基体材料：将镁基基底材料表面打磨、清洗干净，备用；对镁基基底材料的预处理可以采用本领域技术人员公知常用的预处理技术，本发明中可具体按以下过程操作：使用100#、200#、400#、600#、800#、1000#SiC金相砂纸依次抛光基体材料后，将基体材料置于体积比为1∶1的丙酮/无水乙醇混合溶液中超声清洗5～15min，用来除去基体材料上的杂质和油脂，清洗后室温自然干燥备用；(1) Pretreatment base material: the surface of magnesium base base material is polished, cleaned, and ready for use; the pretreatment of magnesium base base material can adopt the well-known and commonly used pretreatment technology known to those skilled in the art, and can be specifically according to the following process in the present invention Operation: Use 100# , 200# , 400# , 600# , 800# , 1000# SiC metallographic sandpaper to polish the base material in turn, then place the base material in a mixed solution of acetone/absolute ethanol with a volume ratio of 1:1 Ultrasonic cleaning for 5 to 15 minutes is used to remove impurities and grease on the base material, and after cleaning, it is naturally dried at room temperature for later use;
(2)配制微弧氧化电解液：微弧氧化电解液是由下述浓度的各成份组成的水溶液：Na3PO40.06～0.19mol/L，NaOH 0.025～0.075mol/L；(2) Preparation of micro-arc oxidation electrolyte: micro-arc oxidation electrolyte is an aqueous solution composed of the following components: Na3 PO4 0.06-0.19mol/L, NaOH 0.025-0.075mol/L;
(3)微弧氧化：以步骤(1)中处理好的镁基基底材料为阳极，不锈钢片为阴极，将阳极和阴极浸没在步骤(2)中配制好的电解液中于室温搅拌下进行恒电流微弧氧化反应，其中两极间距5～15cm，反应电压100～400V，反应电流0.5～3A，占空比10～15％，正向频率600～800Hz，反应时间1～60min，将反应过后的微弧氧化试样冲洗、干燥备用；(3) Micro-arc oxidation: take the magnesium-based base material processed in step (1) as the anode, and the stainless steel sheet as the cathode, immerse the anode and the cathode in the electrolyte prepared in step (2) and carry out under stirring at room temperature Constant current micro-arc oxidation reaction, wherein the distance between two electrodes is 5-15cm, the reaction voltage is 100-400V, the reaction current is 0.5-3A, the duty cycle is 10-15%, the forward frequency is 600-800Hz, and the reaction time is 1-60min. Rinse and dry the micro-arc oxidation samples for later use;
(4)配制电沉积电解液：电沉积电解液是由下述浓度的各成份组成的水溶液：H2PO4-0.0046～0.046mol/L、NaNO30.041～0.112mol/L、Ca2+0.008～0.08mol/L，调节溶液pH值为4.0～7.0，调节pH值时，本领域技术人员可选用常规的酸碱进行调节，本发明中优选质量浓度为1～12％的稀HNO3或(CH2OH)3CNH2。(4) Preparation of electrodeposition electrolyte: The electrodeposition electrolyte is an aqueous solution composed of the following components: H2 PO4- 0.0046～0.046mol/L, NaNO3 0.041～0.112mol/L, Ca2+ 0.008 ～0.08mol/L, adjust the pH value of the solution to be 4.0～7.0, when adjusting the pH value, those skilled in the art can choose conventional acid-base to adjust, preferred mass concentration in the present invention is 1～12% dilute HNOOr (CH2OH )3CNH2.
(5)电沉积：将在步骤(3)中形成的微弧氧化试样作为电沉积反应阴极，石墨片为阳极，将步骤(4)中配制好的电解液加热至50～100℃，将阴极和阳极浸没在电解液中进行恒电流电沉积反应，其中两极间距2～10cm，沉积电流密度1～100mA/cm2，沉积时间1～90min；(5) Electrodeposition: The micro-arc oxidation sample formed in step (3) is used as the electrodeposition reaction cathode, and the graphite sheet is used as the anode, and the electrolyte prepared in step (4) is heated to 50-100 ° C, and the The cathode and anode are immersed in the electrolyte for constant current electrodeposition reaction, where the distance between the two electrodes is 2-10cm, the deposition current density is 1-100mA/cm2 , and the deposition time is 1-90min;
(6)将经步骤(5)沉积过后的试样取出，冲洗、干燥即可。(6) Take out the sample deposited in step (5), rinse and dry.
为使微弧氧化得到的涂层含有钙，为后续电沉积反应提供含钙基底，在上述微弧氧化电解液配方的基础之上，可进一步优化为：步骤(2)中所述微弧氧化电解液中还含有碱性钙盐0.01～0.015mol/L。In order to make the coating obtained by micro-arc oxidation contain calcium and provide a calcium-containing substrate for the subsequent electrodeposition reaction, on the basis of the above-mentioned micro-arc oxidation electrolyte formula, it can be further optimized as follows: the micro-arc oxidation described in step (2) The electrolyte also contains 0.01-0.015 mol/L of alkaline calcium salt.
所述碱性钙盐为CaCO3、Ca(OH)2或其组合。本发明中微弧氧化电解液按照上述优化前或后进行配制，所得电解液的pH值一般在11～13之内。The basic calcium salt is CaCO3 , Ca(OH)2 or a combination thereof. In the present invention, the micro-arc oxidation electrolyte is prepared before or after the above optimization, and the pH value of the obtained electrolyte is generally within 11-13.
步骤(4)的电沉积电解液中，所述H2PO4-选自NH4H2PO4、NaH2PO4中的一种或其组合，所述Ca2+选自无水硝酸钙Ca(NO3)2、四水硝酸钙Ca(NO3)2·4H2O、醋酸钙Ca(CH3COO)2中的一种或其组合。In the electrodeposition electrolyte in step (4), the H2 PO4- is selected from one of NH4 H2 PO4 , NaH2 PO4 or a combination thereof, and the Ca2+ is selected from anhydrous calcium nitrate One or a combination of Ca(NO3 )2 , calcium nitrate tetrahydrate Ca(NO3 )2 ·4H2 O, calcium acetate Ca(CH3 COO)2 .
所述生物活性涂层是含有羟基磷灰石(HA)、磷酸八钙Ca8H(PO4)6·5H2O(简称OCP)、磷酸镁Mg3(PO4)2和氧化镁MgO的生物活性复合涂层。The bioactive coating is composed of hydroxyapatite (HA), octacalcium phosphate Ca8 H(PO4 )6 ·5H2 O (OCP for short), magnesium phosphate Mg3 (PO4 )2 and magnesium oxide MgO Bioactive composite coating.
步骤(3)中，微弧氧化时搅拌速率为20～50转/分钟。In step (3), the stirring rate during the micro-arc oxidation is 20-50 rpm.
步骤(3)和步骤(6)中，试样干燥温度为40～60℃。In step (3) and step (6), the sample drying temperature is 40-60°C.
所述镁基为纯镁或镁合金。The magnesium base is pure magnesium or magnesium alloy.
所述镁合金为Mg-Zn基、Mg-Al基、Mg-Mn基或Mg-Ca基合金。The magnesium alloy is a Mg-Zn-based, Mg-Al-based, Mg-Mn-based or Mg-Ca-based alloy.
本发明中，所述室温均是指25℃，冲洗试样时均是用水冲洗，较好地，优选去离子水或蒸馏水。In the present invention, the room temperature refers to 25°C, and the sample is washed with water, preferably deionized water or distilled water.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)微弧氧化与其他镁合金表面处理方法比较，其综合性能更适合于生物医用环境中镁合金的表面处理，它具有以下的优点：耐腐蚀性、耐磨性好；与基体形成冶金结合，不易脱落；可在金属表面形成粗糙面有利于成骨细胞附着；与通常的阳极氧化处理相比，对材料的疲劳强度降低很小；(1) Compared with other surface treatment methods of magnesium alloy, micro-arc oxidation is more suitable for the surface treatment of magnesium alloy in biomedical environment. It has the following advantages: good corrosion resistance and wear resistance; Combined, not easy to fall off; can form a rough surface on the metal surface, which is conducive to the attachment of osteoblasts; compared with the usual anodizing treatment, the fatigue strength of the material is reduced very little;
(2)微弧氧化后表面具有多孔结构，使电沉积形成的钙磷盐长于孔内，形成钉扎，在钙磷盐生物涂层与微弧氧化层之间形成机械嵌合界面结构，从而提高钙磷盐涂层与基材之间的结合性能，使之比原来单一的长于光滑合金表面的结合力要高；(2) After micro-arc oxidation, the surface has a porous structure, so that the calcium-phosphorus salt formed by electrodeposition is longer than the pores, forming pinning, and forming a mechanical interfacial structure between the calcium-phosphorus salt biological coating and the micro-arc oxidation layer, thereby Improve the bonding performance between the calcium phosphate coating and the substrate, making it higher than the original single bonding force longer than the smooth alloy surface;
(3)微弧氧化层的性能介于医用金属和钙磷盐陶瓷之间，使得复合涂层与基材之间具有更加匹配的机械力学性能；(3) The performance of the micro-arc oxidation layer is between medical metal and calcium phosphate ceramics, which makes the mechanical properties of the composite coating and the substrate more matched;
(4)利用微弧氧化层的腐蚀防护性能提高复合体系的耐腐蚀性能，同时又通过电沉积的钙磷盐对微弧表面的孔洞进行半封孔，进一步改善整个涂层的耐腐蚀性能，另外钙磷盐的类骨特性使得骨细胞在其表面的生长更加容易，从而提高了整体的生物活性和相容性。(4) The corrosion protection performance of the micro-arc oxidation layer is used to improve the corrosion resistance of the composite system, and at the same time, the holes on the surface of the micro-arc are semi-sealed by electrodeposited calcium and phosphate salts to further improve the corrosion resistance of the entire coating. In addition, the bone-like properties of calcium and phosphate salts make it easier for bone cells to grow on the surface, thereby improving the overall biological activity and compatibility.
(5)本发明方法形成的生物活性涂层是复合涂层(HA+OCP+Mg3(PO3)2+MgO)，复合涂层中由于OCP的存在，避免了纯HA降解困难的问题，避免了形成镁合金降解完成后只剩下HA外壳的问题。(5) The biologically active coating formed by the method of the present invention is a composite coating (HA+OCP+Mg3 (PO3 )2 +MgO). In the composite coating, due to the existence of OCP, the problem of difficult degradation of pure HA is avoided, The problem that only the shell of HA is left after the degradation of the magnesium alloy is formed is avoided.
附图说明Description of drawings
图1：实施例1中单一微弧氧化(a)、单一电沉积(b)及本发明微弧氧化-电沉积(c)制备涂层的XRD图谱；Fig. 1: the XRD spectrum of coating prepared by single micro-arc oxidation (a), single electrodeposition (b) and micro-arc oxidation-electrodeposition (c) of the present invention in
图2：实施例1中单一微弧氧化(a)和本发明微弧氧化-电沉积(b，c)制备涂层的典型SEM图；Fig. 2: the typical SEM image of coating prepared by single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b, c) of the present invention in
图3：实施例1中单一微弧氧化(a)和本发明微弧氧化-电沉积(b)制备涂层的典型EDS图；Fig. 3: the typical EDS figure of coating prepared by single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b) of the present invention in
图4：实施例1中刻划法测试涂层结合强度：本发明微弧氧化-电沉积制备涂层0级(a)；单一电沉积制备涂层2级(b)；Fig. 4: Test coating bond strength by scribe method in embodiment 1: micro-arc oxidation-electrodeposition preparation coating grade 0 (a) of the present invention; single electrodeposition preparation coating grade 2 (b);
图5：实施例1中镁合金基体(1)，单一微弧氧化试样(2)及本发明微弧氧化-电沉积试样(3)在模拟体液中的极化曲线；Fig. 5: the polarization curve of magnesium alloy matrix (1) in
图6：实施例4中单一微弧氧化(a)及本发明微弧氧化-电沉积(b)制备涂层的XRD图谱；Fig. 6: XRD patterns of the coating prepared by single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b) of the present invention in
图7：实施例4中单一微弧氧化(a)和本发明微弧氧化-电沉积(b，c)制备涂层的SEM图；Figure 7: SEM images of coatings prepared by single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b, c) of the present invention in Example 4;
图8：实施例4中本发明微弧氧化-电沉积试样在模拟体液中的极化曲线。Fig. 8: The polarization curve of the micro-arc oxidation-electrodeposition sample of the present invention in the simulated body fluid in Example 4.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步说明，所列实施例均是在以本发明技术方案为前提下实施的，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。The present invention will be further described below in conjunction with the examples, and the listed examples are all implemented under the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures have been provided, but the protection scope of the present invention is not limited to the following the described embodiment.
实施例1Example 1
在Mg-2wt％Zn合金表面微弧氧化-电沉积制备生物活性涂层的方法，包括以下步骤：The method for preparing a biologically active coating by micro-arc oxidation-electrodeposition on the surface of Mg-2wt%Zn alloy comprises the following steps:
(1)预处理基体材料：使用100#、200#、400#、600#、800#、1000#SiC金相砂纸依次抛光基体材料后，将基体材料置于体积比为1∶1的丙酮/无水乙醇混合溶液中超声清洗10min，用来除去基体材料上的杂质和油脂，清洗后室温自然干燥备用；(1) Pretreatment of the base material:
(2)配制微弧氧化电解液：微弧氧化电解液是由下述浓度的各成份组成的水溶液：Na3PO40.1mol/L，NaOH 0.05mol/L；(2) Preparation of micro-arc oxidation electrolyte: micro-arc oxidation electrolyte is an aqueous solution composed of the following components: Na3 PO4 0.1mol/L, NaOH 0.05mol/L;
(3)微弧氧化：以步骤(1)中处理好的镁基基底材料为阳极，不锈钢片为阴极，将阳极和阴极浸没在步骤(2)中配制好的电解液中于室温搅拌(35转/分钟)下进行恒电流微弧氧化反应，其中两极间距10cm，反应电压100～250V(反应电压在未起弧之前持续上升，达到起弧电压后开始起弧，此时电压随着涂层越来越厚还是一直上升，最后趋于稳定)，反应电流1A，占空比10％，正向频率800Hz，反应时间30min，将反应过后的微弧氧化试样用去离子水冲洗后在50℃下干燥备用；(3) Micro-arc oxidation: the magnesium-based base material processed in step (1) is used as the anode, and the stainless steel sheet is used as the cathode, and the anode and the cathode are immersed in the electrolyte prepared in step (2) and stirred at room temperature (35 (rev/min) for constant current micro-arc oxidation reaction, in which the distance between the two poles is 10cm, and the reaction voltage is 100-250V (the reaction voltage continues to rise before the arc starts, and the arc starts after reaching the arc starting voltage. At this time, the voltage increases with the coating It is getting thicker or keeps rising, and finally tends to be stable), the reaction current is 1A, the duty cycle is 10%, the forward frequency is 800Hz, and the reaction time is 30min. Dry at ℃ for later use;
(4)配制电沉积电解液：电沉积电解液是由下述浓度的各成份组成的水溶液：NH4H2PO40.01mol/L、NaNO30.08mol/L、Ca(NO3)2·4H2O 0.04mol/L，用质量浓度为7％的稀HNO3或(CH2OH)3CNH2调节溶液pH值为5.0；(4) Preparation of electrodeposition electrolyte: electrodeposition electrolyte is an aqueous solution composed of the following components: NH4 H2 PO4 0.01mol/L, NaNO3 0.08mol/L, Ca(NO3 )2 · 4H2 O 0.04mol/L, use dilute HNO3 or (CH2 OH)3 CNH2 with a mass concentration of 7% to adjust the pH value of the solution to 5.0;
(5)电沉积：将在步骤(3)中形成的微弧氧化试样作为电沉积反应阴极，石墨片为阳极，将步骤(4)中配制好的电解液加热至80℃，将阴极和阳极浸没在电解液中进行恒电流电沉积反应，其中两极间距6cm，沉积电流密度1mA/cm2，沉积时间30min；(5) Electrodeposition: the micro-arc oxidation sample formed in step (3) is used as the electrodeposition reaction cathode, the graphite sheet is the anode, the electrolyte prepared in the step (4) is heated to 80 ° C, and the cathode and The anode is immersed in the electrolyte for constant current electrodeposition reaction, where the distance between the two electrodes is 6cm, the deposition current density is 1mA/cm2 , and the deposition time is 30min;
(6)将经步骤(5)沉积过后的试样取出，用去离子水冲洗干净之后，在50℃下干燥即可。(6) Take out the sample deposited in step (5), rinse it with deionized water, and then dry it at 50°C.
为说明本发明微弧氧化-电沉积复合制备方法的优点，本实施例中在对基底材料进行预处理之后分别按以下2种条件进行对照试验：1、保持本实施例相同的微弧氧化电解液和微弧氧化试验参数相同的条件下进行单一微弧氧化对照试验；2、保持本实施例相同的电沉积电解液和电沉积试验参数相同的条件下进行单一电沉积对照试验。In order to illustrate the advantages of the micro-arc oxidation-electrodeposition composite preparation method of the present invention, in this embodiment, after the base material is pretreated, the control test is carried out according to the following two conditions: 1. Keep the same micro-arc oxidation electrolysis method as in this embodiment. A single micro-arc oxidation control test was carried out under the same conditions of the electrolytic solution and the same parameters of the micro-arc oxidation test; 2. A single control test of electrodeposition was carried out under the same conditions of the same electrodeposition electrolyte and electrodeposition test parameters in this embodiment.
图1是单一微弧氧化(a)、单一电沉积(b)及本发明微弧氧化-电沉积(c)制备涂层的XRD图谱：从图1(a)中可以看出，通过单一微弧氧化形成的涂层中主要包括Mg3(PO4)2和MgO两种物质，从图1(b)中可以看出，通过单一电沉积形成的涂层中主要为HA，而在图1(c)中可以看到除了图(a)和图(b)中出现的物质，还出现了Ca8H(PO4)6·5H2O(OCP)的谱峰。Fig. 1 is the XRD pattern of coating prepared by single micro-arc oxidation (a), single electrodeposition (b) and micro-arc oxidation-electrodeposition (c) of the present invention: as can be seen from Fig. 1 (a), through single micro-arc oxidation The coating formed by arc oxidation mainly includes Mg3 (PO4 )2 and MgO. It can be seen from Figure 1(b) that the coating formed by single electrodeposition mainly contains HA, while in Figure 1 In (c), it can be seen that in addition to the substances appearing in (a) and (b), there is also a spectral peak of Ca8 H(PO4 )6 ·5H2 O(OCP).
图2是单一微弧氧化(a)和本发明微弧氧化-电沉积(b，c)制备涂层的典型SEM图：从图2(a)中可以看出，涂层的表面布满了微孔，此微孔对整体的耐腐蚀性性能有所影响，同时也为电沉积形成的晶体生长提供了场所，在图2(b，c)中可以看到微弧氧化后进行电沉积的表面涂层的生长形貌，从图2(b，c)中可以看出，众多的条状沉积晶体在微弧氧化基底上沉积，微弧氧化的微孔里有大量的沉积物，微孔的凹陷处，说明电沉积形成的钙磷盐对微弧氧化的微孔进行了半封孔，既提高了整体的耐腐蚀性能，又保留了微孔，保持了较大的面积，有利于和植入体的结合，为新生组织的长入提供了通道，提高了植入体的生物相容性，同时在孔中的生长也大大提高了涂层的结合强度。Fig. 2 is the typical SEM figure of coating prepared by single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b, c) of the present invention: as can be seen from Fig. 2 (a), the surface of coating is covered with Micropores, this micropore has an impact on the overall corrosion resistance performance, and also provides a place for the crystal growth formed by electrodeposition. In Figure 2(b, c), you can see the electrodeposition after micro-arc oxidation The growth morphology of the surface coating, as can be seen from Figure 2 (b, c), many strip-like deposition crystals are deposited on the micro-arc oxidation substrate, and there are a large number of deposits in the micro-pores of the micro-arc oxidation. It shows that the calcium-phosphorus salt formed by electrodeposition semi-seals the micropores of micro-arc oxidation, which not only improves the overall corrosion resistance, but also retains the micropores and maintains a larger area, which is beneficial to The combination of the implant provides a channel for the growth of the new tissue, which improves the biocompatibility of the implant, and at the same time, the growth in the hole also greatly improves the bonding strength of the coating.
图3是单一微弧氧化(a)和本发明微弧氧化-电沉积(b)制备涂层的典型EDS图：图3(a)中主要显示了在单一微弧氧化制备的涂层表面只有Mg、P、O、Na、Zn元素，而图3(b)中主要显示了在微弧氧化-电沉积的涂层中出现了Mg、P、O、Na、Ca元素，通过两种方法结合的涂层中出现了大量的Ca元素，说明有生物活性的钙磷盐存在。Fig. 3 is the typical EDS figure of coating prepared by single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b) of the present invention: in Fig. 3 (a), it mainly shows that only Mg, P, O, Na, Zn elements, while Figure 3(b) mainly shows that Mg, P, O, Na, and Ca elements appear in the micro-arc oxidation-electrodeposition coating, which are combined by two methods A large number of Ca elements appeared in the coating of the coating, indicating the presence of biologically active calcium and phosphate salts.
图4是刻划法测试涂层结合强度：本发明微弧氧化-电沉积制备涂层0级(a)及单一电沉积制备涂层2级(b)：在本发明中通过现有划痕法测试涂层的结合强度，从图4(a)中可以看出，微弧氧化-电沉积法制备涂层的切割边缘完全平滑，无一格脱落，可以把该涂层的结合强度等级定为0级，而在图4(b)中单一恒流电沉积在切口的交叉处或沿切口边缘有涂层脱落，受影响交叉切割面积大于5％，所以定为2级。说明通过微弧氧化-电沉积制备涂层的结合强度大大提高。进一步，通过现有剪切拉伸试验测得单一电沉积所得涂层的结合强度为17～19Mpa，微弧氧化-电沉积所得涂层的结合强度60～80Mpa。Fig. 4 is the scoring method to test the bonding strength of the coating: the micro-arc oxidation-electrodeposition of the present invention prepares the coating level 0 (a) and the single electrodeposition prepares the coating level 2 (b): in the present invention, through the existing scratches It can be seen from Figure 4(a) that the cutting edge of the coating prepared by the micro-arc oxidation-electrodeposition method is completely smooth without any falling off, and the bonding strength level of the coating can be determined It is
图5是镁合金基体(1)，单一微弧氧化试样(2)，本发明微弧氧化-电沉积制备涂层(3)在模拟体液中的极化曲线：通过试验曲线可以清楚看到通过两种改性后的镁合金耐腐蚀性能都有所提高，其中通过微弧氧化-电沉积获得材料比基体腐蚀电位提高146mV，腐蚀电流密度降低2个数量级左右。整个极化曲线说明微弧氧化-电沉积制备的涂层通过微弧氧化及电沉积的半封孔作用，提高了整体的耐腐蚀性能，对基体的保护作用更强更稳定了，达到了预期的设计目的。Fig. 5 is the polarization curve of a magnesium alloy substrate (1), a single micro-arc oxidation sample (2), and a coating prepared by micro-arc oxidation-electrodeposition of the present invention (3) in simulated body fluid: it can be clearly seen by the test curve The corrosion resistance of the two modified magnesium alloys is improved, and the corrosion potential of the material obtained by micro-arc oxidation-electrodeposition is 146mV higher than that of the substrate, and the corrosion current density is reduced by about 2 orders of magnitude. The entire polarization curve shows that the coating prepared by micro-arc oxidation-electrodeposition improves the overall corrosion resistance through the semi-sealing effect of micro-arc oxidation and electrodeposition, and has a stronger and more stable protective effect on the substrate, which meets expectations. design purpose.
综上所述，本发明微弧氧化-电沉积复合方法制备的生物活性涂层从结构上要优于单一的微弧氧化和单一的电沉积制备的涂层，同时也弥补了单一电沉积制备的涂层的结合强度不高的缺点。In summary, the bioactive coating prepared by the composite method of micro-arc oxidation-electrodeposition of the present invention is superior to the coating prepared by single micro-arc oxidation and single electrodeposition in structure, and also makes up for the single electrodeposition preparation. The disadvantage of the coating's bonding strength is not high.
实施例2Example 2
在Mg-3wt％Al合金表面微弧氧化-电沉积制备生物活性涂层的方法，包括以下步骤：The method for preparing a bioactive coating by micro-arc oxidation-electrodeposition on the surface of Mg-3wt%Al alloy comprises the following steps:
(1)预处理基体材料：使用100#、200#、400#、600#、800#、1000#SiC金相砂纸依次抛光基体材料后，将基体材料置于体积比为1∶1的丙酮/无水乙醇混合溶液中超声清洗5min，用来除去基体材料上的杂质和油脂，清洗后室温自然干燥备用；(1) Pretreatment of the base material:
(2)配制微弧氧化电解液：微弧氧化电解液是由下述浓度的各成份组成的水溶液：Na3PO40.06mol/L、NaOH 0.025mol/L；(2) Preparation of micro-arc oxidation electrolyte: micro-arc oxidation electrolyte is an aqueous solution composed of the following components: Na3 PO4 0.06mol/L, NaOH 0.025mol/L;
(3)微弧氧化：以步骤(1)中处理好的镁基基底材料为阳极，不锈钢片为阴极，将阳极和阴极浸没在步骤(2)中配制好的电解液中于室温搅拌(20转/分钟)下进行恒电流微弧氧化反应，其中两极间距5cm，反应电压200～350V，反应电流0.5A，占空比12％，正向频率600Hz，反应时间60min，将反应过后的微弧氧化试样冲洗、干燥备用；(3) micro-arc oxidation: take the magnesium-based base material processed in step (1) as the anode, and the stainless steel sheet as the cathode, and the anode and the cathode are immersed in the electrolyte prepared in the step (2) and stirred at room temperature (20 (rev/min) for constant current micro-arc oxidation reaction, wherein the distance between two poles is 5cm, the reaction voltage is 200-350V, the reaction current is 0.5A, the duty cycle is 12%, the forward frequency is 600Hz, and the reaction time is 60min. Rinse and dry the oxidized sample for later use;
(4)配制电沉积电解液：电沉积电解液是由下述浓度的各成份组成的水溶液：NaH2PO40.0046mol/L、NaNO30.041mol/L、无水Ca(NO3)20.008mol/L，用质量浓度为1％的稀HNO3或(CH2OH)3CNH2调节溶液pH值为4.0；(4) Preparation of electrodeposition electrolyte: The electrodeposition electrolyte is an aqueous solution composed of the following components: NaH2 PO4 0.0046mol/L, NaNO3 0.041mol/L, anhydrous Ca(NO3 )2 0.008 mol/L, use dilute HNO3 or (CH2 OH)3 CNH2 with a mass concentration of 1% to adjust the pH value of the solution to 4.0;
(5)电沉积：将在步骤(3)中形成的微弧氧化试样作为电沉积反应阴极，石墨片为阳极，将步骤(4)中配制好的电解液加热至50℃，将阴极和阳极浸没在电解液中进行恒电流电沉积反应，其中两极间距2cm，沉积电流密度60mA/cm2，沉积时间90min；(5) Electrodeposition: the micro-arc oxidation sample formed in step (3) is used as the electrodeposition reaction cathode, the graphite sheet is the anode, the electrolyte prepared in the step (4) is heated to 50 ° C, and the cathode and The anode is immersed in the electrolyte for constant current electrodeposition reaction, where the distance between the two electrodes is 2cm, the deposition current density is 60mA/cm2 , and the deposition time is 90min;
(6)将经步骤(5)沉积过后的试样取出，用去离子水冲洗干净之后，在40℃下干燥即可。(6) Take out the sample deposited in step (5), rinse it with deionized water, and then dry it at 40°C.
实施例3Example 3
在纯镁(99.99wt％)合金表面微弧氧化-电沉积制备生物活性涂层的方法，包括以下步骤：The method for preparing a biologically active coating by micro-arc oxidation-electrodeposition on the surface of pure magnesium (99.99wt%) alloy comprises the following steps:
(1)预处理基体材料：使用100#、200#、400#、600#、800#、1000#SiC金相砂纸依次抛光基体材料后，将基体材料置于体积比为1∶1的丙酮/无水乙醇混合溶液中超声清洗15min，用来除去基体材料上的杂质和油脂，清洗后室温自然干燥备用；(1) Pretreatment of the base material:
(2)配制微弧氧化电解液：微弧氧化电解液是由下述浓度的各成份组成的水溶液：Na3PO40.19mol/L、NaOH 0.075mol/L；(2) Preparation of micro-arc oxidation electrolyte: micro-arc oxidation electrolyte is an aqueous solution composed of the following components: Na3 PO4 0.19mol/L, NaOH 0.075mol/L;
(3)微弧氧化：以步骤(1)中处理好的镁基基底材料为阳极，不锈钢片为阴极，将阳极和阴极浸没在步骤(2)中配制好的电解液中于室温搅拌(50转/分钟)下进行恒电流微弧氧化反应，其中两极间距15cm，反应电压250～400V，反应电流3A，占空比15％，正向频率700Hz，反应时间1min，将反应过后的微弧氧化试样冲洗、干燥备用；(3) Micro-arc oxidation: the magnesium-based base material processed in step (1) is used as the anode, and the stainless steel sheet is used as the cathode, and the anode and the cathode are immersed in the electrolyte prepared in the step (2) and stirred at room temperature (50 (rev/min) for constant current micro-arc oxidation reaction, wherein the distance between two poles is 15cm, the reaction voltage is 250-400V, the reaction current is 3A, the duty cycle is 15%, the forward frequency is 700Hz, and the reaction time is 1min. Rinse and dry the sample for later use;
(4)配制电沉积电解液：电沉积电解液是由下述浓度的各成份组成的水溶液：NH4H2PO40.046mol/L、NaNO30.112mol/L、Ca(CH3COO)20.08mol/L，用质量浓度为12％的稀HNO3或(CH2OH)3CNH2调节溶液pH值为7.0；(4) Preparation of electrodeposition electrolyte: The electrodeposition electrolyte is an aqueous solution composed of the following components: NH4 H2 PO4 0.046mol/L, NaNO3 0.112mol/L, Ca(CH3 COO)2 0.08mol/L, use dilute HNO3 or (CH2 OH)3 CNH2 with a mass concentration of 12% to adjust the pH value of the solution to 7.0;
(5)电沉积：将在步骤(3)中形成的微弧氧化试样作为电沉积反应阴极，石墨片为阳极，将步骤(4)中配制好的电解液加热至100℃，将阴极和阳极浸没在电解液中进行恒电流电沉积反应，其中两极间距10cm，沉积电流密度100mA/cm2，沉积时间1min；(5) Electrodeposition: the micro-arc oxidation sample formed in step (3) is used as the electrodeposition reaction cathode, and the graphite sheet is used as the anode, and the electrolyte prepared in step (4) is heated to 100 ° C, and the cathode and The anode is immersed in the electrolyte for constant current electrodeposition reaction, where the distance between the two electrodes is 10cm, the deposition current density is 100mA/cm2 , and the deposition time is 1min;
(6)将经步骤(5)沉积过后的试样取出，用去离子水冲洗干净之后，在60℃下干燥即可。(6) Take out the sample deposited in step (5), rinse it with deionized water, and then dry it at 60°C.
实施例4Example 4
与实施例1的不同之处在于：步骤(2)中的微弧氧化电解液是由下述浓度的各成份组成的水溶液：Na3PO40.1mol/L、NaOH 0.05mol/L、CaCO30.013mol/L；步骤(4)中，电沉积电解液中以Ca(NO3)2·4H2O和无水Ca(NO3)2的组合代替Ca(NO3)2·4H2O，且浓度分别为Ca(NO3)2·4H2O 0.01mol/L、无水Ca(NO3)20.03mol/L。The difference from Example 1 is that the micro-arc oxidation electrolyte in step (2) is an aqueous solution composed of the following components: Na3 PO4 0.1mol/L, NaOH 0.05mol/L, CaCO3 0.013mol/L; in step (4), the combination of Ca(NO3 )2 4H2 O and anhydrous Ca(NO3 )2 replaces Ca(NO3 )2 4H2 O in the electrodeposition electrolyte, And the concentrations are respectively Ca(NO3 )2 ·4H2 O 0.01 mol/L and anhydrous Ca(NO3 )2 0.03 mol/L.
为说明本发明微弧氧化-电沉积复合制备方法在优化微弧氧化电解液之后所发生的变化，本实施例中在对基底材料进行预处理之后同样在保持本实施例相同的微弧氧化电解液和微弧氧化试验参数相同的条件下进行单一微弧氧化对照试验，结果如下：In order to illustrate the changes in the micro-arc oxidation-electrodeposition composite preparation method of the present invention after optimizing the micro-arc oxidation electrolyte, in this example, after pretreatment of the substrate material, the same micro-arc oxidation electrolysis method as in this example is also maintained. A single micro-arc oxidation control test was carried out under the same conditions as the liquid and micro-arc oxidation test parameters, and the results are as follows:
图6是单一微弧氧化后(a)及本发明微弧氧化-电沉积(b)制备涂层的XRD图谱：从图6(a)可以看出，与实施例1的图1(a)相比，在此优化后的微弧氧化电解液生成的涂层中多出了CaP4O11和CaH2P2O5两个谱峰，说明微弧氧化电解液优化后，确实促进了微弧氧化后涂层中钙盐的形成，而从图6(b)中可以看出在微弧氧化-电沉积的涂层中所包括的产物与实施例1一致。Fig. 6 is the XRD pattern of coating after single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b) of the present invention: as can be seen from Fig. 6 (a), and Fig. 1 (a) of
通过现有剪切拉伸试验测得本实施例中微弧氧化-电沉积所得涂层的结合强度也在60～80Mpa之内。The bonding strength of the coating obtained by micro-arc oxidation-electrodeposition in this embodiment is also within 60-80 MPa as measured by the existing shear tensile test.
图7是单一微弧氧化(a)及本发明微弧氧化-电沉积(b，c)制备涂层的SEM形貌图：在图7(a)中可以看出在涂层表面除了会出现白色点状形貌外，与实施例1的图2(a)结果类似，同样布满了微孔，在图7(b，c)中可以发现，微弧氧化-电沉积制备的涂层除了形成的片状晶体与实施例1中的条状晶体略有不同外，和实施例1结果相比也并无明显变化。Fig. 7 is the SEM topography figure of coating prepared by single micro-arc oxidation (a) and micro-arc oxidation-electrodeposition (b, c) of the present invention: in Fig. 7 (a), it can be seen that in addition to appearing Except for the white dot shape, similar to the result of Figure 2(a) of Example 1, it is also full of micropores. It can be found in Figure 7(b, c) that the coating prepared by micro-arc oxidation-electrodeposition except The plate-shaped crystals formed are slightly different from the strip-shaped crystals in Example 1, and compared with the results of Example 1, there is no obvious change.
图8是微弧氧化-电沉积制备试样在模拟体液中的极化曲线：从图8中可以看出其耐腐蚀性能与基体(图5(1))相比也有所提高。Figure 8 is the polarization curve of the sample prepared by micro-arc oxidation-electrodeposition in simulated body fluid: it can be seen from Figure 8 that its corrosion resistance is also improved compared with the matrix (Figure 5(1)).
实施例5Example 5
与实施例2的不同之处在于：以Mg-2.5wt％Ca为基底材料；步骤(2)中的微弧氧化电解液是由下述浓度的各成份组成的水溶液：Na3PO40.06mol/L、NaOH0.025mol/L、Ca(OH)20.01mol/L。The difference from Example 2 is that: Mg-2.5wt% Ca is used as the base material; the micro-arc oxidation electrolyte in step (2) is an aqueous solution composed of the following components: Na3 PO4 0.06mol /L, NaOH 0.025mol/L, Ca(OH)2 0.01mol/L.
实施例6Example 6
与实施例3的不同之处在于：以Mg-2wt％Mn为基底材料；步骤(2)中的微弧氧化电解液是由下述浓度的各成份组成的水溶液：Na3PO40.06mol/L、NaOH0.025mol/L、CaCO30.008mol/L、Ca(OH)20.007mol/L；步骤(4)中，电沉积电解液中以NH4H2PO4和NaH2PO4的组合代替NH4H2PO4，且浓度分别为NH4H2PO40.02mol/L、NaH2PO40.026mol/L，以Ca(NO3)2·4H2O、无水Ca(NO3)2和Ca(CH3COO)2的组合代替Ca(CH3COO)2，且浓度分别为Ca(NO3)2·4H2O0.01mol/L、无水Ca(NO3)20.03mol/L、Ca(CH3COO)20.04mol/L。The difference from Example 3 is: Mg-2wt%Mn is used as the base material; the micro-arc oxidation electrolyte in step (2) is an aqueous solution composed of the following components: Na3 PO4 0.06mol/ L, NaOH0.025mol/L, CaCO3 0.008mol/L, Ca(OH)2 0.007mol/L; in step (4), the combination of NH4 H2 PO4 and NaH2 PO4 in the electrodeposition electrolyte Instead of NH4 H2 PO4 , and the concentrations are NH4 H2 PO4 0.02mol/L, NaH2 PO4 0.026mol/L, Ca(NO3 )2 ·4H2 O, anhydrous Ca(NO3 )2 and Ca(CH3 COO)2 instead of Ca(CH3 COO)2 , and the concentrations are respectively Ca(NO3 )2 ·4H2 O 0.01mol/L, anhydrous Ca(NO3 )2 0.03mol /L, Ca(CH3 COO)2 0.04 mol/L.
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