Textural and Thermal Properties of the Novel Fucoidan/Nano-Oxides Hybrid Materials with Cosmetic, Pharmaceutical and Environmental Potential

The main purpose of the research was to obtain and study hybrid materials based on three different nano-oxides commonly used in the cosmetic and pharmaceutical industries: Al2O3, TiO2, and ZnO, with the natural bioactive polysaccharide fucoidan. Since the mentioned oxides are largely utilized by industry, there is no doubt that the presented studies are important from an environmental point of view. On the basis of the textural studies (dynamic light scattering DLS, low temperature nitrogen adsorption, X-ray diffraction analysis XRD, scanning electron microscopy SEM) it was proved that the properties of the hybrid materials differ from the pure components of the system. Moreover, the advanced thermal analysis (TG-DTG-DSC) combined with the evolved gas analysis using Fourier transformed infrared spectroscopy (FTIR) and mass spectrometry were applied to describe the thermal decomposition of fucoidan, oxides and hybrid materials. It was found that the interactions between the polymer and the oxides results in the formation of the hybrid materials due to the functionalization of the nanoparticles surface, and that their thermal stability increased when compared to the pure substrates. Such findings definitely fill the literature void regarding the fucoidan based hybrid materials and help the industrial formulators in the preparation of new products.

Plastics in robots: a degradation study of a humanoid skin mask made of soft urethane elastomer

Understanding the degradation of plastic materials is a big challenge for curators, conservators and conservation scientists in museums worldwide aiming to preserve their collections due to the variety of formulations of synthetic polymers and pigments. The conservation of polyurethane (PUR) based objects is challenging because they can suffer from extensive degradation. Particularly PUR elastomers can degrade shortly after their production, as occurred to the mask of the Japanese robot SAYA, which within 8 years suffered from two large tears, discoloration and stickiness. This research aims at studying the degradation phenomena of the androids’ synthetic skin. Better knowledge of the chemical composition of the mask and the chemical and physical decay will contribute to planning a suitable stabilization treatment. Within a multi-analytical approach, colorimetric and microscopic investigations highlighted discolored areas, which showed further color changes within a five months monitoring campaign, confirming the instability of the material likely due to ongoing degradation. Raman microscopy allowed the identification of Pigment White 6 (titanium dioxide TiO2) in the anatase form, known to promote the photosensitivity of PUR substrates towards ultraviolet (UV) light. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy identified the PUR composition of the mask, the presence of phthalates as plasticizers and suggested the formation of quinone chromophores in the polymer structure as a result of photo-oxidation, possibly responsible for the mask yellowing. Evolved gas analysis-mass spectrometry (EGA-MS) and double-shot-gas chromatography/mass spectrometry (TD/Py–GC/MS) analyses support the characterization of the formulation of the mask as being made of methylene diphenyl diisocyanate (MDI) PUR ether elastomer. Plasticizers in high concentration, mainly diisononyl phthalate (DINP) and bis(2-ethylhexyl)phthalate (DEHP), and the UV stabilizer Tinuvin 328 were also detected. In addition, the presence of styrene-acrylonitrile (SAN) could also contribute to the mask’s chemical instability. More amount of UV stabilizer and phthalates were detected at the surface (contributing to its stickiness) than in the inner core. The degradation of the mask results from the light susceptibility of MDI PUR ether and SAN, as well as the higher photochemical activity of anatase. The mask was transferred on to a mannequin and placed in the storage area to prevent light exposure and photo-oxidation. As loose edges had to be stabilized, tests were conducted and adhesive stripes glued with a PUR dispersion were selected for keeping the head’s shape. The novelty of this study is the implementation of conservation science on the study of androids with PUR elastomeric components in robotic collections, which are becoming increasingly popular in technical museums, however still seldomly studied.

Physicochemical Analysis of the Particulate Matter Emitted from Road Vehicle Engines

Air pollution with particulate matter from transport sources is a serious problem in terms of air quality and its impact on human health. The article attempts to test the emitted particles from piston engines in terms of their physical properties and chemical composition. The research test objects were a diesel engine with Euro 5 emission class and a petrol engine, which was a part of the scooter drive system. The conducted research consisted in the analysis of the number, mass, and volume of particles, as well as chemical analysis, using the methods: Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscope with Energy Dispersive Spectroscopy (SEM-EDS), and Evolved gas analysis (EGA). The diesel engine emitted particles in the range of 50–120 nm. With the increase in the engine load, the specific emission of particulate matter increased. In the case of a gasoline engine running without load, the emission of particles smaller than 30 nm was mainly observed. Increasing load of the gasoline engine resulted in an increase in both the concentration of particles and their diameter (average diameter to 90 nm). FTIR analysis showed higher black carbon content in the case of the sample taken from the diesel engine. In order to carry out a more detailed chemical analysis, the EGA and SEM methods were used. On their basis, the chemical composition of particles was presented, and a greater ability to agglomerate of a gasoline engine particles was found.

Detection of organic carbon in Mars-analog paleosols with thermal and evolved gas analysis

Decades of space exploration have shown that surface environments on Mars were habitable billions of years ago. Ancient, buried surface environments, or paleosols, may have been preserved in the geological record on Mars, and are considered high-priority targets for biosignature investigation. Studies of paleosols on Earth that are compositionally similar to putative martian paleosols can provide a reference frame for constraining their organic preservation potential on Mars. However, terrestrial paleosols typically preserve only trace amounts of organic carbon, and it remains unclear whether the organic component of paleosols can be detected with Mars rover-like instruments. Furthermore, the study of terrestrial paleosols is complicated by diagenetic additions of organic carbon, which can confound interpretations of their organic preservation potential. The objectives of this study were a) to determine whether organic carbon in ~30-million-year-old Mars-analog paleosols can be detected with thermal and evolved gas analysis, and b) constrain the age of organic carbon using radiocarbon (14C) dating to identify late diagenetic additions of carbon. Al/ Fe smectite-rich paleosols from the Early Oligocene (33 Ma) John Day Formation in eastern Oregon were examined with a thermal and evolved gas analyzer configured to operate similarly to the Sample Analysis at Mars Evolved Gas Analysis (SAM-EGA) instrument onboard the Mars Science Laboratory Curiosity rover. All samples evolved CO2 with peaks at ~400 °C and ~700° C from the thermal decomposition of refractory organic carbon and small amounts of calcium carbonate, respectively. Evolutions of organic fragments co-occurred with evolutions of CO2 from organic carbon decomposition. Total organic carbon (TOC) ranged from 0.002 - 0.032 ± 0.006 wt. %. Like modern soils, the near-surface horizons of all paleosols had significantly higher TOC relative to subsurface layers. Radiocarbon dating of four samples revealed an organic carbon age ranging between ~6,200 – 14,500 years before present, suggesting there had been inputs of exogenous organic carbon during diagenesis. By contrast, refractory carbon detected with EGA and enrichment of TOC in near-surface horizons of all three buried profiles were consistent with the preservation of trace amounts of endogenous organic carbon. This work demonstrates that near-surface horizons of putative martian paleosols should be considered high priority locations for in-situ biosignature investigation and reveals challenges for examining organic matter preservation in terrestrial paleosols.

Mineralogy and diagenesis of Mars-analog paleosols from eastern Oregon, USA

Ancient (4.1-3.7-billion-year-old) layered sedimentary rocks on Mars are rich in clay minerals which formed from aqueous alteration of the Martian surface. Many of these sedimentary rocks appear to be composed of vertical sequences of Fe/Mg clay minerals overlain by Al clay minerals that resemble paleosols (ancient, buried soils) from Earth. The types and properties of minerals in paleosols can be used to constrain the environmental conditions during formation to better understand weathering and diagenesis on Mars. This work examines the mineralogy and diagenetic alteration of volcaniclastic paleosols from the Eocene-Oligocene (43-28 Ma) Clarno and John Day Formations in eastern Oregon as a Mars-analog site. Here, paleosols rich in Al phyllosilicates and amorphous colloids overlie paleosols with Fe/Mg smectites that altogether span a sequence of ~500 individual profiles across hundreds of meters of vertical stratigraphy. Samples collected from three of these paleosol profiles were analyzed with visible/near-infrared (VNIR) spectroscopy, X-ray diffraction (XRD), and evolved gas analysis (EGA) configured to operate like the SAM-EGA instrument onboard Curiosity Mars Rover. Strongly crystalline Al/Fe dioctahedral phyllosilicates (montmorillonite and nontronite) were the major phases identified in all samples with all methods. Minor phases included the zeolite mineral clinoptilolite, as well as andesine, cristobalite, opal-CT and gypsum. Evolved H2O was detected in all samples and was consistent with adsorbed water and the dehydroxylation of a dioctahedral phyllosilicate, and differences in H2O evolutions between montmorillonite and nontronite were readily observable. Detections of hematite and zeolites suggested paleosols were affected by burial reddening and zeolitization, but absence of illite and chlorite suggest that potash metasomatism and other, more severe diagenetic alterations had not occurred. The high clay mineral content of the observed paleosols (up to 95 wt. %) may have minimized diagenetic alteration over geological time scales. Martian paleosols rich in Al and Fe smectites may have also resisted severe diagenetic alteration, which is favorable for future in-situ examination. Results from this work can help distinguish paleosols and weathering profiles from other types of sedimentary rocks in the geological record of Mars.

Thermal, mechanical, and electrical properties of difunctional and trifunctional epoxy blends with nanoporous materials

In the present study, the aim is to synthesize the particulate nanocomposites with difunctional and trifunctional epoxy blend as matrix and synthesized nanoporous materials as fillers. Organic/inorganic hybrid networks were prepared by the novel solvent free method. Viscoelastic, thermal, and electrical properties of di- and trifunctional epoxy and the effect of different nanoparticles in the particulate nanocomposites have been studied by dynamic mechanical analyzer, thermogravimetry (TGA), and dielectric strength. Epoxy mixed with different compositions of TGPAP and particulate nanocomposites by the addition of different types of nanomaterials shows higher storage modulus than the pure epoxy. The addition of TGPAP and nanofillers decreases the thermal stability of epoxy matrix. The evolved gas analysis (TG-FTIR) was also done in order to study the products formed during degradation. An increase in dielectric strength and impact strength (4%) was also observed in the particulate nanocomposites.

An Exceptionally Stable and Widespread Hydrated Amorphous Calcium Carbonate Precipitated By the Dog Vomit Slime Mold Fuligo Septica (Myxogastria)

Biogenic amorphous calcium carbonate (ACC) is typically metastable and can rapidly transform through aging, dehydration, and/or heating to crystalline calcium carbonate. Gaining insight into its structure and properties is typically hampered by its tendency to crystallize over short time periods once isolated from the host organism, and also by the small quantities that are usually available for study. Here, we describe an exceptionally stable hydrated ACC (HACC) precipitated by the cosmopolitan slime mold, Fuligo septica (L.) F.H. Wigg. (1780). A single slime mold can precipitate up to one gram of HACC over the course of one night. Powder x-ray diffraction (XRD) patterns, transmission electron microscopy (TEM) images, infrared absorption (IR) spectra, and lack of optical birefringence are consistent with an amorphous material. XRD simulations supported by thermogravimetric (TG) and evolved gas analysis (EGA) data suggest an intimate association of organic matter with ~1-nm-sized ACC units that have monohydrocalcite- and calcite-like nano-structural properties. It is postulated that this association imparts the extreme stability of the HACC by preventing loss of H2O and subsequent crystallization. The composition, structure, and thermal behavior of the HACC precipitated by F. septica collected over 8000 km apart, and in markedly different environments, suggests a common structure, as well as similar biochemical and biomineralization mechanisms for the HACC formation.

Evolved Gas Analysis and Kinetics of Catalytic and Non-Catalytic Pyrolysis of Microalgae Chlorella sp. Biomass With Ni/θ-Al2O3 Catalyst via Thermogravimetric Analysis

This study investigates the efficacy of a prepared Ni/θ-Al2O3 catalyst during the pyrolytic conversion of Parachlorella kessleri HY-6 and compares the results with non-catalytic conversion. The catalyst was characterized by techniques such as Brunauer–Emmett–Teller (BET) for surface area, acidity, and X-ray powder diffraction (XRD). Isoconversional and combined kinetic methods were used to study the pyrolytic kinetics of the process. Ni/θ-Al2O3 was used at 10, 20, and 30% of the algal biomass. The addition of Ni/θ-Al2O3 facilitated the conversion by lowering the mean activation energy during pyrolysis. The catalytic effect was more pronounced at lower and higher conversions. The presence of the catalyst facilitated the pyrolysis as indicated by the lower value of activation energy and ∆H, and ∆G. Gases evolved during pyrolysis were qualitatively analyzed by FTIR to see the effect of catalyst on evolved gas composition during the pyrolysis process.

Thermal stability of polymeric carbon nitride (PCN)-Al2O3–ZrO2 nanocomposites used in photocatalysis

Polymeric carbon nitride (PCN) was recently found to have extensive applications in the field of photocatalysis. Knowledge about thermal stability of PCN nanocomposites is crucial for this application and designing the final product. In this work, the thermal stability of PCN-Al2O3–ZrO2 nanocomposites was investigated. PCN nanocomposites were obtained in two steps: (1) microwave hydrothermal synthesis of co-precipitated AlOOH and ZrO2 precursors, followed by drying; (2) mixing the nanopowders with melamine powder and annealing in air in a tube furnace at 400, and 450 °C. The PCN nanocomposites were examined by attenuated total reflection technique of Fourier transformed infrared spectroscopy. Also, the evolved gas analysis was performed combining differential scanning calorimetry and thermogravimetry coupled with mass spectroscopy and FTIR. The results show that only PCN-Al2O3–ZrO2 nanocomposite obtained at 400 °C is stable from room temperature up to 490 °C and during thermal decomposition, in one step releases ammonia (NH3), cyanic acid (HNCO), water (H2O), and carbon dioxide (CO2). The limitation of the PCN-Al2O3–ZrO2 thermal stability and performance is AlOOH–ZrO2 used as a nanocomposite component.