CN101302638A - A kind of preparation method of nano HAP coating/magnesium alloy composite biological material - Google Patents
A kind of preparation method of nano HAP coating/magnesium alloy composite biological materialDownload PDFInfo
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Abstract
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Translated fromChinese技术领域technical field
本发明属于镁合金生物材料制备技术领域，具体涉及一种纳米HAP(HAP为羟基磷灰石)涂层/镁合金复合生物材料的制备方法。The invention belongs to the technical field of magnesium alloy biomaterial preparation, and in particular relates to a preparation method of nanometer HAP (HAP is hydroxyapatite) coating/magnesium alloy composite biomaterial.
背景技术Background technique
生命医学材料涉及到人类的健康和生命质量的提高，是一类新发展的高技术新材料，正发展成为21世纪经济的一个支柱性产业。人工骨骼材料植入人体内，必须满足两个基本条件：(1)植入材料应具有良好的生物相容性和高的生物活性；(2)植入材料应具有合适的力学性能和一定的化学稳定性。目前最常用的内固定金属材料主要有不锈钢、Co-Cr合金、钛及合金，相比于陶瓷和聚合物，它们有着较高的力学性能，更适合作为骨植入材料。但它们的缺点也逐渐显现出来，如应力遮挡、电解腐蚀、二次手术等。Life medical materials are related to the improvement of human health and life quality. They are a kind of newly developed high-tech new materials and are developing into a pillar industry of the 21st century economy. The implantation of artificial bone materials into the human body must meet two basic conditions: (1) the implant material should have good biocompatibility and high bioactivity; (2) the implant material should have suitable mechanical properties and certain chemical stability. At present, the most commonly used metal materials for internal fixation are mainly stainless steel, Co-Cr alloy, titanium and alloys. Compared with ceramics and polymers, they have higher mechanical properties and are more suitable as bone implant materials. But their shortcomings have gradually emerged, such as stress shielding, electrolytic corrosion, and secondary surgery.
可降解生物材料已经被许多发达国家列为21世纪重点发展对象。镁及镁合金是一种可在体内环境降解的金属材料，作为生物材料，可以有效地避免上述不良反应，并具有和人骨相近的力学性能以及良好的生物相容性：(1)组织韧性比陶瓷生物材料好；另外弹性模量和抗压强度也比其他金属植入材料更接近人骨，可以避免将金属植入人体内因材料的弹性模量不匹配产生的应力屏蔽现象。(2)镁及镁合金的密度约为1.7g/cm3，在所有结构材料中最小，与人体致密骨的密度1.75g/cm3最为接近，远低于Ti6Al4V的密度4.47g/cm3。(3)镁合金具有体内可降解性，不需要进行二次手术。(4)镁元素本身就是人体所必需的元素，在体内含量仅次于钾，它参与体内一系列的新陈代谢，包括加速骨细胞的形成，骨细胞的愈合等。镁元素还与神经、肌肉和心脏关系密切。所以将镁植入人体，不仅不用考虑微量金属离子对人体细胞的毒性，而且植入材料中镁离子的微量释放还对人体有益。Degradable biomaterials have been listed as key development targets in the 21st century by many developed countries. Magnesium and magnesium alloys are metal materials that can be degraded in the internal environment. As biomaterials, they can effectively avoid the above adverse reactions, and have similar mechanical properties to human bone and good biocompatibility: (1) Tissue toughness ratio Ceramic biomaterials are good; in addition, the elastic modulus and compressive strength are closer to human bones than other metal implant materials, which can avoid the stress shielding phenomenon caused by the mismatch of elastic modulus of materials when implanting metals into the human body. (2) The density of magnesium and magnesium alloys is about 1.7g/cm3 , which is the smallest among all structural materials, and is closest to the density of 1.75g/cm3 of human compact bone, which is far lower than the density of 4.47g/cm3 of Ti6Al4V. (3) Magnesium alloys are biodegradable in vivo and do not require secondary surgery. (4) Magnesium itself is an essential element for the human body, and its content in the body is second only to potassium. It participates in a series of metabolism in the body, including accelerating the formation of bone cells and the healing of bone cells. Magnesium is also closely related to nerves, muscles and heart. Therefore, implanting magnesium into the human body not only does not need to consider the toxicity of trace metal ions to human cells, but also the trace release of magnesium ions in the implanted material is beneficial to the human body.
Zreiqat等(Zreiqat H，Howlett CR，Zannettino A，et al.Mechanisms ofmagnesium stimulated adhesion of osteoblastic cells to commonly usedorthopaedic implantsJ.J Biomed Mater Res.2002，622：175-184.)、Yamasak等(Yamasaki Y，Yoshida Y，Okazaki M，et al.Synthesis of functionally gradedMgCO3 apatite accelerating osteoblast adhesionJ.J Biomed Mater Res，2002，621：99-105.)通过实验表明含有镁离子的生物陶瓷种植体、胶原的表面成骨细胞黏附增加，整合素表达及信号传导蛋白基因表达增高，骨整合能力增强。常晓峰等采用动物实验认为，早期补充镁可以加快骨痂牵引成骨的速度，促进骨质的成熟与功能的发挥。Sul等(Sul YT，Johansson C，Albrektsson T.Whichsurface properties enhance bone response to implants Comparison of oxidizedmagnesium，Tiunite and Osseotite implant surfaces J.Int J Prosthodont.2006，19)通过动物实验表明，在钛或者镁种植体表面镀含镁离子陶瓷膜可提高骨整合能力，并能够提供早期的功能负荷。Witte等(Witte F，Kaese V，Haferkamp H，et al.In vivo corrosionoffour magnesium alloys and the associated bone responseJ.Biomaterials，2005，26 17：3557-3563.)的实验证明镁基种植体较聚乳酸表面有更多钙磷酸盐形成，周围骨量增加，提示高浓度的镁离子可提高成骨细胞的活性；在体外环境中镁可促进磷酸钙沉积，增加成骨作用，同时改善原位耐蚀性。Zreiqat et al. (Zreiqat H, Howlett CR, Zannettino A, et al. Mechanisms ofmagnesium stimulated adhesion of osteoblastic cells to commonly used orthopedic implants J.J Biomed Mater Res. 2002, 622: 175-184.), Yamasak et al. (Yamasaki Y, Yoshida Yama , Okazaki M, et al.Synthesis of functionally gradedMgCO3 apatite accelerating osteoblast adhesion J.J Biomed Mater Res, 2002, 621:99-105.) Experiments show that bioceramic implants containing magnesium ions, collagen surface osteoblast adhesion Increased, integrin expression and signal transduction protein gene expression increased, osseointegration ability enhanced. Chang Xiaofeng et al. used animal experiments to believe that early magnesium supplementation can accelerate the speed of callus traction and osteogenesis, and promote the maturation and function of bone. Sul et al. (Sul YT, Johansson C, Albrektsson T. Which surface properties enhance bone response to implants Comparison of oxidized magnesium, Tiunite and Osseotite implant surfaces J. Int J Prosthodont. 2006, 19) showed through animal experiments that on the surface of titanium or magnesium implants Magnesium-ion-coated ceramic membranes can improve osseointegration and provide early functional loading. Experiments by Witte et al. (Witte F, Kaese V, Haferkamp H, et al. In vivo corrosion offour magnesium alloys and the associated bone response J. Biomaterials, 2005, 26 17: 3557-3563.) proved that magnesium-based implants are more effective than polylactic acid surfaces. More calcium phosphate was formed, and the surrounding bone mass increased, suggesting that high concentrations of magnesium ions can increase the activity of osteoblasts; in vitro, magnesium can promote calcium phosphate deposition, increase osteogenesis, and improve in situ corrosion resistance.
综上所述，镁及镁合金具有足够的强度，良好的生物相容性和体内可降解性，有望成为新型骨植入材料。但是由于骨组织完全修复需要12-18周，而在pH值为7.4-7.6的体液环境中纯镁的降解速度较快，还没等骨组织修复完全就被降解完全，限制了镁及镁合金作为骨修复和骨植入材料的应用。因此，要使镁代替现有的生物植入材料成为可能，就必须对金属镁进行合金化或表面改性来提供腐蚀性能和生物相容性。In summary, magnesium and magnesium alloys have sufficient strength, good biocompatibility and in vivo degradability, and are expected to become new bone implant materials. However, since it takes 12-18 weeks for the complete repair of bone tissue, and the degradation rate of pure magnesium is relatively fast in the body fluid environment with a pH value of 7.4-7.6, it will be completely degraded before the bone tissue repair is complete, which limits the development of magnesium and magnesium alloys. Applications as bone repair and bone implant materials. Therefore, to make it possible for magnesium to replace existing bioimplant materials, it is necessary to alloy or surface modify magnesium metal to provide corrosion performance and biocompatibility.
表面改性是一种有效控制镁基材料降解速率，改善生物相容性的途径。HAP涂层在体液PH＝7.4环境下稳定，对镁合金的耐腐蚀性能有一定的提高，同时它具备良好的生物相容性，能与骨组织形成化学键，对骨组织在镁合金表面沉积有积极的诱导作用，促进骨的生长并缩短治愈时间。但HAP材料的力学性能较差，抗折强度和断裂韧性指标均低于人体致密骨，因而限制了在人体硬组织上的应用。因此，采用HAP涂层对镁合金进行表面改性使材料既具有金属的强度和韧性，又有HAP良好的生物相容性，同时还具备体内植入的可降解性，非常适合于临床医学上植入材料的应用。Surface modification is an effective way to control the degradation rate of magnesium-based materials and improve biocompatibility. The HAP coating is stable in the environment of body fluid PH=7.4, and it can improve the corrosion resistance of magnesium alloy to a certain extent. At the same time, it has good biocompatibility, can form chemical bonds with bone tissue, and has a good effect on the deposition of bone tissue on the surface of magnesium alloy. Positive induction, promotes bone growth and shortens healing time. However, the mechanical properties of HAP materials are poor, and the flexural strength and fracture toughness indexes are lower than those of human compact bone, thus limiting the application in human hard tissues. Therefore, the surface modification of magnesium alloy with HAP coating makes the material not only have the strength and toughness of metal, but also have the good biocompatibility of HAP, and also have the degradability of implantation in vivo, which is very suitable for clinical medicine. Application of implant materials.
HAP涂层的制备方法很多，镁合金的熔点低且耐蚀性差，作为镁基可降解材料，其涂层制备方法的选择更加至关重要。除了等离子喷涂、激光熔敷等高温制备方法会造成基体过热和涂层高温相变，导致力学性能下降、生物活性降低；溶胶-凝胶法常常伴随着高温热处理，也不适合于镁合金；对于仿生生长法，由于镁合金在仿生溶液中腐蚀较快，也容易形成局部腐蚀而影响力学性能。采用电化学法，通过对镁合金基体的预处理，涂层制备过程工艺参数的控制以，能实现涂层的低温制备，避免基体过热和涂层相变。通过工艺参数控制，可以制备Ca/P原子比呈现非化学计量比。There are many preparation methods for HAP coatings. Magnesium alloys have low melting points and poor corrosion resistance. As magnesium-based degradable materials, the choice of coating preparation methods is even more important. In addition to high-temperature preparation methods such as plasma spraying and laser cladding, which will cause overheating of the substrate and high-temperature phase transformation of the coating, resulting in a decrease in mechanical properties and biological activity; the sol-gel method is often accompanied by high-temperature heat treatment, which is not suitable for magnesium alloys; In the biomimetic growth method, since the magnesium alloy corrodes quickly in the biomimetic solution, it is also easy to form localized corrosion and affect the mechanical properties. Using electrochemical method, through the pretreatment of the magnesium alloy substrate and the control of the process parameters of the coating preparation process, the low-temperature preparation of the coating can be realized, and the overheating of the substrate and the phase change of the coating can be avoided. By controlling the process parameters, the Ca/P atomic ratio can be prepared to present a non-stoichiometric ratio.
Shirkhanzadeh等(Shirkhanzadeh M.J.Mater Sci Let，1993，12：16)首先用电沉积法以医用钛合金Ti6Al4V为阴极，铂片为阳极，获得非常均匀的、由尺寸为15～20μm的片状无定向晶体组成的磷酸钙涂层，Ca/P比为1.63。Royer等(Royer P，Pey C.Surface and Coating Technology，1991，45：171在pH值为7.8，沉积液温度20～70℃，电压-3V的条件下，于钛的表面沉积了磷酸钙生物活性陶瓷。)Hidexi等(Hideki M.J Ceram Soc Jap，1993，101：737)报道了用电沉积法在不锈钢表面沉积缺钙磷灰石的工艺，改变电沉积工艺条件，可获得椭圆型、针状或细小颗粒状的磷灰石晶体涂层。Shirkhanzadeh et al. (Shirkhanzadeh M.J. Mater Sci Let, 1993, 12:16) first used the electrodeposition method to use the medical titanium alloy Ti6Al4V as the cathode and the platinum sheet as the anode to obtain very uniform flake-like amorphous crystals with a size of 15-20 μm. The composition of the calcium phosphate coating has a Ca/P ratio of 1.63. Royer et al. (Royer P, Pey C. Surface and Coating Technology, 1991, 45: 171) deposited calcium phosphate on the surface of titanium under the conditions of pH value 7.8, deposition solution temperature 20-70°C, and voltage -3V. Ceramics.) Hidexi et al. (Hideki M.J Ceram Soc Jap, 1993, 101:737) reported the process of depositing calcium-deficient apatite on the surface of stainless steel by electrodeposition, changing the electrodeposition process conditions, and obtaining elliptical, acicular or Coating of finely grained apatite crystals.
“一种类骨HAP/镁合金涂层生物材料及其制备方法”的专利申请(申请号为200710189682.5)披露了一种采用恒流的电化学法可以在镁合金表面沉积上良好的羟基磷灰石涂层的方法，其电沉积步骤为，在加热的电解液至中放入石墨(阳极)及处理好的基体材料(阴极)，根据电流密度和试样表面积计算沉积电流(电流＝电流密度×表面积)，电流密度设为1.0～2.5mA/cm2，打开电源调节电流后记时沉积，时间设为0.5～2h，用去离子水漂洗，干燥即可。但在电沉积过程中当沉积电位较高时试样表面会出现较为严重的析氢现象，这大大影响了磷酸盐的成核，使涂层不是很致密，且结合强度较低，而析氢反应产生的OH又是形成羟基磷灰石晶体必需的。The patent application of "a bone-like HAP/magnesium alloy coating biomaterial and its preparation method" (application number 200710189682.5) discloses a constant current electrochemical method that can deposit good hydroxyapatite on the surface of magnesium alloys The method of coating, its electrodeposition step is, puts graphite (anode) and the matrix material (cathode) that has processed in the electrolytic solution that heats up, calculates deposition current according to current density and sample surface area (current=current density× Surface area), the current density is set to 1.0-2.5mA/cm2 , and the deposition time is recorded after turning on the power supply to adjust the current. The time is set to 0.5-2h, rinsed with deionized water, and dried. However, during the electrodeposition process, when the deposition potential is high, more serious hydrogen evolution phenomenon will appear on the surface of the sample, which greatly affects the nucleation of phosphate, making the coating not very dense, and the bonding strength is low, while the hydrogen evolution reaction produces The OH is again necessary for the formation of hydroxyapatite crystals.
发明内容Contents of the invention
本发明的目的在于提供一种既有利于HAP表面沉积，又大大减少沉积过程中析氢反应，能制备出涂层致密且性能良好的纳米HAP涂层/镁合金复合生物材料的方法。The purpose of the present invention is to provide a method that is beneficial to the surface deposition of HAP, greatly reduces the hydrogen evolution reaction in the deposition process, and can prepare a nano-HAP coating/magnesium alloy composite biological material with a dense coating and good performance.
为了实现上述目的，本发明采用的技术方案如下。In order to achieve the above object, the technical scheme adopted by the present invention is as follows.
制备纳米HAP涂层/镁合金复合生物材料的方法，包括以下步骤：The method for preparing nano HAP coating/magnesium alloy composite biological material comprises the following steps:
(1)涂层电解液的配制(1) Preparation of coating electrolyte
电解液各成分如下，电解液由磷酸二氢氨(99.5％)、硝酸钠(99％)和四水硝酸钙(99％)配制而成，电解液中钙磷原子比按1.6～2.5配制，每升溶液中各成分的含量为：NH4H2PO40.54g～5.4g，NaNO33.2g～9.6g，Ca(NO3)2·4H2O1.86g～18.6g，用HNO3或(CH2OH)3CNH2调节溶液pH值为3.0～7.0，充分搅拌均匀，备用；The components of the electrolyte are as follows. The electrolyte is prepared from ammonium dihydrogen phosphate (99.5%), sodium nitrate (99%) and calcium nitrate tetrahydrate (99%). The atomic ratio of calcium and phosphorus in the electrolyte is prepared according to 1.6-2.5. The contents of each component in each liter of solution are: NH4 H2 PO4 0.54g~5.4g, NaNO3 3.2g~9.6g, Ca(NO3 )2 4H2 O 1.86g~18.6g, use HNO3 or (CH2 OH)3 CNH2 to adjust the pH value of the solution to 3.0-7.0, stir well and set aside;
(2)基体材料的预处理(2) Pretreatment of the base material
选用镁合金基板作基体材料，先用100～1000SiC金相砂纸依次打磨抛光，用去离子水洗；按0.5～1∶1的体积比配置丙酮、酒精混合溶液，将基体材料置于该混合溶液中超声清洗5～25min除油，在室温下干燥；并在室温下放入20％～40％氢氟酸溶液活化处理5～30min，然后用去离子水洗，自然干燥；Choose the magnesium alloy substrate as the base material, first use 100-1000 SiC metallographic sandpaper to polish and polish in turn, and wash with deionized water; prepare a mixed solution of acetone and alcohol at a volume ratio of 0.5-1:1, and place the base material in the mixed solution Ultrasonic cleaning for 5-25 minutes to remove oil, and drying at room temperature; and activation treatment in 20%-40% hydrofluoric acid solution at room temperature for 5-30 minutes, then washing with deionized water, and natural drying;
(3)电沉积(3) Electrodeposition
将上述配置的涂层电解液在水浴锅中加热至60℃～95℃，将石墨(阳极)及经过步骤(2)处理好的基体材料(阴极)放入电解液中，先在恒电位-5V～-1V条件下预镀5～30min，将所获得的预镀层用二次蒸馏水清洗，干燥后置于0.1～1mol/L的NaOH碱溶液中在60～95℃处理2～3h，使电沉积前躯体转变为HAP样品；样品用二次蒸馏水洗净，自然晾干，然后采用连续双电位阶跃进行电沉积制备HAP涂层，先从开路电位E1＝0V阶跃至E2为-5V～-1V，停留一定时间记作t1为5～60s；再阶跃回E1＝0V，维持一段时间，记作t2为5～60s，如此反复连续的循环阶跃，电沉积时间控制在0.5～3h，到时间后取出用去离子水漂洗，在室温下干燥，制得试样；Heat the above-mentioned coated electrolyte in a water bath to 60°C-95°C, put the graphite (anode) and the substrate material (cathode) treated in step (2) into the electrolyte, Pre-plating at 5V~-1V for 5~30min, wash the obtained precoating layer with double distilled water, dry it and place it in 0.1~1mol/L NaOH alkali solution at 60~95℃ for 2~3h to make the electrode The pre-deposition body is transformed into a HAP sample; the sample is washed with double distilled water, dried naturally, and then the HAP coating is prepared by electrodeposition using continuous bipotential steps, first stepping from the open circuit potential E1 = 0V to E2 as - 5V～-1V, stay for a certain time as t1 is 5～60s; then step back to E1 =0V, maintain for a period of time, record t2 as 5～60s, such repeated and continuous cycle steps, the electrodeposition time Control it within 0.5-3 hours, take it out after the time is up, rinse it with deionized water, and dry it at room temperature to prepare the sample;
(4)碱处理(4) Alkali treatment
碱液处理采用0.1～1mol/L的NaOH溶液，加热至60-95℃，将步骤(3)制备的试样放入NaOH溶液中浸泡2～8h后取出，用去离子水漂洗数次，直至其表面的碱液清洗干净，然后放入60～120℃的干燥箱中烘4～24h取出，即制得纳米HAP/镁合金涂层复合材料。Alkali treatment uses 0.1-1mol/L NaOH solution, heats to 60-95°C, puts the sample prepared in step (3) into NaOH solution for 2-8 hours, takes it out, rinses it with deionized water several times, until The lye on the surface is cleaned, and then put into a drying oven at 60-120° C. for 4-24 hours and taken out to obtain the nanometer HAP/magnesium alloy coating composite material.
其中，镁合金为基体为Mg-(Zn、Al、Mn、Ca)基合金；涂层为纳米HAP，其晶粒尺寸为10-100纳米。用上述方法制得的纳米HAP涂层/镁合金复合生物材料可用于人体骨的植入和修复中。Wherein, the magnesium alloy is a Mg-(Zn, Al, Mn, Ca) base alloy as the matrix; the coating is nano-HAP, and its grain size is 10-100 nanometers. The nanometer HAP coating/magnesium alloy composite biomaterial prepared by the above method can be used in the implantation and repair of human bone.
与现有的技术相比，本发明的优点在于：Compared with the prior art, the present invention has the advantages of:
1.在镁合金基体表面成功制备了结合强度较好、表面涂层均匀致密的纳米HAP涂层。该涂层不含杂质相，结晶度高(95％以上)，结晶晶粒为纳米级针状HAP，钙磷比较高在1.6～1.67之间可调；涂层具备良好的生物活性。1. A nano-HAP coating with good bonding strength and uniform and dense surface coating was successfully prepared on the surface of the magnesium alloy substrate. The coating does not contain impurity phases, has high crystallinity (above 95%), the crystal grains are nanoscale needle-shaped HAP, and the calcium-phosphorus ratio is adjustable between 1.6 and 1.67; the coating has good biological activity.
2.利用电化学法和低温碱处理相结合，实现涂层的低温制备，避免基体过热和涂层相变。2. Using the combination of electrochemical method and low-temperature alkali treatment to realize the low-temperature preparation of the coating, avoiding the overheating of the substrate and the phase change of the coating.
3.采用了重复多次的双电位阶跃的循环操作，可以改变析氢反应给涂层沉积的破坏，可使HAP在镁合金表面更好地结晶、稳定生长，获得性能良好的致密涂层。同时可以实现镁离子对羟基磷灰石的原位掺杂，在镁合金表面生成镁的磷酸盐过渡层，增加结合强度。3. The cycle operation of repeated double potential steps can be used to change the damage of the hydrogen evolution reaction to the coating deposition, to make HAP better crystallize and grow stably on the surface of the magnesium alloy, and to obtain a dense coating with good performance. At the same time, the in-situ doping of magnesium ions to hydroxyapatite can be realized, and a magnesium phosphate transition layer can be formed on the surface of the magnesium alloy to increase the bonding strength.
附图说明Description of drawings
图1为纳米HAP涂层/镁合金复合生物材料制备的双电位阶跃法的E-t曲线图。Figure 1 is the E-t curve diagram of the bipotential step method prepared by the nano-HAP coating/magnesium alloy composite biomaterial.
图2为优化工艺下得到的纳米HAP涂层/镁合金复合生物材料SEM图。Figure 2 is the SEM image of the nano-HAP coating/magnesium alloy composite biomaterial obtained under the optimized process.
图1中，采用重复多次的双电位阶跃的循环操作在镁合金表面沉积HAP，将E2设定为-5V～-1V左右，E1的电位设定为0V，设t1＝t2，该方法改善沉积过程的析氢现象，能够制备出涂层致密且性能良好的HAP涂层。同时可以实现镁离子对羟基磷灰石的掺杂，在镁合金表面生成镁的磷酸盐过渡层，增加结合强度。In Fig. 1, HAP is deposited on the surface of the magnesium alloy by repeated bipotential step cycles, and E2 is set at about -5V to -1V, the potential of E1 is set at 0V, and t1 =t2 , The method improves the hydrogen evolution phenomenon in the deposition process, and can prepare a HAP coating with a dense coating and good performance. At the same time, the doping of magnesium ions to hydroxyapatite can be realized, and a magnesium phosphate transition layer can be formed on the surface of the magnesium alloy to increase the bonding strength.
图2中，纳米HAP涂层呈花瓣状向外辐射，晶粒呈细小针状得到充分生长且在针状上可以看到更为细小的针状晶体生长；这种针状形貌与骨磷灰石的晶体特征更为相似，而且在基体表面形成交连的多孔网状结构，能提供更大的表面积，从而更有利于体内骨质的沉积，具有更好的生物相容性。In Figure 2, the nano-HAP coating radiates outward in the shape of petals, and the crystal grains are fully grown in the shape of fine needles, and finer needle-like crystals can be seen growing on the needles; this needle-like morphology is similar to that of bone phosphorus The crystal characteristics of limestone are more similar, and an interlinked porous network structure is formed on the surface of the matrix, which can provide a larger surface area, which is more conducive to the deposition of bone in the body and has better biocompatibility.
具体实施方法Specific implementation method
下面结合实施例对本发明作进一步描述，但不限于下列实施例。The present invention will be further described below in conjunction with the examples, but not limited to the following examples.
实施例1：Example 1:
以AZ31镁合金作为基体材料，其合金成分(wt％)为：Al 3.13％，Zn 1.21％，Mn 0.47％，Si 0.04％，Mg余量。AZ31 magnesium alloy is used as the base material, and its alloy composition (wt%) is: Al 3.13%, Zn 1.21%, Mn 0.47%, Si 0.04%, Mg balance.
(1)配制涂层电解液：称取NH4H2PO4(99.5％)0.54g，NaNO3(99％)6.38g，Ca(NO3)2.4H2O(99％)1.89g，配置成稀溶液750ml，即调整钙磷原子比为1.67，用玻璃棒搅拌均匀；用HNO3或(CH2OH)3CNH2调节溶液的PH值为5.0，充分搅拌均匀，获得待用电解液。(1) Preparation of coating electrolyte: weigh NH4 H2 PO4 (99.5%) 0.54g, NaNO3 (99%) 6.38g, Ca(NO3 )2 .4H2 O (99%) 1.89g, Configure 750ml of dilute solution, that is, adjust the calcium-phosphorus atomic ratio to 1.67, and stir evenly with a glass rod; adjust the pH value of the solution to 5.0 with HNO3 or (CH2 OH)3 CNH2 , stir well, and obtain the ready-to-use electrolyte .
(2)基体材料预处理：AZ31镁合金基板线切割成的矩形块，用100-1000金相砂纸依次打磨抛光，用去离子水洗后，配置丙酮、酒精混合溶液，其体积比为1∶1，将基体材料置于该混合溶液中超声清洗10min除油，在室温下干燥；并在室温下放入40％氢氟酸溶液活化处理10min，然后用去离子水洗，量取基体长度2.5cm，宽度1.0cm，高度0.7cm，多余部分用硅橡胶覆盖，自然干燥。(2) Substrate material pretreatment: AZ31 magnesium alloy substrate is wire-cut into rectangular blocks, polished and polished sequentially with 100-1000 metallographic sandpaper, washed with deionized water, and prepared with acetone and alcohol mixed solution, the volume ratio of which is 1:1 , place the matrix material in the mixed solution for ultrasonic cleaning for 10 minutes to remove oil, and dry at room temperature; put 40% hydrofluoric acid solution at room temperature for activation treatment for 10 minutes, then wash with deionized water, measure the length of the matrix to 2.5cm, The width is 1.0cm, and the height is 0.7cm. The excess part is covered with silicone rubber and dried naturally.
(3)电沉积：将配制的涂层电解液在水浴锅中加热至80℃，将石墨(阳极)及处理好的基体材料(阴极)放置电解液中，先在恒电位-3V条件下预镀20min，将所获得的预镀层用二次蒸馏水清洗，干燥后置于0.5mol/L的NaOH碱溶液中在80℃处理2h，使电沉积前躯体转变为HAP样品；样品用二次蒸馏水洗净，自然晾干。然后采用连续双电位阶跃法进行电沉积HAP涂层，先从开路电位E1＝0V阶跃至E2为-3.2V，停留20s(t1)，再阶跃回E1＝0V，维持20s(t2)，如此循环阶跃1h后取出用去离子水漂洗，室温下干燥。(3) Electrodeposition: Heat the prepared coating electrolyte to 80°C in a water bath, place the graphite (anode) and the treated substrate material (cathode) in the electrolyte, and pre- Plating for 20 minutes, the obtained pre-plating layer was washed with double distilled water, dried and placed in 0.5mol/L NaOH alkali solution at 80°C for 2 hours to convert the electrodeposited precursor into a HAP sample; the sample was washed with double distilled water Clean and dry naturally. Then use the continuous bipotential step method to electrodeposit HAP coating, first step from the open circuit potential E1 = 0V to E2 at -3.2V, stay for 20s (t1 ), then step back to E1 = 0V, and maintain 20s (t2 ), after such a cycle step for 1h, take it out, rinse it with deionized water, and dry it at room temperature.
(4)碱处理：碱液处理采用0.5mol/L的NaOH溶液，加热至80℃，将制备的试样放入溶液中浸泡5h后取出，用去离子水漂洗数次，清洗掉表面的碱液，然后放入80℃的干燥箱中烘10h取出，即制得纳米HAP/镁合金涂层复合材料。(4) Alkali treatment: 0.5mol/L NaOH solution is used for alkali treatment, heated to 80°C, the prepared sample is soaked in the solution for 5 hours, taken out, rinsed with deionized water several times, and the alkali on the surface is cleaned solution, and then put it into a drying oven at 80°C for 10 hours and take it out to obtain a nanometer HAP/magnesium alloy coating composite material.
实施例2：Example 2:
以ZK60镁合金作为基体材料，其合金成分(wt％)为：Zn 5.83％，Zr 0.45％，Mn 0.04％，Ca 0.02％，Mg余量。Using ZK60 magnesium alloy as the base material, its alloy composition (wt%) is: Zn 5.83%, Zr 0.45%, Mn 0.04%, Ca 0.02%, Mg balance.
(1)电解液的配置：称取NH4H2PO4(99.5％)2.7g，NaNO3(99％)3.2g，Ca(NO3)2.4H2O(99％)9.45g，配置成稀溶液750ml，即调整钙磷原子比为1.67，用玻璃棒搅拌均匀，用HNO3或(CH2OH)3CNH2调节溶液的PH值为6.0，充分搅拌均匀，获得待用电解液。(1) Electrolyte configuration: weigh NH4 H2 PO4 (99.5%) 2.7g, NaNO3 (99%) 3.2g, Ca(NO3 )2 .4H2 O (99%) 9.45g, configure Dilute solution to 750ml, that is, adjust the calcium-phosphorus atomic ratio to 1.67, stir evenly with a glass rod, adjust the pH value of the solution to 6.0 with HNO3 or (CH2 OH)3 CNH2 , stir well, and obtain a ready-to-use electrolyte.
(2)基体材料的预处理：AZ31镁合金基板线切割成的矩形块，用100-1000金相砂纸依次打磨抛光，用去离子水洗后，配置丙酮：酒精体积比为0.8∶1的混合溶液，将基体材料置于该混合溶液中超声清洗5min除油，在室温下干燥；并在室温下放入30％氢氟酸溶液活化处理20min，然后用去离子水洗；量取基体长度2.5cm，宽度1.0cm，高度0.7cm，多余部分用硅橡胶覆盖，自然干燥。(2) Pretreatment of substrate materials: AZ31 magnesium alloy substrates are cut into rectangular pieces by wire, polished and polished sequentially with 100-1000 metallographic sandpaper, washed with deionized water, and mixed with acetone:alcohol with a volume ratio of 0.8:1. , place the matrix material in the mixed solution for ultrasonic cleaning for 5 minutes to remove oil, and dry at room temperature; put 30% hydrofluoric acid solution at room temperature for activation treatment for 20 minutes, and then wash with deionized water; measure the length of the matrix to 2.5cm, The width is 1.0cm, and the height is 0.7cm. The excess part is covered with silicone rubber and dried naturally.
(3)电沉积：将配制的涂层电解液在水浴锅中加热至95℃，将石墨(阳极)及处理好的基体材料(阴极)放置电解液中，先在恒电位-5V条件下预镀10min，将所获得的预镀层用二次蒸馏水清洗，干燥后置于0.8mol/L的NaOH碱溶液中在90℃处理2h，使电沉积前躯体转变为HAP；样品用二次蒸馏水洗净，自然晾干；然后采用连续双电位阶跃法进行电沉积HAP涂层，先从开路电位E1＝0V阶跃至E2为-3.8V，停留10s(t1)；再阶跃回E1＝0V，维持10s(t2)，如此循环阶跃，时间控制在0.5h，到时间后取出用去离子水漂洗，室温下干燥。(3) Electrodeposition: Heat the prepared coating electrolyte to 95°C in a water bath, place the graphite (anode) and the treated substrate material (cathode) in the electrolyte, and pre-coat under the condition of constant potential -5V. After plating for 10 minutes, wash the obtained pre-plating layer with double distilled water, dry it, place it in 0.8mol/L NaOH alkali solution and treat it at 90°C for 2 hours, so that the body before electrodeposition can be converted into HAP; the sample is washed with double distilled water , dry naturally; then use the continuous bipotential step method to electrodeposit the HAP coating, first step from the open circuit potential E1 = 0V to E2 is -3.8V, stay for 10s (t1 ); then step back to E1 = 0V, maintain for 10s (t2 ), cycle step by step in this way, the time is controlled at 0.5h, after the time is up, take it out, rinse it with deionized water, and dry it at room temperature.
(4)碱处理：碱液处理采用0.25mol/L的NaOH溶液，加热至90℃，将制备的试样放入溶液中浸泡8h后取出，用去离子水漂洗数次，清洗表面的碱液。试样放入120℃的干燥箱中烘20h取出，即制得纳米HAP/镁合金涂层复合材料。(4) Alkali treatment: 0.25mol/L NaOH solution is used for lye treatment, heated to 90°C, the prepared sample is soaked in the solution for 8 hours, then taken out, rinsed with deionized water several times, and the lye on the surface is cleaned . Put the sample into a drying oven at 120°C for 20 hours and take it out to obtain a nano-HAP/magnesium alloy coating composite material.
实施例3：Example 3:
以AZ80镁合金为基体材料，其合金成分(wt％)为，Al 7.98％，Zn 0.32％，Mn 0.23％，Mg余量。AZ80 magnesium alloy is used as the base material, and its alloy composition (wt%) is: Al 7.98%, Zn 0.32%, Mn 0.23%, Mg balance.
(1)电解液的配置：称取NH4H2PO4(99.5％)0.54g，NaNO3(99％)9.6g，Ca(NO3)2.4H2O(99％)2.26g，配置成稀溶液750ml，即调整钙磷原子比为2.0，用玻璃棒搅拌均匀，用HNO3或(CH2OH)3CNH2调节溶液的PH值为4.2，充分搅拌均匀，获得待用电解液。(1) Electrolyte configuration: weigh NH4 H2 PO4 (99.5%) 0.54g, NaNO3 (99%) 9.6g, Ca(NO3 )2 .4H2 O (99%) 2.26g, configure Dilute the solution to 750ml, that is, adjust the calcium-phosphorus atomic ratio to 2.0, stir evenly with a glass rod, adjust the pH value of the solution to 4.2 with HNO3 or (CH2 OH)3 CNH2 , stir well, and obtain the ready-to-use electrolyte.
(2)基体材料的预处理：AZ31镁合金基板线切割成的矩形块，用100-1000金相砂纸依次打磨抛光，用去离子水洗后，配置丙酮：酒精体积比为0.5∶1的混合溶液，将基体材料置于该混合溶液中超声清洗15min除油，在室温下干燥；并在室温下放入40％氢氟酸溶液活化处理20min，然后用去离子水洗；量取基体长度2.5cm，宽度1.0cm，高度0.7cm，多余部分用硅橡胶覆盖，自然干燥。(2) Pretreatment of substrate materials: AZ31 magnesium alloy substrate wire-cut rectangular blocks, polished and polished sequentially with 100-1000 metallographic sandpaper, washed with deionized water, and prepared with a mixed solution of acetone:alcohol with a volume ratio of 0.5:1 , place the matrix material in the mixed solution for ultrasonic cleaning for 15 minutes to remove oil, and dry at room temperature; put 40% hydrofluoric acid solution at room temperature for activation treatment for 20 minutes, and then wash with deionized water; measure the length of the matrix to 2.5cm, The width is 1.0cm, and the height is 0.7cm. The excess part is covered with silicone rubber and dried naturally.
(3)电沉积：将配制的涂层电解液在水浴锅中加热至90℃，将石墨(阳极)及处理好的基体材料(阴极)放置电解液中，先在恒电位-1V条件下预镀30min，将所获得的预镀层用二次蒸馏水清洗，干燥后置于1mol/L的NaOH碱溶液中在95℃处理2h，使电沉积前躯体转变为HAP；样品用二次蒸馏水洗净，自然晾干；然后采用连续双电位阶跃法进行电沉HAP涂层，先从开路电位E1＝0V阶跃至E2为-1.2V，停留一定时间记作t1为60s；再阶跃回E1＝0V，维持一段时间，记作t2为60s，如此循环阶跃，时间控制为3h，到时间后取出用去离子水漂洗，室温下干燥。(3) Electrodeposition: Heat the prepared coating electrolyte to 90°C in a water bath, place the graphite (anode) and the treated substrate material (cathode) in the electrolyte, and pre- After plating for 30 minutes, the obtained pre-plating layer was washed with double distilled water, dried and placed in 1mol/L NaOH alkali solution at 95°C for 2 hours, so that the precursor of electrodeposition was converted into HAP; the sample was washed with double distilled water, Dry naturally; then use the continuous bipotential step method to carry out the electrodeposition HAP coating, first step from the open circuit potential E1 = 0V to E2 is -1.2V, and stay for a certain time as t1 is 60s; then step Back to E1 =0V, maintain for a period of time, recorded as t2 is 60s, such a cycle step, time control is 3h, after the time is up, take it out, rinse with deionized water, and dry at room temperature.
(4)碱处理：碱液处理采用1mol/L的NaOH溶液，加热至70℃，将制备的试样放入溶液中浸泡2h后取出，用去离子水漂洗数次，清洗表面的碱液。试样放入60℃的干燥箱中烘24h取出，即制得纳米HAP/镁合金涂层复合材料。(4) Alkali treatment: 1 mol/L NaOH solution was used for alkali treatment, heated to 70°C, the prepared sample was soaked in the solution for 2 hours, then taken out, rinsed with deionized water several times, and the surface was cleaned of alkali. Put the sample into a drying oven at 60°C for 24 hours and take it out to obtain the nano-HAP/magnesium alloy coating composite material.
实施例4：Example 4:
以AM60镁合金为基体材料，其合金成分(wt％)为，Al 6.08％，Mn 0.13％，Mg余量。Using AM60 magnesium alloy as the base material, its alloy composition (wt%) is 6.08% of Al, 0.13% of Mn, and the balance of Mg.
(1)涂层电解液的配制：称取NH4H2PO4(99.5％)2.7g，NaNO3(99％)6.38g，Ca(NO3)2.4H2O(99％)11.3g，配置成稀溶液750ml，即调整钙磷原子比为2.0，用玻璃棒搅拌均匀；用HNO3或(CH2OH)3CNH2调节溶液的PH值为3.0，充分搅拌均匀，获得待用电解液。(1) Preparation of coating electrolyte: weigh NH4 H2 PO4 (99.5%) 2.7g, NaNO3 (99%) 6.38g, Ca(NO3 )2 .4H2 O (99%) 11.3g , configured into 750ml of dilute solution, that is, adjust the calcium-phosphorus atomic ratio to 2.0, and stir evenly with a glass rod; adjust the pH value of the solution to 3.0 with HNO3 or (CH2 OH)3 CNH2 , stir well, and obtain the ready-to-use electrolytic liquid.
(2)基体材料的预处理：AZ31镁合金基板线切割成的矩形块，用100-1000金相砂纸依次打磨抛光，用去离子水洗后，配置丙酮、酒精混合溶液，其体积比为1∶1，将基体材料置于该混合溶液中超声清洗5min除油，在室温下干燥；并在室温下放入25％氢氟酸溶液活化处理16min，然后用去离子水洗，量取基体长度2.5cm，宽度1.0cm，高度0.7cm，多余部分用硅橡胶覆盖，自然干燥。(2) Pretreatment of substrate materials: AZ31 magnesium alloy substrates are cut into rectangular pieces by wire, polished and polished sequentially with 100-1000 metallographic sandpaper, washed with deionized water, and mixed with acetone and alcohol in a volume ratio of 1: 1. Place the matrix material in the mixed solution for ultrasonic cleaning for 5 minutes to remove oil, and dry at room temperature; put 25% hydrofluoric acid solution at room temperature for activation treatment for 16 minutes, then wash with deionized water, measure the length of the matrix to 2.5cm , width 1.0cm, height 0.7cm, the excess part is covered with silicone rubber and dried naturally.
(3)电沉积：将配制的涂层电解液在水浴锅中加热至65℃，将石墨(阳极)及处理好的基体材料(阴极)放置电解液中，先在恒电位-2V条件下预镀15min，将所获得的预镀层用二次蒸馏水清洗，干燥后置于0.8mol/L的NaOH碱溶液中在70℃处理2.5h，使电沉积前躯体转变为HAP；样品用二次蒸馏水洗净，自然晾干；然后采用连续双电位阶跃法进行电沉HAP涂层，先从开路电位E1＝0V阶跃至E2为-4.5V，停留一定时间记作t1为15s；再阶跃回E1＝0V，维持一段时间，记作t2为15s，如此循环阶跃。时间设为2h，到时间后取出用去离子水漂洗，室温下干燥。(3) Electrodeposition: Heat the prepared coating electrolyte to 65°C in a water bath, place the graphite (anode) and the treated substrate material (cathode) in the electrolyte, and pre-coat under the condition of constant potential -2V. After plating for 15 minutes, the obtained pre-plating layer was washed with double distilled water, dried and placed in 0.8mol/L NaOH alkali solution at 70°C for 2.5 hours to convert the electrodeposited precursor into HAP; the sample was washed with double distilled water Clean and dry naturally; then use the continuous bipotential step method to carry out electrodeposition HAP coating, first step from the open circuit potential E1 = 0V to E2 is -4.5V, and stay for a certain time as t1 is 15s; Step back to E1 =0V, maintain for a period of time, recorded as t2 as 15s, and so on. The time is set to 2h, and when the time is up, take it out, rinse it with deionized water, and dry it at room temperature.
(4)碱处理：碱液处理采用0.5mol/L的NaOH溶液，加热至85℃，将制备的试样放入溶液中浸泡7h后取出，用去离子水漂洗数次，清洗表面的碱液。试样放入110℃的干燥箱中烘8h取出，即制得纳米HAP/镁合金涂层复合材料。(4) Alkali treatment: 0.5 mol/L NaOH solution is used for alkali treatment, heated to 85°C, the prepared sample is soaked in the solution for 7 hours, then taken out, rinsed with deionized water several times, and the alkali solution on the surface is cleaned . Put the sample into a drying oven at 110°C for 8 hours and take it out to obtain a nano-HAP/magnesium alloy coating composite material.
实施例5：Example 5:
以AZ91镁合金为基体材料，其合金成分(wt％)为：Al 9.06％，Zn 1.05％，Mn 0.18％，Si 0.01％，Mg余量。AZ91 magnesium alloy is used as the base material, and its alloy composition (wt%) is: Al 9.06%, Zn 1.05%, Mn 0.18%, Si 0.01%, Mg balance.
(1)涂层电解液的配制：称取NH4H2PO4(99.5％)1.08g，NaNO3(99％)5.60g，Ca(NO3)2.4H2O(99％)5.66g，配置成稀溶液750ml，即调整钙磷原子比为2.5，用玻璃棒搅拌均匀；用HNO3或(CH2OH)3CNH2调节溶液的PH值为5.0，充分搅拌均匀，获得待用电解液。(1) Preparation of coating electrolyte: weigh NH4 H2 PO4 (99.5%) 1.08g, NaNO3 (99%) 5.60g, Ca(NO3 )2 .4H2 O (99%) 5.66g , configured into 750ml of dilute solution, that is, adjust the calcium-phosphorus atomic ratio to 2.5, and stir evenly with a glass rod; adjust the pH value of the solution to 5.0 with HNO3 or (CH2 OH)3 CNH2 , stir well, and obtain the ready-to-use electrolytic liquid.
(2)基体材料的预处理：AZ31镁合金基板线切割成的矩形块，用100-1000金相砂纸依次打磨抛光，用去离子水洗后，配置丙酮、酒精混合溶液，其体积比为0.9∶1，将基体材料置于该混合溶液中超声清洗20min除油，在室温下干燥；并在室温下放入35％氢氟酸溶液活化处理25min，然后用去离子水洗，量取基体长度2.5cm，宽度1.0cm，高度0.7cm，多余部分用硅橡胶覆盖，自然干燥。(2) Pretreatment of the base material: AZ31 magnesium alloy substrate wire-cut rectangular block, polished and polished sequentially with 100-1000 metallographic sandpaper, washed with deionized water, and then configured with acetone and alcohol mixed solution, the volume ratio of which is 0.9: 1. Place the matrix material in the mixed solution for ultrasonic cleaning for 20 minutes to remove oil, and dry it at room temperature; put it into 35% hydrofluoric acid solution for activation treatment at room temperature for 25 minutes, then wash it with deionized water, and measure the length of the matrix to 2.5cm , width 1.0cm, height 0.7cm, the excess part is covered with silicone rubber and dried naturally.
(3)电沉积：将配制的涂层电解液在水浴锅中加热至75℃，将石墨(阳极)及处理好的基体材料(阴极)放置电解液中，先在恒电位-3.8V条件下预镀25min，将所获得的预镀层用二次蒸馏水清洗，干燥后置于0.3mol/L的NaOH碱溶液中在90℃处理2.8h，使电沉积前躯体转变为HAP；样品用二次蒸馏水洗净，自然晾干；然后采用连续双电位阶跃法进行电沉HAP涂层，先从开路电位E1＝0V阶跃至E2为-3.8V，停留一定时间记作t1为25s；再阶跃回E1＝0V，维持一段时间，记作t2为25s，如此循环阶跃。时间设为1.5h，到时间后取出用去离子水漂洗，室温下干燥。(3) Electrodeposition: Heat the prepared coating electrolyte to 75°C in a water bath, place the graphite (anode) and the treated substrate material (cathode) in the electrolyte, and first place it under the condition of constant potential -3.8V Pre-plating for 25 minutes, the obtained pre-plating layer was washed with double distilled water, dried and placed in 0.3mol/L NaOH alkali solution at 90°C for 2.8 hours to convert the electrodeposited precursor into HAP; the sample was washed with double distilled water Wash and dry naturally; then use the continuous bipotential step method to carry out electrodeposition HAP coating, first step from the open circuit potential E1 = 0V to E2 is -3.8V, and stay for a certain time as t1 is 25s; Then step back to E1 =0V, maintain for a period of time, record t2 as 25s, and repeat the steps like this. The time is set to 1.5h, and after the time is up, it is taken out, rinsed with deionized water, and dried at room temperature.
(4)碱处理：碱液处理采用0.75mol/L的NaOH溶液，加热至95℃，将制备的试样放入溶液中浸泡5h后取出，用去离子水漂洗数次，清洗表面的碱液；试样放入95℃的干燥箱中烘15h取出，即制得纳米HAP/镁合金涂层复合材料。(4) Alkali treatment: 0.75mol/L NaOH solution is used for lye treatment, heated to 95°C, the prepared sample is soaked in the solution for 5h, then taken out, rinsed with deionized water several times, and the lye on the surface is cleaned ; Put the sample into a drying oven at 95°C for 15 hours and take it out to obtain a nano-HAP/magnesium alloy coating composite material.
对产物的试验检测分析表明：The test detection analysis to product shows:
1.采用双电位阶跃可以得到针状致密的纳米HAP涂层，低温碱处理能促进前驱体向HAP转化，可以提高钙磷原子比最高达到1.67，为自然骨的钙磷原子比；1. A needle-like dense nano-HAP coating can be obtained by using a bipotential step. Low-temperature alkali treatment can promote the conversion of the precursor to HAP, and can increase the calcium-phosphorus atomic ratio to a maximum of 1.67, which is the calcium-phosphorus atomic ratio of natural bone;
2.腐蚀电化学系统测试结果表明HAP涂层能提高镁合金在模拟体液(SBF)中的腐蚀电位200mV，说明涂层能够较好的保护基体；2. The test results of the corrosion electrochemical system show that the HAP coating can increase the corrosion potential of magnesium alloys in simulated body fluid (SBF) by 200mV, indicating that the coating can better protect the substrate;
3.粘结拉伸法测定了HAP/镁合金涂层材料的结合强度，表明了优化的工艺制得的涂层与基体的结合性能良好，可达到20.8MPa，满足体内植入的基本要求；3. The bonding strength of the HAP/magnesium alloy coating material was measured by the bonding tensile method, which showed that the bonding performance of the coating made by the optimized process and the substrate was good, which could reach 20.8MPa, which met the basic requirements of implantation in the body;
4.模拟体液浸泡试验表明，有涂层的试样其腐蚀呈现由慢到快的趋势，浸泡前2周有涂层的试样均有明显增重，一个月后失重和增重才趋于缓和。在浸泡初期，沉积起主导作用，后期腐蚀起主导作用。4. The immersion test in simulated body fluids shows that the corrosion of the coated samples shows a trend from slow to fast. The coated samples all have obvious weight gain 2 weeks before immersion, and the weight loss and weight gain tend to reach a certain level after one month. ease. In the early stage of immersion, deposition plays a leading role, and later corrosion plays a leading role.
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