Dimitrios N. Bikiaris

Ochre-differentiation through micro-Raman and micro-FTIR spectroscopies: application on wall paintings at Meteora and Mount Athos, Greece

The most widely-used inorganic pigments of Byzantine and post-Byzantine hagiography are earth pigments called ochres such as, red and yellow ochres, limonite, goethite, raw and burnt sienna, caput mortuum and hematite. The present experimental work proposes a technique of differentiation that allows one to distinguish among all the different kinds of iron oxides, thereby providing a better understanding of the painting technique used on portable icons and wall paintings. The ratios between the main spectroscopic peaks, attributable to the major components usually present in ochres, were calculated and compared, one against the another, from the spectra obtained through micro-Raman spectroscopy. Elementary composition is also revealed through a scanning electron microscopy (SEM) analysis. The possibility for detailed study on a particular Byzantine ochre palette can thus be performed based on the small differences in its nature and composition. These differences can first be observed and then measured among all of the natural earth pigments, through microRaman and microFTIR spectroscopies.

Microstructure and Properties of Polypropylene/Carbon Nanotube Nanocomposites

In the last few years, great attention has been paid to the preparation of polypropylene (PP) nanocomposites using carbon nanotubes (CNTs) due to the tremendous enhancement of the mechanical, thermal, electrical, optical and structural properties of the pristine material. This is due to the unique combination of structural, mechanical, electrical, and thermal transport properties of CNTs. However, it is well-known that the properties of polymer-based nanocomposites strongly depend on the dispersion of nanofillers and almost all the discussed properties of PP/CNTs nanocomposites are strongly related to their microstructure. PP/CNTs nanocomposites were, mainly, prepared by melt mixing and in situ polymerization. Young’s modulus, tensile strength and storage modulus of the PP/CNTs nanocomposites can be increased with increasing CNTs content due to the reinforcement effect of CNTs inside the polymer matrix. However, above a certain CNTs content the mechanical properties are reduced due to the CNTs agglomeration. The microstructure of nanocomposites has been studied mainly by SEM and TEM techniques. Furthermore, it was found that CNTs can act as nucleating agents promoting the crystallization rates of PP and the addition of CNTs enhances all other physical properties of PP. The aim of this paper is to provide a comprehensive review of the existing literature related to PP/CNTs nanocomposite preparation methods and properties studies.

LDPE/plasticized starch blends containing PE-g-MA copolymer as compatibilizer

In the present study a series of polyethylene/plasticized starch blends were prepared using a poly(ethylene-g-maleic anhydride) copolymer as a reactive compatibilizer. Uncompatibilized blends were also prepared for comparison purposes. The prepared blends were studied using mechanical properties measurements and SEM microscopy to determine their morphology. The blends were also exposed to activated sludge to determine their biodegradability.

Properties of Fatty-Acid Esters of Starch and Their Blends with LDPE

In the present study, starch octanoates OCST1.8 and OCST2.7 with degrees of substitution (d.s.) of 1.8 and 2.7, respectively, and dodecanoate DODST2.7 (d.s. A 2.7), were prepared by esterification of native starch with fatty acid chlorides. Our analyses, including elemental analysis, FTIR, contact angle, DSC, and TGA measure- ments confirmed the esterification reaction of starch and the degree of substitution. The ester group was found to act like an internal plasticizer, with an increase in the number and the size of fatty acyl chains grafted onto starch. These starch esters were mixed with low density polyethylene (LDPE) at various proportions in a Haake Rheo- mixer. Water and moisture absorption, thermal and mechanical properties, and biodeg- radation were investigated as a function of blend composition. The DODST2.7/LDPE blends showed, in general, better thermal stability and higher elongation, but lower tensile strength and water absorption, than did corresponding OCST/LDPE blends. The addition of starch esters to LDPE led to a very slow rate of biodegradation of these blends. q 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 705-721, 1997

Recent Modifications of Chitosan for Adsorption Applications: A Critical and Systematic Review

Chitosan is considered to be one of the most promising and applicable materials in adsorption applications. The existence of amino and hydroxyl groups in its molecules contributes to many possible adsorption interactions between chitosan and pollutants (dyes, metals, ions, phenols, pharmaceuticals/drugs, pesticides, herbicides, etc.). These functional groups can help in establishing positions for modification. Based on the learning from previously published works in literature, researchers have achieved a modification of chitosan with a number of different functional groups. This work summarizes the published works of the last three years (2012–2014) regarding the modification reactions of chitosans (grafting, cross-linking, etc.) and their application to adsorption of different environmental pollutants (in liquid-phase).

Properties of octanoated starch and its blends with polyethylene

Octanoated starch (OCST) was prepared by esterification of native starch with octanoyl chloride. The new material was characterised by 1H NMR, FTIR, and elemental analysis. This showed that the esterification had proceeded to a degree of substitution of 2.7. The octanoated starch was subsequently mixed with low density polyethylene (LDPE) at various proportions in a Haake Rheomixer. Similar blends of LDPE were also prepared with plasticised starch (PLST) for comparison purposes. The thermomechanical properties were determined as a function of blend composition. The prepared LDPE/OCST blends show better mechanical properties compared to their respective LDPE/PLST blends. In particular, the elongation at breaking is significantly higher in the LDPE/OCST blends. The latter exhibit also a higher thermal stability and a low water absorption.

Solid dispersions, Part I: recent evolutions and future opportunities in manufacturing methods for dissolution rate enhancement of poorly water-soluble drugs

Introduction: In recent years, the number of active pharmaceutical ingredients with high therapeutic impact, but very low water solubility, has increased significantly. Thus, a great challenge for pharmaceutical technology is to create new formulations and efficient drug-delivery systems to overcome these dissolution problems. Areas covered: Drug formulation in solid dispersions (SDs) is one of the most commonly used techniques for the dissolution rate enhancement of poorly water-soluble drugs. Generally, SDs can be defined as a dispersion of active ingredients in molecular, amorphous and/or microcrystalline forms into an inert carrier. This review covers literature which states that the dissolution enhancement of SDs is based on the fact that drugs in the nanoscale range, or in amorphous phase, dissolve faster and to a greater extent than micronized drug particles. This is in accordance to the Noyes–Whitney equation, while the wetting properties of the used polymer may also play an important role. Expert opinion: The main factors why SD-based pharmaceutical products on the market are steadily increasing over the last few years are: the recent progress in various methods used for the preparation of SDs, the effect of evolved interactions in physical state of the drug and formulation stability during storage, the characterization of the physical state of the drug and the mechanism of dissolution rate enhancement.

Mechanical properties and viscoelastic behavior of basalt fiber-reinforced polypropylene

In the present article, a series of commercial-grade polypropylenes (PP) filled with different contents of short basalt fibers were studied. This composite material presented deterioration of both mechanical characteristics, for example, stress and strain at yield with increasing of the fiber content. On the other hand, the impact strength was fourfold higher than that of unfilled PP. A poor adhesion between the PP matrix and the basalt fibers was detected. This is why interfacial interactions were promoted by the adding of poly(propylene-g-maleic anhydride) (PP-g-MA). It was observed that the tensile properties of the obtained materials and their impact strengths increased significantly with increasing of the amount of PP-g-MA in the blend. The adhesion improvement was confirmed by scanning electron microscopy as well. Fourier transform infrared spectroscopy was applied to assess if any chemical interactions in the system PP/PP-g-MA/basalt fibers exist. Dynamic mechanical thermal analysis data showed an increase of the storage modulus with increasing fiber content. The conclusion was made that the modification of the PP matrix led to a higher stiffness but its value remained constant, irrespective of the PP-g-MA content. With increasing fiber content, damping in the β-region decreased, but increase of the coupling agent content restored its value back to that of PP. The loss modulus spectra presented a strong influence of fiber content on the α-relaxation process of PP. The position of the peaks of the above-mentioned relaxation processes are discussed as well.

Optimization of chitosan and β-cyclodextrin molecularly imprinted polymer synthesis for dye adsorption

In this study, two types of novel molecularly imprinted polymers (MIPs) were prepared, for toxic and carcinogenic dyes adsorption. Substrates of the polymeric matrix of the two MIPs were β-cyclodextrin and chitosan. The conditions in the polymerization/imprinting stage and in the rebinding/adsorption step were optimized. The effect of a range of parameters (polymer, cross-linker, and initiator concentrations, reaction time and pH) on the selectivity and adsorption capacity of the dye-MIPs were investigated. Their dye rebinding properties were demonstrated by equilibrium batch experiments (fitting with Freundlich model) and their kinetic rates were exported by the pseudo-first order model. Additionally, a thermodynamic evaluation was carried out through the determination of enthalpy, entropy, and free energy. The selectivity of MIPs was elucidated by their different rebinding capabilities in a trichromatic mixture (composed of related structurally dyes). Regeneration/reuse of the dye-loaded polymers was evaluated via sequential adsorption-desorption cycles.

Poly(itaconic acid)-grafted chitosan adsorbents with different cross-linking for Pb(II) and Cd(II) uptake.

Two novel chitosan (CS) adsorbents were prepared in powder form, after modification with the grafting of itaconic acid (CS-g-IA) and cross-linking with either glutaraldehyde (CS-g-IA(G)) or epichlorohydrin (CS-g-IA(E)). Their adsorption properties were evaluated in batch experiments for Cd(II) or Pb(II) uptake. Characterization techniques were applied to the prepared adsorbents as swelling experiments, TGA, SEM, XRD, and FTIR. Adsorption mechanisms were suggested for different pH conditions. Various adsorption parameters were determined as the effect of pH, contact time, and temperature. The maximum adsorption capacities for Cd(II) uptake were 405 and 331 mg/g for CS-g-IA(G) and CS-g-IA(E), respectively, revealing the capacity enhancement after grafting (124 and 92 mg/g were the respective values before grafting, respectively). A similar grafting effect was observed for Pb(II) uptake, proving its adsorption effectiveness on the CS backbone. The reuse of adsorbents was tested with 20 adsorption-desorption cycles.