Beitrag zur Charakterisierung von Oxidschichten auf dem Stahl X6CrNiTi18 10 in wäßrigen Elektrolyten bis 250°C und unter dem Einfluß von korrosionsinduzierenden und -inhibierenden Spezies

Der Untersuchung der Heißwasserkorrosion wird mit Hinblick auf ihre praktische Bedeutung in der Chemie- und Kraftwerksindustrie ein großes Interesse gewidmet. Bei dem Betrieb von KKW- Druckwasserreaktoren stellen die häufig auftretenden Verfügbarkeitseinschränkungen bzw. nötigen Erneuerungen von Dampferzeugern (DE) aufgrund von korrosiven Schädigungen der Nadelrohre ein weltweites Problem dar /1/. Dampferzeugernadelrohre, die Primär- und Sekundärkreislauf trennen, sind wegen ihrer geringen Wandstärke (1,4 mm) die einen möglichst großen Wärmeübergang realisieren soll, eine besondere Schwachstelle im System /2/

Acid Treatments of Ti-Based Metallic Glasses for Improving Corrosion Resistance in Implant Applications

Ti-based bulk metallic glasses are promising materials for metallic bone implants, mainly due to their mechanical biofunctionality. A major drawback is their limited corrosion resistance, with high sensitivity to pitting. Thus, effective surface treatments for these alloys must be developed. This work investigates the electrochemical treatment feasibility of nitric acid (HNO3) solution for two bulk glass-forming alloys. The surface states obtained at different anodic potentials are characterized with electron microscopy and Auger electron spectroscopy. The corrosion behavior of the treated glassy alloys is analyzed via comparison to non-treated states in phosphate-buffered saline solution (PBS) at 37 °C. For the glassy Ti47Zr7.5Cu38Fe2.5Sn2Si1Ag2 alloy, the pre-treatment causes pseudo-dealloying, with a transformation from naturally passivated surfaces to Ti- and Zr-oxide nanoporous layers and Cu-species removal from the near-surface regions. This results in effective suppression of chloride-induced pitting in PBS. The glassy Ti40Zr10Cu34Pd14Sn2 alloy shows lower free corrosion activity in HNO3 and PBS due to Pd stabilizing its strong passivity. However, this alloy undergoes pitting under anodic conditions. Surface pre-treatment results in Cu depletion but causes enrichment of Pd species and non-homogeneous surface oxidation. Therefore, for this glassy alloy, pitting cannot be completely inhibited in PBS. Concluding, anodic treatments in HNO3 are more suitable for Pd-free glassy Ti-based alloys

Corrosion Fatigue Studies on a Bulk Glassy Zr-Based Alloy under Three-Point Bending

Corrosion fatigue (CF) tests were carried out on bulk glassy Zr52.5Cu17.9Al10Ni14.6Ti5 (Vitreloy 105) samples under load-controlled three-point bending conditions with a load ratio of R = 0.1 in 0.01 M Na2SO4 + 0.01 M NaCl electrolyte. During cyclic testing, the bar-shaped specimens were polarized in situ at constant potentials and the current was monitored. Three different anodic potentials within the interval between the pitting potential EP and the repassivation potential ER and three different load amplitudes were applied. In some cases, in situ microscopic observations revealed the formation of black corrosion products in the vicinity of the crack tip during anodic polarization. Fractographic analysis revealed a clear distinction between two modes of crack growth characterized by smooth dissolution induced regions on the one hand and slim fast fracture areas on the other hand. Both alternating features contributed to a broad-striated CF fracture surface. Moreover, further fatigue tests were carried out under free corrosion conditions yielding additional information on crack initiation and crack propagation period by means of the open circuit potential (OCP) changes. Thereby, a slight increase in OCP was detected after rupture of the passive layer due to bare metal exposed to the electrolyte. The electrochemical response increased continuously according to stable crack propagation until fracture occurred. Finally, the fracture surfaces of the CF samples were investigated by energy dispersive X-ray with the objective of analyzing the elemental distribution after anodic dissolution. Interestingly, anodic polarization at a near repassivation potential of −50 mV vs. saturated calomel electrode (SCE), which commands a constant electric potential of E = 0.241 V vs. standard hydrogen electrode (SHE), led to favorable effects on the fatigue lifetime. In conclusion, all results are conflated to a CF model for bulk glassy Vitreloy 105 under anodic polarization in chloride-containing electrolyte and compared to the previously proposed stress corrosion mechanisms under similar conditions. © 2017 Grell, Wilkin, Gostin, Gebert and Kerscher

Corrosion Fatigue Studies on a Bulk Glassy Zr-Based Alloy under Three-Point Bending

Corrosion fatigue (CF) tests were carried out on bulk glassy Zr52.5Cu17.9Al10Ni14.6Ti5 (Vitreloy 105) samples under load-controlled three-point bending conditions with a load ratio of R = 0.1 in 0.01 M Na2SO4 + 0.01 M NaCl electrolyte. During cyclic testing, the bar-shaped specimens were polarized in situ at constant potentials and the current was monitored. Three different anodic potentials within the interval between the pitting potential EP and the repassivation potential ER and three different load amplitudes were applied. In some cases, in situ microscopic observations revealed the formation of black corrosion products in the vicinity of the crack tip during anodic polarization. Fractographic analysis revealed a clear distinction between two modes of crack growth characterized by smooth dissolution induced regions on the one hand and slim fast fracture areas on the other hand. Both alternating features contributed to a broad-striated CF fracture surface. Moreover, further fatigue tests were carried out under free corrosion conditions yielding additional information on crack initiation and crack propagation period by means of the open circuit potential (OCP) changes. Thereby, a slight increase in OCP was detected after rupture of the passive layer due to bare metal exposed to the electrolyte. The electrochemical response increased continuously according to stable crack propagation until fracture occurred. Finally, the fracture surfaces of the CF samples were investigated by energy dispersive X-ray with the objective of analyzing the elemental distribution after anodic dissolution. Interestingly, anodic polarization at a near repassivation potential of −50 mV vs. saturated calomel electrode (SCE), which commands a constant electric potential of E = 0.241 V vs. standard hydrogen electrode (SHE), led to favorable effects on the fatigue lifetime. In conclusion, all results are conflated to a CF model for bulk glassy Vitreloy 105 under anodic polarization in chloride-containing electrolyte and compared to the previously proposed stress corrosion mechanisms under similar conditions. © 2017 Grell, Wilkin, Gostin, Gebert and Kerscher

Controlling the Young’s modulus of a ß-type Ti-Nb alloy via strong texturing by LPBF

The ß-type Ti-42Nb alloy was processed by laser powder bed fusion (LPBF) with an infrared top hat laser configuration aiming to control the Young’s modulus by creating an adapted crystallographic texture. Utilizing a top hat laser, a microstructure with a strong 〈0 0 1〉 texture parallel to the building direction and highly elongated grains was generated. This microstructure results in a strong anisotropy of the Young’s modulus that was modeled based on the single crystal elastic tensor and the experimental texture data. Tensile tests along selected loading directions were conducted to study the mechanical anisotropy and showed a good correlation with the modeled data. A Young’s modulus as low as 44 GPa was measured parallel to the building direction, which corresponds to a significant reduction of over 30% compared to the Young’s modulus of the Gaussian reference samples (67–69 GPa). At the same time a high 0.2% yield strength of 674 MPa was retained. The results reveal the high potential of LPBF processing utilizing a top hat laser configuration to fabricate patient-specific implants with an adapted low Young’s modulus along the main loading direction and a tailored mechanical biofunctionality

Novel low modulus beta-type Ti–Nb alloys by gallium and copper minor additions for antibacterial implant applications

This study aims to develop novel low-modulus, corrosion-resistant Ti-based alloys with enhanced antimicrobial properties for bone-related implant applications. Novel β-type (Ti–45Nb)-based alloys with minor additions of the antibacterial elements Ga and/or Cu (up to 4 wt.%) were produced by a two-step casting process followed by homogenization treatment. Three nominal compositions (Ti–45Nb)96-4 Ga, (Ti–45Nb)96–4Cu and (Ti–45Nb)96-2 Ga–2Cu (wt.%) were prepared based on alloy design approach using [Mo]eq and electron per atom (e/a) ratio. The influence of Ga and/or Cu addition on the phase constitution, mechanical response and corrosion characteristics in simulated body fluids (PBS, 37.5 °C) has been investigated. X-ray diffraction studies displayed a single β phase structure for all alloys, with an observed lattice contraction evidenced by the reduction of lattice parameters during Rietveld analysis. Homogenous equiaxed microstructures with grain sizes ranging from 55 μm up to 323 μm were observed for (Ti–45Nb)96-4 Ga, (Ti–45Nb)96-2 Ga–2Cu and (Ti–45Nb)96–4Cu alloys. The alloys displayed excellent plasticity with no cracking, or fracturing during compression tests. Their tensile strength, Young's modulus, maximum tensile strain and elastic energy were measured in the ranges of 544–681 MPa, 73–78 GPa, 17–28% and 2.5–3.7 MJ/m3, in the order (Ti–45Nb)96-4 Ga > (Ti–45Nb)96-2 Ga–2Cu > (Ti–45Nb)96–4Cu. In addition, it has been observed that micro-alloying Ti–Nb alloy with Ga and/or Cu posed no deleterious effect on the corrosion resistance in simulated body fluid conditions. The improvement in strength of the developed alloys has been discussed based on grain boundary and solid-solution strengthening, whereas the improved plasticity is attributed to work hardening