Mechanistic studies of corrosion product flaking on copper and copper-based alloys in marine environments

AbstractThe mechanism of corrosion product flaking on bare copper sheet and three copper-based alloys in chloride rich environments has been explored through field and laboratory exposures. The tendency for flaking is much more pronounced on Cu and Cu–4wt%Sn than on Cu–15wt%Zn and Cu–5wt%Al–5wt%Zn. This difference is explained by the initial formation of zinc and zinc–aluminum hydroxycarbonates on Cu15Zn and Cu5Al5Zn, which delays the formation of CuCl, a precursor of Cu2(OH)3Cl. As a result, the observed volume expansion during transformation of CuCl to Cu2(OH)3Cl, and concomitant corrosion product flaking, is less severe on Cu15Zn and Cu5Al5Zn than on Cu and Cu4Sn

Remote Assessment of Cultural Heritage Environments with Wireless Sensor Array Networks

The logistics and cost of environmental monitoring can represent challenges for heritage managers, partly because of the sheer number of environmental parameters to consider. There is a need for a system, capable of monitoring the holistic impact of the environment on cultural materials while remaining relatively easy to use and providing remote access. This paper describes a dosimetric system based on piezoelectric quartz crystal technology. The prototype sensing module consists of an array of piezoelectric quartz crystals (PQC) coated with different metals (Fe, Cu, Ni and Sn) and includes a temperature and relative humidity sensor. The communication module involves an 802.15.4 low-power radio and a GPRS gateway which allows real time visualisation of the measurements online. An energy management protocol ensures that the system consumes very low power between measurements. The paper also describes the results and experiences from two heritage field deployments, at Apsley House in London, UK, and at the Royal Palaces of Abomey in Benin. Evaluation of PQC measurements, temperature, relative humidity and the rate of successful transmission over the communication systems are also reported

Die Behandlung der Schizophrenie vor Einführung antipsychotischer Medikamente:(im Zeitraum von 1928 - 1940)

In der vorliegenden Studie wurde die Behandlung der Schizophrenie vor Einführung der Neuroleptika untersucht. Die damaligen Therapiemethoden wie die Fieberkur, der Dauerschlaf, die Sedativagabe, die Insulinschocktherapie und die Arbeitstherapie stellten dabei einen Untersuchungsschwerpunkt dar. Auffällig war eine eher bescheidene Prognose. Für keine der verschiedenen Behandlungsmethoden konnte ein statistisch fassbarer Prognosevorteil gezeigt werden, wenngleich diese damals durchaus als wirksam angesehen wurden. In einem weiteren Kapitel wurde betrachtet, in welchem Ausmaß die Patienten der psychiatrischen Universitätsklinik Münster im Dritten Reich durch eugenische Maßnahmen betroffen waren. Dabei waren die Patienten mit einer positiven Familienanamnese und die Patienten, welche „gegen ärztlichen Rat" entlassen wurden, signifikant häufiger betroffen

Characterization of surface films that develop on pre-oxidized copper in anoxic simulated groundwater with sulphide

Surface films formed on pre-oxidized copper in anoxic simulated groundwater with sulphide were characterized by field emission gun scanning electron microscopy (FEG-SEM), Fourier transform infrared spectroscopy (FT-IR), open circuit potential (OCP) measurements, and via analysing the water chemistry and weight changes in the specimens. Additionally, films developed under identical conditions on pre-oxidized and ground copper specimens were characterized by glow discharge optical emission spectroscopy (GDOES). The results revealed that the sulphide content in the groundwater significantly influences the morphology, composition and thickness of the surface film. The build-up of Cu2S was evidenced at the sulphide contents of 32 mg/L and 320 mg/L. GDOES depth profiling revealed that sulphur and oxygen coexisted in the film all through its thickness, yet the surface was essentially rich in sulphur. The results from characterization are presented in detail in this paper and discussed from the perspective of capabilities of the used methods

Penetration of corrosive species into copper exposed to simulated O2-free groundwater by time-of-flight secondary ion mass spectrometry (ToF-SIMS)

ToF-SIMS analysis of copper samples after exposures to simulated groundwater with and without sulfide addition was performed to investigate the penetration of corrosive species containing H, S, O, and Cl, into copper. Depth profiles show extent of penetration and 2D/3D images reveal local elemental distribution of the corrosive species at different depths inside copper. Pre-oxidation did not reduce the penetration while sulfide additional in groundwater and exposure at 60 \ub0C significantly promoted the penetration. The extent of penetration of the corrosive species into copper demonstrates the need for risk assessment of complex corrosion forms such as sulfide-induced embrittlement and cracking

Corrosion and runoff rates of Cu and three Cu-alloys in marine environments with increasing chloride deposition rate

AbstractBare copper sheet and three commercial Cu-based alloys, Cu15Zn, Cu4Sn and Cu5Al5Zn, have been exposed to four test sites in Brest, France, with strongly varying chloride deposition rates. The corrosion rates of all four materials decrease continuously with distance from the coast, i.e. with decreasing chloride load, and in the following order: Cu4Sn>Cu sheet>Cu15Zn>Cu5Al5Zn. The patina on all materials was composed of two main layers, Cu2O as the inner layer and Cu2(OH)3Cl as the outer layer, and with a discontinuous presence of CuCl in between. Additional minor patina constituents are SnO2 (Cu4Sn), Zn5(OH)6(CO3)2 (Cu15Zn and Cu5Al5Zn) and Zn6Al2(OH)16CO3·4H2O/Zn2Al(OH)6Cl·2H2O/Zn5Cl2(OH)8·H2O and Al2O3 (Cu5Al5Zn). The observed Zn- and Zn/Al-containing corrosion products might be important factors for the lower sensitivity of Cu15Zn and Cu5Al5Zn against chloride-induced atmospheric corrosion compared with Cu sheet and Cu4Sn.Decreasing corrosion rates with exposure time were observed for all materials and chloride loads and attributed to an improved adherence with time of the outer patina to the underlying inner oxide. Flaking of the outer patina layer was mainly observed on Cu4Sn and Cu sheet and associated with the gradual transformation of CuCl to Cu2(OH)3Cl of larger volume. After three years only Cu5Al5Zn remains lustrous because of a patina compared with the other materials that appeared brownish–reddish.Significantly lower release rates of metals compared with corresponding corrosion rates were observed for all materials. Very similar release rates of copper from all four materials were observed during the fifth year of marine exposure due to an outer surface patina that with time revealed similar constituents and solubility properties

Time Dependent Surface Corrosion Analysis and Modelling of Automotive Steel Under a Simplistic Model of Variations in Environmental Parameters

This research presents time-dependent corrosion analysis of automotive steel utilised in a large military vehicle in real operating environment, followed by simulated environmental tests and simplistic surface corrosion modelling. Time-dependent surface corrosion accumulated on this specific component was observed to be approximately 250 µm thick, with the identification of surface contaminants such as chlorine and sulphur. Simulated environmental tests considering temperature and relative humidity variations were performed to evaluate quantitative corrosion damage to the structure of the vehicle. The relationship of various temperatures and relative humidity with respect to time, within the context of corrosion initiation and propagation, has been presented. A mathematical model to incorporate corrosion accumulation on the surfaces derived from the simulated environmental tests is presented

Anxiety and depression in children and adults: influence of serotonergic and neurotrophic genes?

There are two major hypotheses regarding the etiology of anxiety and depression: the mono-amine hypothesis and the hypothesis of an abnormal stress response acting partly via reduced neurogenesis. Association studies have focused on genes involved in these processes, but with inconclusive results. This study investigated the effect of 45 single nucleotide polymorphisms (SNPs) in genes encoding for serotonin receptors 1A, 1D, 2A, catechol-O-methyltransferase (COMT), tryptophane hydroxylase type 2 (TPH2), brain derived neurotrophic factor (BDNF), PlexinA2 and regulators of G-protein-coupled signaling (RGS) 2, 4, 16. Anxious depression (A/D) symptoms were assessed five times in 11 years in over 11 000 adults with 1504 subjects genotyped and at age 7, 10, 12 and during adolescence in over 20 000 twins with 1078 subjects genotyped. In both cohorts, a longitudinal model with one latent factor loading on all A/D measures over time was analysed. The genetic association effect modeled at the level of this latent factor was 60% and 70% heritable in the children and adults, respectively, and explained around 50% of the total phenotypic variance. Power analyses showed that the samples contained 80% power to detect an effect explaining between 1.4% and 3.6% of the variance. However, no SNP showed a consistent effect on A/D. To conclude, this longitudinal study in children and adults found no association of SNPs in the serotonergic system or core regulators of neurogenesis with A/D. Overall, there has been no convincing evidence, so far, for a role of genetic variation in these pathways in the development of anxiety and depression