Adsorption and protein-induced metal release from chromium metal and stainless steel

A research effort is undertaken to understand the mechanism of metal release from, e.g., inhaled metal particles or metal implants in the presence of proteins. The effect of protein adsorption on the metal release process from oxidized chromium metal surfaces and stainless steel surfaces was therefore examined by quartz crystal microbalance with energy dissipation monitoring (QCM-D) and graphite furnace atomic absorption spectroscopy (GFAAS). Differently charged and sized proteins, relevant for the inhalation and dermal exposure route were chosen including human and bovine serum albumin (HSA, BSA), mucin (BSM), and lysozyme (LYS). The results show that all proteins have high affinities for chromium and stainless steel (AISI 316) when deposited from solutions at pH 4 and at pH 7.4 where the protein adsorbed amount was very similar. Adsorption of albumin and mucin was substantially higher at pH 4 compared to pH 7.4 with approximately monolayer coverage at pH 7.4, whereas lysozyme adsorbed in multilayers at both investigated pH. The protein-surface interaction was strong since proteins were irreversibly adsorbed with respect to rinsing. Due to the passive nature of chromium and stainless steel (AISI 316) surfaces, very low metal release concentrations from the QCM metal surfaces in the presence of proteins were obtained on the time scale of the adsorption experiment. Therefore, metal release studies from massive metal sheets in contact with protein solutions were carried out in parallel. The presence of proteins increased the extent of metals released for chromium metal and stainless steel grades of different microstructure and alloy content, all with passive chromium(III)-rich surface oxides, such as QCM (AISI 316), ferritic (AISI 430), austentic (AISI 304, 316L), and duplex (LDX 2205).     

Surface chemistry and diffusion of trace and alloying elements during in vacuum thermal deoxidation of stainless steel

Removal of the native surface oxide from steel is an important initial step during vacuum brazing. Trace and alloying elements in steel, such as Mn, Si, and Ni, can diffuse to the surface and influence the deoxidation process. The detailed surface chemical composition and grain morphology of the common stainless-steel grade 316L is imaged and spectroscopically analyzed at several stages of in-vacuum annealing from room temperature up to 850°C. Measurements are performed using synchrotron-based X-ray photoemission and low-energy electron microscopy (XPEEM/LEEM). The initial native Cr surface oxide is amorphous and unaffected by the underlying Fe grain morphology. After annealing to ~700°C, the grain morphology is seen at the surface, persisting also after the complete oxygen removal at 850°C. The surface concentration of first Mn and then Si increases significantly when annealing to 500°C and 700°C, respectively, while Ni and Cr concentrations do not change. Mn and Si are not located only in grain boundaries or clusters but are distributed across over the surface. Both Mn and Si appear as oxides, while Cr oxide becomes metallic Cr. Annealing from 500°C up to 850°C leads to the removal of first the Mn and then Si oxides from the surface, while Cr and Fe are completely reduced to metals. Deoxidation of Cr occurs faster at the grain boundaries, and the final Cr metal surface content varies between the grains. The findings are summarized in a general qualitative model, relevant for austenite steels.     

Application of thermal analysis techniques to study the oxidation/reduction phenomena during sintering of steels containing oxygen-sensitive alloying elements

For the consolidation of steel parts manufactured by powder metallurgy (PM) techniques, removal of the surface oxides covering metallic powder particles is a necessary prerequisite. In PM steels with conventional compositions, reduction of the oxides is easily achieved in traditional sintering furnaces. However, processing steels containing alloying elements with a high oxygen affinity represents a big challenge that requires a deeper understanding of the chemical processes occurring during sintering. In the present work, thermogravimetry analysis coupled with mass spectrometry is used to describe the oxidation/reduction phenomena that take place when sintering steel powders and how these processes are modified by the addition of admixed particles containing oxygen-sensitive elements. Carbothermal reduction processes are studied using pure oxides (Fe₂O₃, MnO₂, Cr₂O₃ and SiO₂) as well as water-atomized Fe powders mixed with small amounts—4 mass/%—of Cr, Mn and Si powders or Fe–Mn–Si–(Cr) master alloy powders. The results show that there is an oxygen transfer from the base iron particles to the oxidation-sensitive elements—“internal getter effect”—taking place mostly through the gas phase. Different alloying elements (Cr, Mn, Si) show different temperature ranges of susceptibility to oxidation. Combination of these oxygen-sensitive alloying elements in the form of a master alloy powder reduces their sensitivity to oxidation. Also, the use of master alloys promotes the concentration of the oxides on the surface of the alloying particles and not in the grain boundaries of the surrounding iron particles—as occurs when using Mn carriers—which should have a beneficial impact on the final mechanical performance.     

RE-Al对含钨高铬铸铁变质效果的试验研究

考察了RE，Al对含钨高铬铸铁组织、冲击韧度、硬度、耐磨性等性能的影响。结果表明：铸态未变质的铸铁组织中，奥氏体含量多，碳化物呈粗大板条状分布，晶粒比较粗大；变质后残余奥氏体量明显减少，初生奥氏体显著细化，碳化物由粗大板条状向细板条状、菊花状转变；RE，Al复合变质处理可使铬钨合金白口铸铁的硬度、冲击韧度、耐磨性都得到提高。     

镧在含残余锡、锑GCr15钢中的作用

在Gleeble-1500热模拟机上测定了残余元素锡、锑对GCr15钢热塑性的影响,以及镧对残余元素的作用。用SEM及EDS观察研究了实验钢的断口形貌及在断裂处形成的夹杂物。结果表明,随着残余元素含量增加,GCr15钢的热塑性降低,镧可以与钢中较低含量的锑形成化合物,稀土元素可以降低残余元素对轴承钢热塑性的危害。实验还研究了镧对原奥氏体晶粒、变形后再结晶晶粒大小以及对淬火组织的影响,镧能细化变形后的晶粒大小以及随后的马氏体组织。     

肿瘤患者放疗前后血清八种微量元素含量的研究

对临床、病理、放射线或CT检查确诊的82名癌肿患者，在放疗前后和对42名健康人进行了微量元素铁、锌、铜、锰、硒，铬、钴、镍的分析。研究结果显示：1．癌肿患者血清铜、镍、锰、铬、钴的含量比健康人高，而血清锌、铁、硒的含量却比健康人低；2．血清Cu／Zn、Cr／Zn、Co／Zn、Ni／Zn的比值癌肿患者均比健康人高，而Fe、Zn、Se／Zn的比值却相反。因此，可根据血清铜升高、血清锌降低，血清铜／锌比值升高的特点。用于癌肿的早期诊断；3．癌肿患者放疔后血清铁、锌含量进一步下降，铜、锰、铬的含量也出现降低，唯有硒的含量有所上升。因此，放疗时应注意补充铁、锌、铜元素。     

太阳能甲烷重整中催化活性吸收体的表面特性

以AISI316泡沫金属为基体为太阳能甲烷重整反应制备出系列Ru基和Ni基催化活性吸收体(Ru/Al2O3/AISI316,Ni/Al2O3(MgO)/AISI316),着重利用XRD、TPR、TPD和CO2脉冲吸脱附等技术对所制整体式催化剂的表面特性进行了表征和分析.结果表明:以AISI316泡沫金属为基体可增加活性组分与涂层载体Al2O3的相互作用以及活性物种的分散度.对于Ni基催化活性吸收体,在涂层载体中添加MgO助剂可显著地提高Ni/Al2O3/AISI316的催化活性;Al2O3涂层载体含量的增加可提高活性组分NiO的分散性.相对Ni/Al2O3/AISI316,Ru/Al2O3/AISI316催化活性吸收体对CO2的吸附和活化能力更强,因而具有相对更高的催化活性.     

微纳米多孔不锈钢表面高效吸附活性生物大分子

不锈钢(AISI 316L)是目前在医药器械中应用最为广泛的商业化材料. 下一代的不锈钢智能材料将特殊功能的生物活性分子(或纳米粒子)修饰在金属表面以模拟组织功能、提高生物/细胞相容性, 这是目前材料科学研究的热点领域之一. 本文研究了具有微纳米多孔表面结构的316L 不锈钢对抗体和生物酶分子的吸附作用,并与这些生物分子在光滑表面以及镀金表面的吸附进行了比较. 研究发现不锈钢可通过简单的电化学腐蚀方法在表面产生微纳米多孔结构. 微纳米孔不锈钢表面可稳定地吸附抗体或辣根过氧化物酶分子, 其吸附量与喷镀金表面相当或更好. 用表面活性剂(10%牛血清白蛋白(BSA)或0.2% Tween-20)洗涤不能除去吸附的蛋白.用5% Tween-20 预处理金属表面, 则可减少一半的抗体吸附量; 但表面活性剂预处理对辣根过氧化物酶的吸附没有影响. 吸附蛋白质后的金属表面湿润度大大增加; 蛋白质修饰的微纳米孔不锈钢表面表现出了很好的亲水性(水接触角小于50°), 指示了很好的生物相容性. 而金属表面的湿润度则主要取决于蛋白质物种, 并与蛋白质的吸附量正相关. 吸附于不锈钢微纳米孔表面的抗体仍保持了良好的生物活性; 用此种方式制备的抗CD34抗体修饰的不锈钢血管支架可以高密度并高选择性地吸附其目标细胞(如KG-1细胞). 本文工作为未来制备新型的无高聚物涂层的不锈钢智能医学生物材料提供了基础.     

Comparative XPS analysis of passive layers composition formed on AISI 304 L SS after standard and high‐current density electropolishing

In the paper, there are described chemical compositions of passive surface layers formed on AISI 304 L (EN 1.4307) stainless steel after standard (EP50; i = 50 A/dm²) and high‐current density (EP1000; i = 1000 A/dm²) electropolishing. For the studies, a mixture of orthophosphoric and sulfuric acid electrolyte in proportion 1:4 was used. The survey and high‐resolution spectra of Cr 2p, Fe 2p, S 2p, P 2p, Ni 2p and C 1s are presented. On the basis of the obtained results it was noted that the chromium‐to‐iron ratio (Cr/Fe) after EP50 was about 3.5 times higher than that after EP1000 treatment. The phosphorus‐to‐sulfur ratios after EP50 and EP1000 electropolishing were 0.13 and 0.3, respectively, and nickel to the sum of chromium and iron coefficient (Ni/Cr + Fe) for both electrochemical polishing was equal to 0.04. Copyright © 2014 John Wiley & Sons, Ltd.     

纳米颗粒对Ni基复合镀渗层耐冲蚀性能的影响

采用复合镀渗工艺在316L不锈钢表面分别制备了两种纳米颗粒(非晶nano-SiO2颗粒和nano-SiC颗粒)增强的Ni基复合镀渗合金层. 利用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察了两种复合镀渗合金层的微观组织特征. 通过外加电位(+0.2 V)条件下的电流密度、冲蚀条件下的极化曲线和冲蚀后的交流阻抗谱表征了这两种复合镀渗层在单相流(3.5%(w, 质量分数)NaCl溶液)与料浆流(3.5%NaCl+10%(w)石英砂)中的电化学腐蚀特征, 并采用SEM观察两种复合镀渗层冲蚀后的截面形貌, 探讨这两种纳米颗粒增强的Ni基复合镀渗层在料浆流中的冲蚀机理. 电化学测试结果表明: 静态条件下, 电刷镀含纳米SiO2颗粒的复合镀渗层的耐蚀性能低于单一合金层, 而动态冲蚀条件下, 结果与之相反; 电刷镀含SiC颗粒的复合镀渗层的耐蚀性能在静态和动态冲蚀条件下均低于单一合金层. 对两种复合镀渗层的冲蚀截面形貌观察表明: 弥散分布的纳米SiO2颗粒能明显改善Ni基合金层的耐冲蚀性能; 而添加纳米SiC颗粒在渗金属过程中已完全分解, 导致三元硅化物(Cr6.5Ni2.5Si)和碳化物(Cr23C6)的析出, 而析出相在冲蚀过程易于脱落, 加速了Ni基合金层的质量流失.     

Characterization of deposits build-up on austenitic stainless steel AISI 316L exposed in high purity water system

For the characterization of deposit layers on AISI 316L surfaces in high purity water systems, operating up to 80 °C Mössbauer spectroscopy (ME), scanning electron microscopy (SEM), X-ray fluorescence (XRF) and X-ray photoelectron spectroscopy (XPS) are used. Austenitic steel particles were identified on the surfaces of systems not properly cleaned before start-up. Long exposition of austenitic surfaces to high purity water promotes the build-up, composed by trivalent iron and chromium oxidehydroxides and oxide. The oxidehydroxide phase is located mainly at the solid-water interface, whereas oxide phase is in direct contact with metal. Spheroid-like morphology of particles in these layers and the lack of metal attack suggest that coagulation and crystallization processes are the way for oxide production from existing dissolved species.     

正常妊娠与妊高征患者血清中8种必需微量元素水平的研究

７８例正常妊娠妇女和４０例妊高征患者血清中铁、锌、铜、锰、硒、铬、钴和镍的含量与健康未孕妇女比较，正常妊娠妇女和妊高征患者均是铜和锰的含量升高，铁、锌、硒、铬、钴和镍含量降低；妊高征患者与正常妊娠妇女比较，则是铁、铜和锰的含量升高，锌、硒、铬、钴和镍的含量降低。     

过敏性哮喘患者血清中10种必需微量元素水平的研究

３４例过敏性哮喘患者血清中铁，锌、铜，锰硒铬，钴镍，钡，钼的含量水平与对照组比较，揭示：（１）铁，铜，铬的含量升高；（２）硒，镍，钴、钒的钼的含量降低；（３）锌和锰的含量差异无显著性，Ｐ〉０．０５。     

116例冠心病患者血清中10种必需微量元素水平的研究

１１６例冠心病患者血清中１０种必需微量元素的含量与正常值比较，具有如下特点：（１）铁，锌、铬，镍含量升高；２硒钴，钒，钼含量降低；（３）铜和锰差异无显著性。     

锂离子二次电池碳负极材料的改性

作为锂离子二次电池的碳负极材料，其改性方面的研究内容主要有：引入非金属元素，引入金属元素，处理表面及其它方面。纺入的非金属元素有硼，硅，氮，磷和硫。引入的金属元素有钾，铝，镓和钒，镍，钴，铜，铁等过渡金属元素。表面处理的方法包括氧化，形成表面层等。     

On-line electrolytic dissolution of alloys in flow-injection analysis. Part 3. Multi-elemental analysis of stainless steels by inductively coupled plasma atomic emission spectrometry

The simultaneous determination of chromium, nickel, manganese, silicon and iron in stainless steels was achieved by inductively coupled plasma atomic emission spectrometry (ICP-AES) after on-line electrodissolution using an improved flow-through electrolytic cell. The solution containing the electrodissolved ions was impelled by an air carrier stream in a flow-injection manifold towards a mixing-dilution chamber. From this chamber, the diluted and homogenized solution was aspirated and nebulized into the ICP torch. A quantification procedure is proposed for direct solid analysis without the use of certified reference materials. Under the proposed electrolysis conditions, up to 60 solid samples can be analysed per hour. Results obtained for alloying elements in austenitic and ferritic stainless steels were in good agreement with the certified values.     

Use of spectroscopy of gamma-radiation from the inelastic scattering of reactor fast neutrons for elemental analysis

Gamma-spectra of stainless-steel and soil samples have been measured to study the potentialities of using spectroscopy of γ-radiation from the inelastic scattering of reactor fast neutrons for element analysis of various materials. Contents of iron, chromium, nickel, manganese, silicon and titanium in stainless steel, and those of silicon, iron, aluminium, magnesium, calcium, sodium, titanium, carbon and oxygen in soil have been determined by comparing the spectra of the samples with those of specially prepared mixtures of elements. The distinguishing features, advantages, and limitations of this method are discussed.     

Zone refining of plutonium metal

An experiment demonstrated the possibility of developing a zone refining process that would produce the first plutonium metal of extremely high purity. Plutonium rods containing known amounts of impurities were melted inside tantalum boats and passed horizontally through a three-turn, high-frequency coil so as to cause a narrow molten zone to pass through each rod 10 times. The impurity elements cobalt, chromium, iron, nickel, neptunium, and uranium moved in the same direction as the molten zone, as predicted; the elements aluminum, americium, and gallium moved in the opposite direction of the molten zone, as predicted. As the impure alloy was zone refined, δ-phase plutonium metal crystals formed.     

Effects of various elements on arsenic accumulation of the alga Dunaliella salina

The effect of 23 various elements (nitrogen, manganese, magnesium, molybdenum, zinc, selenium, gallium, nickel, cobalt, lithium, strontium, vanadium, tin, antimony, bismuth, cadmium, chromium, lead, iron, silver, copper, potassium and calcium) in water on growth and arsenic accumulation in Dunaliella saline was investigated. The order of growth inhibition of D. salina by these elements was Ag>Cd>Co>Ni>Cu>Zn>Fe>Sb>Ga>Cr>Bi>Sr>Mn>Sn>Se>Pb>V>Ca, Mg, Mo, K, Li. Arsenic accumulation in D. salina was unaffected by an increase in calcium and chromium. Also, the arsenic content in D. salina decreased at a potassium concentration of 100 mg dm^?3, and was also reduced by the addition of cadmium and nitrogen; however, it was increased by the addition of lithium at 100 mg dm^?3, tin, gallium, bismuth, strontium, vanadium, iron and manganese at 10 mg md^?3, lead, antimony, zinc, copper cobalt and nickel at 1 mg dm^?3, selenium at 0.1 mg dm^?3, and silver at 0.005 mg dm^?3, respectively. These results imply that arsenic accumulation by D. salina depends upon biological activity and physical adsorption.