Oxidation and Cross-Linking in the Curing of Air-Drying Artists' Oil Paints

In this study, the chemistry of air-drying artist's oil paint curing and aging up to 24 months was studied. The objective is to improve our molecular understating of the processes that lead to the conversion of the fluid binder into a dry film and how this evolves with time, which is at the base of a better comprehension of degradation phenomena of oil paintings and relevant to the artists' paint manufacturing industry. To this aim, a methodological approach based on thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), gas chromatography-mass spectrometry (GC-MS), and analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS) was implemented. Model paintings based on linseed oil and safflower oil (a drying and a semidrying oil, respectively) mixed with two historically relevant pigments - lead white (a through drier) and synthetic ultramarine blue (a pigment often encountered in degraded painting layers) - were investigated. The oil curing under accelerated conditions (80 °C under air flow) was followed by isothermal TG analysis. The oxygen uptake profiles were fit by a semiempiric equation that allowed to study the kinetics of the oil oxidation and estimate oxidative degradation. The DSC signal due to hydroperoxide decomposition and radical recombination was used to monitor the radical activity over time and to evaluate the stability of peroxides formed in the paint layers. GC-MS was performed at 7 and 24 months of natural aging to investigate the noncovalently cross-linked fractions and Py-GC-MS to characterize the whole organic fraction of the model paintings, including the cross-linked network. We show that the oil-pigment combination may have a strong influence on the relative degree of oxidation of the films formed with respect to its degree of cross-linking, which may be correlated with the literature on the stability of painting layers. Undocumented pathways of oxidation are also highlighted

Valorization of not soluble byproducts deriving from green keratin extraction from poultry feathers as filler for biocomposites

The valorization of poultry feathers wastes is very important to reduce the environmental pollution deriving from their disposal. In this frame, we present the production process of completely natural, biodegradable, biocompatible, and eco-friendly composites made by not soluble keratin (NSK) and poly(lactic acid) (PLA). NSK has been obtained as a byproduct of a microwave-assisted keratin extraction from poultry feathers and it has been added to PLA pellets without adding any additional compatibilizers or plasticizers, unlike from the other works reported in the literature until now. The mixture has been used to obtain homogeneous NSK-based PLA filaments by means of hot-melt extrusion technology. The filaments have been subsequently 3D printed to explore applications in the additive manufacturing field. All the samples have unaltered thermal stability, but reduced toughness with respect to neat PLA. Other tested parameters (water adsorption, glass transition, and crystallinity) are dependent on NSK content and fabrication technology. Besides, Fourier Transform Infrared Spectroscopy highlights the differences in the structure of the NSK-based PLA filaments and 3D printed samples

State of Utah Space Environment & Contamination Study (SUSpECS) MISSE-6 Payload to Investigate Their Effects on Electron Emission and Resistivity of Spacecraft Materials

A study of the effects of prolonged exposure to the space environment and of charge-enhanced contamination on the electron emission and resistivity of spacecraft materials, the State of Utah Space Environment & Contamination Study (SUSpECS), is planned for flight aboard the MISSE-6 payload. The Materials International Space Station Experiment (MISSE-6) program is designed to characterize the performance of candidate new space materials over the course of approximately four to eight month exposure periods on-orbit on the International Space Station, with a target flight date of mid-2006. The study is conducted by the Utah State University Materials Physics Group, in cooperation with the USU Get-Away Special Program and ATK Thiokol. Electron emission and transport properties of materials are key in determining the likelihood of deleterious spacecraft charging effects and are essential parameters in modeling these effects with engineering tools like NASCAP-2K code. While preliminary ground-based studies have shown that contamination can lead to catastrophic charging effects under certain circumstances, little direct information is presently available on the effects of sample deterioration and contamination on emission properties for materials flown in space. Approximately 40 samples will be mounted on panels on both the ram and wake sides of the ISS. They have been carefully chosen to provide needed information for different ongoing studies and a broad cross-section of prototypical materials used on the exteriors of spacecrafts. Much of the pre-flight testing has already been done in conjunction with previous studies through the NASA Space Environments and Effects Program and other projects. The materials will be tested for resistivity and dielectric strength, and for electron-, ion-, and photon-induced electron emission yield curves and emission spectra. Characterization measurements include optical and electron microscopy, reflection spectroscopy, resistivity and Auger electron spectroscopy. In addition, studies of the service life of composite and ceramic materials of the ATK Thermal Protection Systems and Lightweight Structure System

Hexavalent chromium release over time from a pyrolyzed Cr-bearing tannery sludge

Pyrolysis in an inert atmosphere is a widely applied route to convert tannery wastes into reusable materials. In the present study, the Cr(III) conversion into the toxic hexavalent form in the pyrolyzed tannery waste referred to as KEU was investigated. Ageing experiments and leaching tests demonstrated that the Cr(III)–Cr(VI) inter-conversion occurs in the presence of air at ambient temperature, enhanced by wet environmental conditions. Microstructural analysis revealed that the Cr-primary mineral assemblage formed during pyrolysis (Cr-bearing srebrodolskite and Cr-magnetite spinel) destabilized upon spray water cooling in the last stage of the process. In the evolution from the higher to the lower temperature mineralogy, Cr is incorporated into newly formed CrOOH flakes which likely react in air forming extractable Cr(VI) species. This property transforms KEU from an inert waste to a hazardous material when exposed to ordinary ambient conditions

Artificial intelligence for dementia drug discovery and trials optimization

Drug discovery and clinical trial design for dementia have historically been challenging. In part these challenges have arisen from patient heterogeneity, length of disease course, and the tractability of a target for the brain. Applying big data analytics and machine learning tools for drug discovery and utilizing them to inform successful clinical trial design has the potential to accelerate progress. Opportunities arise at multiple stages in the therapy pipeline and the growing availability of large medical data sets opens possibilities for big data analyses to answer key questions in clinical and therapeutic challenges. However, before this goal is reached, several challenges need to be overcome and only a multi-disciplinary approach can promote data-driven decision-making to its full potential. Herein we review the current state of machine learning applications to clinical trial design and drug discovery, while presenting opportunities and recommendations that can break down the barriers to implementation

Artificial intelligence for dementia drug discovery and trials optimization

Drug discovery and clinical trial design for dementia have historically been challenging. In part these challenges have arisen from patient heterogeneity, length of disease course, and the tractability of a target for the brain. Applying big data analytics and machine learning tools for drug discovery and utilizing them to inform successful clinical trial design has the potential to accelerate progress. Opportunities arise at multiple stages in the therapy pipeline and the growing availability of large medical data sets opens possibilities for big data analyses to answer key questions in clinical and therapeutic challenges. However, before this goal is reached, several challenges need to be overcome and only a multi-disciplinary approach can promote data-driven decision-making to its full potential. Herein we review the current state of machine learning applications to clinical trial design and drug discovery, while presenting opportunities and recommendations that can break down the barriers to implementation

Aquazol as a binder for retouching paints. An evaluation through analytical pyrolysis and thermal analysis

Aquazol poly (2-ethyl-oxazoline) is a tertiary aliphatic amide, with physical and chemical properties that are exploited in a variety of ways, from pharmaceutical applications to the conservation of cultural heritage. In this study, we evaluated the use of Aquazol as a new binder for retouching paint in the restoration of artworks. Aquazol 500 admixed with various formulations of organic red pigments was used to prepare paint replicas which were artificially aged and investigated by a multi-analytical approach based on analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS), and thermogravimetry (TG), complemented by FTIR and LIBS spectroscopy. This is the first study on the ageing phenomena of Aquazol 500 using analytical pyrolysis and thermogravimetric analysis. The influence of the pigments' components on the pyrolysis behavior of Aquazol was also investigated. The paint replicas did not show significant modifications during artificial ageing. This thus highlights the optimal properties of Aquazol 500 as a binder for retouching, in addition to its already established suitability as a filler or consolidant in the restoration of artifacts. Interestingly, when Aquazol 500 is used in formulations containing organic pigments, Aquazol-pigment interactions are observed, strongly depending on the pigment used

One-pot process: Microwave-assisted keratin extraction and direct electrospinning to obtain keratin-based bioplastic

Poultry feathers are among the most abundant and polluting keratin-rich waste bio-masses. In this work, we developed a one-pot microwave-assisted process for eco-friendly keratin extraction from poultry feathers followed by a direct electrospinning (ES) of the raw extract, without further purification, to obtain keratin-based bioplastics. This microwave-assisted keratin extraction (MAE) was conducted in acetic acid 70% v/v. The effects of extraction time, solvent/feathers ratio, and heating mode (MAE vs conventional heating) on the extraction yield were investigated. The highest keratin yield (26 ± 1% w/w with respect to initial feathers) was obtained after 5 h of MAE. Waste-derived keratin were blended with gelatin to fabricate keratin-based biodegradable and bio-compatible bioplastics via ES, using 3-(Glycidyloxypropyl)trimethoxysilane (GPTMS) as a cross-linking agent. A full characterization of their thermal, mechanical, and barrier properties was performed by differential scanning calorimetry, thermogravimetric analysis, uniaxial tensile tests, and water permeability measurements. Their morphology and protein structure were investigated using scanning electron microscopy and attenuated total reflection-infrared spectroscopy. All these characterizations highlighted that the properties of the keratin-based bioplastics can be modulated by changing keratin and GPTMS concentrations. These bioplastics could be applied in areas such as bio-packaging and filtration/purification membranes