Influence of environment on the corrosion of glass–metal connections

'Glass sensors' of the eighteenth century Backer glass and the sixteenth century enamel from Limoges have been chosen for a series of experiments. Combinations of these materials with different base materials such as copper and bronze has been investigated. To create surface changes on the 'glass sensor', a corrosion process was induced in a controlled environment. A variety of corrosive agents such as hydrochloric acid, sulfuric acid, water and formaldehyde were used. The sample immersed in the corrosive solution was exposed alternately to light and high temperature for a total of 38 weeks. During this period, macroscopic and microscopic observations were made and series of tests such as SEM/EDS and Raman spectroscopy were performed on the surface of the samples. ICP-MS methods were used to determine the change in the chemical composition of the solutions where the samples had corroded. The primary aim of this study was to identify the impact of a number of external corrosive variables such as temperature, humidity and local environment to identify the most damaging environments for glass–metal objects. The obtained results showed the chemical and physical phenomena acting on the surface of the glass, metal or in the place of their joints. Information obtained on this study was used to explain the influence of the environment on the surface of glass–metal materials. Results can be used in the design of conservation work as well as for sustainable conservation

Transition from Endothermic to Exothermic Dissolution of Hydroxyapatite Ca5(PO4)3OH–Johnbaumite Ca5(AsO4)3OH Solid Solution Series at Temperatures Ranging from 5 to 65 °C

Five crystalline members of the hydroxyapatite (HAP; Ca5(PO4)3OH)–johnbaumite (JBM; Ca5(AsO4)3OH) series were crystallized at alkaline pH from aqueous solutions and used in dissolution experiments at 5, 25, 45, and 65 °C. Equilibrium was established within three months. Dissolution was slightly incongruent, particularly at the high-P end of the series. For the first time, the Gibbs free energy of formation ΔGf0, enthalpy of formation ΔHf0, entropy of formation Sf0, and specific heat of formation Copf were determined for HAP–JBM solid solution series. Based on the dissolution reaction, Ca5(AsO4)m(PO4)3−mOH = 5Ca2+(aq) + mAsO43−(aq) + (3 − m)PO43−(aq) + OH−(aq), their solubility product Ksp,298.15 was determined. Substitution of arsenic (As) for phosphorus (P) in the structure of apatite resulted in a linear increase in the value of Ksp: from HAP logKsp,298.15 = −57.90 ± 1.57 to JBM logKsp,298.15 = −39.22 ± 0.56. The temperature dependence of dissolution in this solid solution series is very specific; in the temperature range of 5 °C to 65 °C, the enthalpy of dissolution ΔHr varied around 0. For HAP, the dissolution reaction at 5 °C and 25 °C was endothermic, which transitioned at around 40 °C and became exothermic at 45 °C and 65 °C

Analysis of cross-sectional layers of corrosion using metallographic microscope

The aim of this study was to identify and recognize the phenomena of corrosion between glass-metal connections. Experiments were carried out on historical and contemporary samples treated with corrosion catalysts and the results helped to identify the most corrosive conditions for historic objects. Microscopic observations were carried out on cross-sectional layers of specially prepared samples of enamel on copperplate, corresponding to the chemical composition of historic samples-enamel from Limoges. Subsequently, a series of techniques were implemented improving the quality of the image. A 20-micron thick corrosion layer can be observed and recorded using this method. Observations allowed to determine the quality and technology aspects of the enamel exposed to the processes. The diagnosis of corrosion processes is extremely important in order to determine the application technique of enamel on the metal substrate.Microscopic images therefore revealed the formation of corrosion products. This proved an efficient and effective way to provide information on the thickness, color and structure of the observed layers. Micro-photographs from a metallographic microscope allowed for further planning and the subsequent use of a Scanning Electron Microscope (SEM) with an Energy Dispersive Spectrometer (EDS) and Raman Spectrometer (RS) - mitigating the need for the analysis of the entire sample's surface. Most corroded places have been identified and the metal proved to be more reactive material. The impact of factors such as: the technique of layering the enamel, structural inclusions, pitting corrosion, temperature and the environment's impact have been clearly linked to the overlap of the corrosion processes

Weathering in a regolith on the Werenskioldbreen Glacier forefield (SW Spitsbergen). 2. Speciation of Fe, Mn, Pb, Cu and Zn in the chronosequence

The evolution of chemical speciation of Fe, Mn, Pb, Cu, and Zn was investigated in the chronosequence of young sediments, exposed by a currently retreating Arctic glacier on Spitsbergen. Werenskioldbreen is a 27 km2 subpolar, land-terminated, polythermal glacier in recession, located near the SW coast of West Spitsbergen. Three samples of structureless till were collected at locations exposed for 5, 45 and 70 years. Four grain-size fractions were separated: > 63, 20–63, 2–20, and < 2 µm. Speciation of Fe, Mn, Pb, Cu, and Zn was determined using a 6-step sequential chemical extraction method: 1) 1 M sodium acetate, 2) 1 M hydroxylamine hydrochloride in acetic acid, 3) sodium dithionite in buffer, 4) acid ammonium oxalate, 5) boiling HCl, 6) residuum. The weathering in the proglacial area of the retreating glacier is very fast. The geochemical fates of the metals in question correlate with each other, reflecting a) the geochemical similarities between them, b) the similarities of their primary mineral sources, c) the significant role of incongruent dissolution. The weathering processes dominating the system are redox reactions and incongruent dissolution, followed by precipitation of secondary phases and partial sorption of aqueous species. As a result, the elements released from weathering minerals are only partially transported away from the system. The remaining part transforms by weathering from the coarse-grained fraction (dominated by fragments of primary minerals) into the fine-grained fraction (in the form of secondary, authigenic minerals or as species sorbed onto a mineral skeleton). This is very strongly pronounced within the chronosequence: the content of each of the metals studied correlates identically with the grain size, despite the differences in their chemical character and affinities. The microscope study presented herein indicates that the role of incongruent dissolution previously was underestimated. Also, the formation of coatings of secondary phases on primary mineral surfaces was observed. All these rapid weathering processes affect the mineral speciation of initial soils as well as the composition of mineral suspensions transported away by rivers to the nearby ocean