Deamidation at Asparagine and Glutamine As a Major Modification upon Deterioration/Aging of Proteinaceous Binders in MuralPaintings

Proteomic strategies are herein proved to be a complementary approach to the well established amino acid composition analysis for the characterization of the aging and deterioration phenomena occurring to proteinaceous materials in works-of-art. Amino acid analyses on several samples demonstrated that proteins in the frescoes from the Camposanto Monumentale in Pisa are deteriorated as revealed by the decrease in Met, Lys, and Tyr content and by the presence in all the samples of amino malonic acid as a result of Ser, Phe, and Cys oxidation. Proteomic analysis identified deamidation at Asn and Gln as a further major event occurred. This work paves the way to the exploitation of proteomic strategies for the investigation of the molecular effects of aging and deterioration in historical objects. Results show that proteomic searches for deamidation by liquid chromatography-tandem mass spectrometry (LC-MS/MS) could constitute a routine analysis for paintings or any artistic and historic objects where proteins are present. Peptides that can be used as molecular markers when casein is present were identified

Improvement in Wear Resistance of Grade 37 Titanium by Microwave Plasma Oxy-Carburizing

Grade 37 titanium is widely used in racing applications thanks to its oxidation resistance up to 650 °C, but it suffers from poor wear and fretting resistance, especially at high temperature. In this paper, different surface modification techniques, namely, carburizing, coating by PVD-ZrO2 and a novel microwave plasma oxy-carburizing treatment, are investigated in terms of hardness, wear resistance and scratch hardness, compared to the untreated substrate. Numerical simulation allowed optimization of the design of the microwave plasma source, which operated at 2.45 GHz at atmospheric pressure. The proposed microwave plasma oxy-carburizing treatment is localized and can serve to improve the tribological properties of selected regions of the sample; compared to untreated Grade 37 titanium, the oxy-carburized layer presents a decrease in the wear rate at 450 °C against alumina of 54% and an increase in scratch hardness of more than three times

A mass spectrometric study on tannin degradation within dyed woolen yarns

Natural tannins from various plants have been used throughout human history in textile dyeing, often as mordant dyes. The ageing behavior of these dyes is a challenge in conservation science, requiring a thorough knowledge of the textile–mordant-dye system. In this work, we analyzed reference wool yarns dyed with natural tannins from oak gallnuts, walnut (Juglans regia), and catechu (Acacia catechu), after artificial ageing. To gain insights on the composition of the dyestuffs and on how they aged, an analytical procedure based on extraction with Na2EDTA/DMF (ethylenediaminetetraacetic acid/dimethylformamide) and high-performance liquid chromatography (HPLC) analysis using high-resolution mass spectrometry detection was used. Since conventional reversed-phase (RP) columns usually show poor retention efficiency of highly polar compounds such as tannins, an RP-amide embedded polar group stationary phase was used to achieve optimal retention of the most polar compounds. Tannins from oak gallnuts showed little degradation after ageing, while a significant increase in the content of hydroxybenzoic acids was observed for tannins from walnut and catechu. Finally, the analytical procedure was applied to characterize the tannin dyes in historical tapestries from the 15th to 16th century, and the results were discussed in comparison with the reference yarns

The analysis of the Saltzman Collection of Peruvian dyes by high performance liquid chromatography and ambient ionisation mass spectrometry

Yarn samples from the Saltzman Collection of Peruvian dyes were characterized by several different analytical techniques: high performance liquid chromatography with both diode array detection (HPLC-DAD) and electrospray ionisation with tandem mass spectrometry (HPLC-ESI-Q-ToF), direct analysis in real time (DART) mass spectrometry and paper spray mass spectrometry. This report serves primarily as a database of chemical information about the colorants in these dye materials for those studying ancient South American textiles and their colorants. We also provide a comparison of the results obtained by currently widespread HPLC techniques with those of two different ambient ionisation direct mass spectrometry methods to highlight the advantages and disadvantages of these approaches

A novel microwave and induction heating applicator for metal making: Design and testing

The use of microwave heating in primary metallurgy is gaining an increasing interest due to the possibility to selectively process ores and to volumetrically heat large amounts of low-thermal conductivity minerals. In this paper the study, development and testing of a new applicator combining the use of microwave and induction heating for rapid reduction of metal containing oxides is described. Numerical simulation was used in order to achieve the proper control over heat generation, considering the use of microwave solid state generators. A prototype, with a capacity up to 5 liters of standard input feed but with the predisposition for continuous processing has been designed, built and tested on reference loads like iron oxide powders and pellets. Results on the microwave heating part of the applicator indicate that it allows to efficiently and rapidly process these kinds of loads, which change from dielectric to conductors as reduction proceeds. The use of variable frequency solid state microwave generators allows to maximize energy efficiency and to controllably change the heating pattern inside the load

Laser hardening of steel sintered parts

The possibility of applying rapid and localized laser hardening to near-net shape parts, like the ones deriving from powder metallurgy (P/M) is investigated, demonstrating that even low alloyed steels (Fe + 2% Cu + 0,7% C) can be successfully heat treated with minimal or no dimensional variations. Laser hardening conditions have been selected on the basis of the results of the previous research, carried out by means of an Nd-YAG high power system [1]. To avoid some carbon loss, observed on previous activities, the samples have been protected by neutral atmosphere. The microstructural features of the laser hardened steels have been analyzed by optical microscopy, whereas the surface micro-geometry has been characterized by scanning electron microscope. Hardened depth (HD), hardened width (HW) and hardened area (HA) have been measured as well. As expected, the micro-hardness profiles present a sharp drop at low distance from the hardened surface. The typical splitting between hardened zone and heat-Affected zone (HAZ), well known from laser hardened fully dense steels, has been observed also on low-Alloy sintered steels. The use of a protective atmosphere has been helpful to control surface decarburization and to prevent oxidation. The research confirm that Laser transformation Hardening (LTH) is a suitable hardening process of P/M components, through the action of a scanning laser beam. The short heating time and the modest volume fraction structurally modified can contribute to avoid part distortion, in comparison with other hardening methods

Microwave-assisted preparation of multi principal element alloys by powder metallurgy approach

According to literature, the synthetic route to produce High entropy alloys (HEAs) should guarantee short alloying time, efficient cooling and capability to operate in controlled atmosphere. Such conditions can be achieved using high frequency electromagnetic fields, like microwave heating. In this work FeCoNiCrAl and FeCoNiCuAl, both equiatomic and reinforced by the 10% wt. of SiC were prepared by microwave assisted techniques. Results show that direct microwave heating of the powder precursors occurs, until the ignition conditions are reached. The temperature and duration of the microwave-assisted process result much lower than other conventional powder metallurgy routes, but at the cost of a higher residual porosity. Sample characterization confirmed that the powder metallurgy approach is suitable to retain the shape of the load imparted during forming by uniaxial pressing. The homogeneity of the samples resulted in being good in all cases, without the dendritic segregation typically occurring by liquid phase processing. © 2017 European Powder Metallurgy Association (EPMA

High entropy alloys obtained by field assisted powder metallurgy route: SPS and microwave heating

The aim of this work was to investigate the field assisted powder metallurgy route for producing HEAs at equimolar composition, i.e. FeCoNiCrAl, starting from metal powders. Both mixed, mechanically activated and mechanically alloyed powders have been used. The powders obtained by mechanical alloying were synthesized only by SPS, whereas the remaining ones were sintered by SPS or microwave heating. The investigated field assisted sintering techniques allowed an extremely short alloying time, high energy density on the load and negligible contamination by the surrounding environment. Both the conducted sintering-synthesis technology resulted not definitive to produce chemical homogeneity and to obtain a single stable structure. Thus a subsequently heat treatment was required. The post heat treatment, indeed, led to a single crystalline structure (FCC) and the material was fully recrystallized. After heat treatment samples are isomorphic: they exhibit two different phases with the same FCC cell, but different chemical composition, in detail Fe-Cr richer and Al-Ni richer. SPS-ed samples present a reduced porosity, while microwave processed ones are much more porous and this is reflected in the mechanical properties