Hank‘s人工模拟体液中离子注氮对4种植入金属材料腐蚀行为的影响

采用电化学测试技术研究了离子注氮对SUS316L不锈钢，Co-Cr合金，工业纯钛和Ti-6Al-4V植入合金在Hank’s人工模拟体液中腐蚀行为的影响。腐蚀电位和极化曲线的测量结果表明，注氮使4种植入金属材料的腐蚀电位正移，钝化电位区间扩大，耐蚀性明显提高。注氮的工业纯钛和Ti-6Al-4V合金的耐蚀性最佳，其钝化区拓宽为4V以上。通过AES分析发现，离子注氮后钛及其合金表面形成的氮化钛膜层及弥散的氮化钛析出相的化学效应，使基体电化学性能得到提高。注氮的Co-Cr合金的耐蚀性略优于SUS316L不锈钢。Co-Cr合金表面形成的钴氮化合物相对基体起到保护作用，降低了腐蚀速率。SUS316L不锈钢表面形成铁和铬氮化合物膜，有效地阻止了Cr^3 的水解，且氮离子注入促进Fe3O4的产生，提高了耐腐蚀性能。     

不同模拟体液及pH值变化对人体用金属生物材料耐蚀性能的影响

采用Ringer's溶液,PBS(-)溶液和Hank's溶液,研究了不同模拟体液和pH值对316L不锈钢、Co-Cr合金和Ti-6Al-4V合金生物医学材料耐蚀性能的影响。结果表明,不同模拟体液的侵蚀性是不同的,侵蚀性由强到弱的顺序为Ringer's>PBS(-)>Hank's溶液。RBS(-)和Hank's溶液中的HPO 4~(2-)、H_2PO_4~(2-)和SO_4~(2-)、葡萄糖,对生物材料的腐蚀起到一定的缓蚀作用。pH降低,对316L不锈钢和Co-Cr合金的耐蚀性能有较大的影响,而对Ti-6Al-4V合金影响较小。     

人工模拟体液中Ti,Ti-6Al-4V合金和Ti-Ni形状记忆合金的缝隙腐蚀行为（英文）EI北大核心CSCD

采用电化学方法研究了工业纯钛、Ti-6Al-4V合金和Ti-Ni SMA在Ringer’s人工模拟体液中缝隙腐蚀行为。Ringer’s人工体液中恒电位400 m V的试验结果表明,工业纯钛、Ti-6Al-4V合金和Ti-Ni SMA缝隙试样均发生缝隙腐蚀,随着介质温度的升高,缝隙腐蚀倾向加剧。在Ringer’s人工模拟体液中Ti-6Al-4V合金的腐蚀电位较正,反应电阻增大,阳极极化性能优于工业纯钛和Ti-Ni SMA,提高了抗缝隙腐蚀性能。在Ringer’s人工模拟体液中推导出工业纯钛、Ti-6Al-4V合金和Ti-Ni SMA缝隙试样的缝隙腐蚀动力学方程为:iT,CPTi=0.028 e-2×10-4 t,iT,Ti-6Al-4V=0.0149 e-3×10-4 t,和iT,Ti-Ni SMA=0.4712 e-7×10-4 t表明缝隙腐蚀过程受缝隙表面氯化物盐膜的溶解控制。     

人工模拟体液中Ti,Ti-6Al-4V合金和Ti-Ni形状记忆合金的缝隙腐蚀行为（英文）

采用电化学方法研究了工业纯钛、Ti-6Al-4V合金和Ti-Ni SMA在Ringer’s人工模拟体液中缝隙腐蚀行为。Ringer’s人工体液中恒电位400 m V的试验结果表明,工业纯钛、Ti-6Al-4V合金和Ti-Ni SMA缝隙试样均发生缝隙腐蚀,随着介质温度的升高,缝隙腐蚀倾向加剧。在Ringer’s人工模拟体液中Ti-6Al-4V合金的腐蚀电位较正,反应电阻增大,阳极极化性能优于工业纯钛和Ti-Ni SMA,提高了抗缝隙腐蚀性能。在Ringer’s人工模拟体液中推导出工业纯钛、Ti-6Al-4V合金和Ti-Ni SMA缝隙试样的缝隙腐蚀动力学方程为:iT,CPTi=0.028 e-2×10-4 t,iT,Ti-6Al-4V=0.0149 e-3×10-4 t,和iT,Ti-Ni SMA=0.4712 e-7×10-4 t表明缝隙腐蚀过程受缝隙表面氯化物盐膜的溶解控制。     

Ti-6Al-4V合金氮离子注入后在Tyrode’s体液中的耐蚀耐磨性能

Ti-6Al-4V合金注入氮离子后,生物相容性、抗磨损性、抗疲劳性及抗腐蚀性均有所提高,其植入人体后在体液中的耐蚀耐磨性能尤为重要,目前对此研究较少。对Ti-6Al-4V合金进行氮离子注入,并在人工模拟体液Tyrode’s溶液中进行摩擦磨损和电化学试验,研究了注氮Ti-6Al-4V合金的耐蚀耐磨性能。采用扫描电镜观察腐蚀形貌,用其自带的能谱仪分析注氮层的元素组成,采用X射线衍射仪分析注氮层的结构。结果表明:Ti-6Al-4V氮离子注入后表面形成主要由TiC,Ti及少量TiO2组成的膜层,硬度提高,在Tyrode’s溶液中的腐蚀电位升高、极化电阻增大,阳极极极化电流密度降低;在Tyrode’s溶液中摩擦后的注氮Ti-6Al-4V合金的阳极极化电流密度大于未摩擦的,极化电阻减小;Ti-6Al-4V合金氮离子注入后的摩擦系数明显降低,比磨损率减少。     

模拟人体体液中放电等离子烧结生物医用Ti2448合金的腐蚀行为研究

利用动电位极化曲线和电化学阻抗谱方法研究了放电等离子烧结技术(SPS)制备的生物医用Ti-24Nb-4Zr-8Sn(Ti2448)合金在Hank's模拟人体体液中的电化学腐蚀行为及腐蚀机理,并与工业纯钛(TA1)和Ti-6Al-4V(TC4)合金进行了比较。结果表明:与TA1和TC4合金相比,在37℃的Hank's溶液中SPS烧结Ti2448合金具有最小的腐蚀电位与致钝电流密度、接近的腐蚀电流密度以及最大的极化电阻,3种材料耐腐蚀性能好坏依次为Ti2448TC4TA1。     

Ti-6Al-4V和Monel K500合金在海水环境中与316不锈钢对磨时的腐蚀磨损性能(英文)

研究Ti-6Al-4V和Monel K500合金在海水和纯水环境下的腐蚀磨损性能,对偶材料为316不锈钢,实验装置为环-块摩擦磨损试验机。研究结果表明,Ti-6Al-4V和Monel K500合金在海水中的摩擦因数明显小于在纯水中的摩擦因数,在海水中的磨损量明显大于纯水中的磨损量,这主要是由于摩擦作用破坏了金属表面的钝化膜,增加了摩蚀速度。磨损和腐蚀产生交互作用,交互作用量随着腐蚀速度的加快而增加。当和Monel K500配副时,316不锈钢的磨损严重,而和Ti-6Al-4V配副时磨损相对较小。     

钛及钛合金海水腐蚀的电化学研究

为使Ti在海洋工程上广泛应用和进一步认识这些材料在海水中的腐蚀特性。本研究选用常规的和自设计的电化学方法,研究了纯钛(TA2),Ti-6Al-4V(TC4),Ti-4Al-3Mo-1V(BT14)、Ti-4Al-0.005B(TA5),Ti-0.2Pd,Ti-0.3Mo-0.8Ni(Ti-12),Ti-3Al-2.5V(T-3-2),Cu70Ni30(B30),不锈钢(18-8)等材料在天然海水中的极化特性、腐蚀电位以及相互间偶对的电偶腐蚀效应,测试并描绘了稳定电位、电偶腐蚀的开路电位、电偶电流与时间曲线,计算了自腐蚀率和偶合后腐蚀率。实验表明:在天然海水中,Ti的腐蚀电位急剧正移,明显高于B30、18-8。具有良好的抗海水腐蚀性能,Ti、B30、18-8互相偶对,Ti-Ti偶合效应最小,Ti-18-8偶合效应次之,Ti-B30偶合效应最大,Ti本身不腐蚀,但加速了B30和18-8腐蚀。本文对Ti的海水腐蚀电化学研究方法作了评价。     

油气开采用钛合金石油管材料耐腐蚀性能研究

选取5种油气开发常用钛合金材料(Ti-6Al-4V、Ti-6Al-4V-0.1Ru、Ti-6Al-2Sn-4Zr-6Mo、Ti-3Al-8V-6Cr-4Zr-4Mo和Ti-5.5Al-4.5V-2Zr-1Mo)为研究对象,使用高温高压釜模拟国内典型严酷服役工况环境,研究了不同钛合金材料耐均匀腐蚀、局部腐蚀、点蚀、应力腐蚀开裂(SCC)及缝隙腐蚀的性能,通过使用扫描电镜和能谱分析等手段对腐蚀形貌和腐蚀产物进行了分析,并使用电化学方法对不同合金的耐腐蚀机理进行了研究。结果显示,在所测试工况条件下,所有钛合金材料腐蚀反应均为阳极控制过程,均匀腐蚀速率均低于0.001mm/a,并且对应力腐蚀开裂均有良好的抗力。Ti-6Al-4V和Ti-5.5Al-4.5V-2Zr-1Mo合金出现明显的点蚀和缝隙腐蚀问题。对腐蚀机理研究表明,在工况条件温度下,随着pH值的降低,所有钛合金均发生自腐蚀电位降低,极化电阻减小,腐蚀电流增大,耐腐蚀性能下降,其中Ti-6Al-4V耐腐蚀性能下降的最为明显,研究结果为油气开发工况下钛合金石油管的选材和缝隙腐蚀问题防治提供理论基础。     

粉末冶金制备Ti-Fe二元合金的耐腐蚀性能

采用粉末冶金模压烧结技术制备了Ti-(2~20)Fe二元合金,探讨了Fe含量对合金的力学性能及耐腐蚀性能的影响,并与铸造CP Ti和Ti-6Al-4V合金的耐腐蚀性能进行了对比。结果表明,随着Fe含量的增加,合金a相含量逐渐降低,b相含量逐渐提高。当Fe含量达到20%时,基本形成单一b相合金。随Fe含量的升高,粉末冶金Ti-(2~20)Fe二元合金的强度及塑性趋于升高,而弹性模量趋于降低。相对而言,Ti-15Fe合金的综合性能最佳,其抗压强度为2702 MPa,压缩率为32.7%,弹性模量为64.6 GPa。随着Fe含量在2%~15%范围内提高,合金的自腐蚀电位正向移动,腐蚀电流密度降低,极化电阻不断增大,腐蚀速率不断降低,耐蚀性能逐渐提高,而Ti-20Fe合金耐腐蚀性能与Ti-15Fe合金接近。Ti-15Fe合金在模拟口腔液(FAS)、磷酸盐缓冲溶液(PBS)、模拟体液(SBF)以及0.9%NaCl溶液(SS)中的腐蚀速率分别为1.7×10~(-3)、7.1×10~(-4)、1.2×10~(-3)和3.5×10~(-4)mm/y。与铸造CP Ti和Ti-6Al-4V合金相比,Ti-15Fe合金具有较正的自腐蚀电位、较小的腐蚀电流密度和腐蚀速率及较大的极化电阻,耐蚀性能明显优于CPTi和Ti-6Al-4V合金。     

Effects of different simulated fluids on anticorrosion biometallic materials

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AISI 316不锈钢和Ti6Al4V合金在海水环境中的腐蚀与腐蚀磨损行为(英文)

采用立式万能销盘腐蚀磨损试验机研究AISI 316不锈钢和Ti6Al4V合金在海水中与Al2O3陶瓷对磨时的腐蚀与腐蚀磨损行为,重点讨论腐蚀磨损之间的交互作用。结果表明,摩擦作用使得Ti6Al4V合金和316不锈钢的开路电位大幅下降,腐蚀磨损过程中的电流密度远高于静态腐蚀时的电流密度,摩擦明显促进了合金的腐蚀。两种合金在海水中的磨损量远大于在纯水中的磨损量,腐蚀促进了磨损,并且Ti6Al4V合金的耐磨性优于316不锈钢的耐磨性,腐蚀磨损之间的交互作用是材料损失的一个重要因素。本实验所用的摩擦装置为单向滑动的面面接触方式,这使得摩擦对腐蚀的促进作用在总磨损量中所占的比例很小。     

The examination of corrosion behaviors of hap coated Ti implant materials and 316L SS by sol-gel method

In this research, hydroxyapatite (HAP) coatings have been produced on Ti, Ti6Al4V alloy and 316L stainless steel substrates by sol-gel method. (NH₄) · H₂PO₄ is taken as P precursor and Ca(NO₃)₂ · 4H₂O is taken as Ca precursor to obtain HAP coating. Additionally, three different pretreatment processes (HNO₃, anodic polarization, base-acide (BA)) have been applied to Ti, Ti6Al4V alloy and 316L stainless steel substrates. The corrosion behaviors of bare and HAP coated samples are examined in Ringer and 0.9% NaCl. HAP coated Ti have showed over 87.85% inhibition. HAP coated Ti6Al4V alloys have showed over 87.33% inhibition. In Ringer solution, 99.24% inhibition has been showed in HAP coated anodic pretreatment for 316L stainless steel. All pretreatment processes are effective on clinging of HAP coating to the surface. It is seen that impedance values have increased in HAP coatings (Ti and Ti6Al4V). HAP coatings have raised the corrosion resistance of Ti and Ti6Al4V. The values of polarization resistance in HAP coated samples have increased for 316L stainless steel in 0.9% NaCl and Ringer solutions. It is seen in SEM images that open pores and attachments among pores have been observed in the coating, which increases osteointegration. It is noted in EDX analyses of the surfaces of the HAP coated samples that there is only Ca, O, and P on the surface. Ca/P ratio varies in 1.84–2.00 ranges. As Ca/P ratio increases, the inhibition increases too. It is seen in XRD images of HAP powder that there are HA ate structures. Additionally, it is seen in FTIR analysis, characteristic HA absorption bands have occurred in sintered powders.     

模拟体液中纯钛及Ti6A14V合金的腐蚀行为

采用电化学测试技术研究了人体医用金属材料工业纯钛和Ti6A14V合金在人工模拟体液中的腐蚀行为,结果表明,阳极极化后两种合金均未发现点蚀,工业纯钛的维钝电流密度小于于Ti6A14V合金,前者的阳极极化性能优于后者,Ti6A14V合金缝隙试样在阳极电位超过＋2000mV(vsSCE)后,电流开始急剧增大,发生了缝隙腐蚀;通过电子探针分析发现,在缝隙内Al和V两种元素发生活性溶解。工业纯钛在电位达到＋4000mV/(vsSCE）时仍没有发生缝隙腐蚀。     

Corrosion behaviour of Ti DLC deposition on prenitrided 316L stainless steel and Ti–6Al–4V alloy

Abstract

316L and Ti–6Al–4V are widely used as biomaterials and materials of various mechanical components. In biomedical applications, they are used to manufacture coronary and pulmonary stents, hip prosthesis, screws and external fixations. However, Cr, Al and V are released from the alloys to the body environment and these ions mix into the blood stream. Release of even small amounts of these ions may cause local irritation of the tissues surrounding the implant. This situation may be prevented by applying suitable surface treatments to the biomaterials. The overall objective of the present paper is to examine the corrosion properties of duplex treated (nitrided and with a diamond-like carbon coating) 316L stainless steel and Ti–6Al–4V alloy. Diamond-like carbon films were deposited on nitrided samples using closed field unbalanced magnetron sputtering system. The corrosion behaviour of duplex treated samples was tested using the potentiodynamic method in ringer’s solution at 37°C. The corrosion resistance of duplex treated samples was significantly improved in comparison with the uncoated and single treated samples. In addition, the corroded surfaces were investigated by SEM where small pits were observed on all samples.     

Fe41Co7Cr15Mo14C15B6Y2块体非晶合金在HCl溶液中的腐蚀行为

采用电化学极化曲线和电化学阻抗(EIS)测试方法研究Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2块体非晶合金在0.5,1,2以及4 mol/L HCl溶液中的腐蚀行为,并比较了1 mol/L HCl溶液中非晶合金和不锈钢的腐蚀行为.极化曲线测试结果表明,Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2块体非晶合金在各种浓度的HCl溶液中都具有很好的耐蚀性,阳极极化曲线表现出明显的钝化特征.随着HCl溶液浓度的增大,其耐蚀性能逐渐下降.在1 mol/L HCl溶液中,非晶合金的自腐蚀电位高于不锈钢,自腐蚀电流密度比不锈钢小1个数量级.EIS结果显示,在开路电位下,Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2非晶合金和不锈钢的Nyquist图均由单一的容抗弧构成,但非晶合金的电化学转移电阻Rt比不锈钢的大2个数量级,这一结果与极化曲线结果一致,说明非晶合金在HCl溶液中的耐蚀性能优于不锈钢.     

316L不锈钢表面激光熔覆Stellite-F合金层的电化学腐蚀行为

采用CO₂激光器在316L不锈钢表面熔覆Stellite-F合金,通过电化学方法研究了Stellite-F熔覆合金层在5wt%NaCl溶液中的腐蚀行为。结果表明:与316L不锈钢相比,与基材呈冶金结合的Stellite-F合金层自腐蚀电位较正、自腐蚀电流密度较小,无点腐蚀现象出现,耐海水腐蚀性能较好;研究发现,熔覆合金层物相主要由γ-Co固溶体与Ni₃C、Cr₂₃C₆碳化物构成,在盐溶液中其腐蚀失效机制为选择性腐蚀,即固溶体合金相作为阳极被腐蚀浸出,碳化物相得到阴极保护暴露析出,同时固溶体相中的Co、Ni组分优先被腐蚀浸出,其余组分形成海绵状结构。     

The Tribological Performance of Surface Treated Ti6A14V as Sliding Against Si<Subscript>3</Subscript>N<Subscript>4</Subscript> Ball and 316L Stainless Steel Cylinder

Closed field unbalanced magnetron sputtering was used to deposit diamond-like carbon (Ti-C:H) coatings on Ti6Al4V alloy and gas nitrided Ti6Al4V alloy. Four different specimens were prepared, namely untreated Ti6Al4V alloy (Ti6Al4V), gas nitrided Ti6Al4V alloy (N-Ti6Al4V), Ti-C:H-coated Ti6Al4V alloy (Ti-C:H/Ti6Al4V) and Ti-C:H-coated gas nitrided Ti6Al4V alloy (Ti-C:H/N-Ti6Al4V). The tribological properties of the four specimens were evaluated using a reciprocating wear tester sliding against a Si₃N₄ ball (point contact mode) and 316L stainless steel cylinder (line contact mode). The wear tests were performed in a 0.89 wt.% NaCl solution. The results showed that the nitriding treatment increased the surface roughness and hardness of the Ti6Al4V alloy and improved the wear resistance as a result. In addition, the Ti-C:H coating also improved the tribological performance of Ti6Al4V. For example, compared to the untreated Ti6Al4V sample, the Ti-C:H coating reduced the wear depth and friction coefficient by 340 times and 10 times, respectively, in the point contact wear mode, and 151 times and 9 times, respectively, in the line contact wear mode. It is thus inferred that diamond-like carbon coatings are of significant benefit in extending the service life of artificial biomedical implants.     

不锈钢表面Cr-Pd合金电沉积及镀层在强还原性介质中的耐蚀性

通过选择络合剂、缓冲剂及采用方波脉冲电流和优化电镀工艺, 在酸性镀液中实现了Cr-Pd共镀, 并在不锈钢表面制备出均匀致密且与基体结合良好的Cr-Pd合金镀层. 通过改变镀液中铬盐和钯盐的相对含量, 可以大范围改变镀层成分. Cr-Pd合金镀层可显著提高不锈钢在高温还原性腐蚀介质中的耐蚀性, 在沸腾的20%(质量分数)H₂SO₄溶液中, Cr-Pd合金镀层使316L不锈钢的腐蚀速率降低了4个数量级以上. 镀层中的Cr和Pd对致钝具有协同促进作用, 当镀层中含有2.5%Pd(质量分数)时即具有明显的促进钝化效果, 含33.3%Pd镀层对不锈钢的保护效果与纯Pd镀层相当.