Click Crosslinked Chitosan/Gold Nanocomposite Hydrogels

Preparation of novel nanocomposite hydrogels opens up new avenues to next generation of biocompatible materials to be used in bioengineering and drug delivery. Toward this goal, chitosan nanocomposite hydrogels using click chemistry inspired cross‐linking are prepared. To enable this, Diels–Alder reaction of furan‐containing chitosan and maleimide‐coated gold nanoparticles is employed. The viscoelastic properties of the obtained nanocomposites as well as the effect of the nanoparticles as cross‐linkers are studied, indicating that they play significant role in hydrogel formation and stability. Nanoparticle‐enriched hydrogels are also found to demonstrate pH‐sensitivity therefore showing their potential for future biosensing applications.

     

Numerical analysis of an elasto‐piezoelectric problem with damage

In this paper, we analyze an algorithm for the quasistatic evolution of the mechanical state of an elasto‐piezoelectric body with damage. Both damage, caused by the development and the growth of internal microcracks, and piezoelectric effects, are included in the model. The mechanical problem is expressed as an elliptic system for the displacement field coupled with a non‐linear parabolic partial differential equation for the damage field and a linear partial differential equation for the electric potential. The variational formulation leads to a coupled system composed of two linear variational equations for the displacement field and the electric potential, and a non‐linear parabolic variational equation for the damage field. The existence of a unique weak solution is stated. Then, a fully discrete scheme is introduced by using the finite element method to approximate the spatial variable and an Euler scheme to discretize the time derivatives. Error estimates are derived on the approximate solutions, from which the linear convergence of the algorithm is deduced under suitable regularity conditions. Finally, some numerical simulations are performed, in one, two and three dimensions, to demonstrate the accuracy of the scheme and the behaviour of the solution. Copyright © 2008 John Wiley & Sons, Ltd.     

What does the NRTL model look like? Determination of boundaries for different fluid phase equilibrium regions

The adequate correlation of experimental phase equilibrium data by using any thermodynamic model represents a key point for the rigorous design of the chemical processes. However, this data correlation process remains a challenging problem, due to the high nonlinearity of the models used and the consequent problems of convergence. The present work analyzes the nonrandom two-liquids mode (NRTL) model to check the relation between the values of the binary interaction parameters and the corresponding phase equilibria that the NRTL model can or cannot reproduce. Additionally, in the case of the LLE, empirical equations have been established as a function of the nonrandomness parameter, to model the trajectory of the different miscibility boundaries observed. These functions can be used as constraints in the experimental data correlation procedure to reduce the search space and guarantee the consistency of the obtained binary interaction parameters with the experimental behavior of the system under study.     

Template removal in MCM-41 type materials by solvent extraction: Influence of the treatment on the textural properties of the material and the effect on its behaviour as catalyst for reducing tobacco smoking toxicity

In this work a series of MCM-41 catalysts have been prepared by eliminating the template by calcination and by different extraction treatments. The extracted samples were also calcined and aluminium ion exchanged. A hydrothermal stability test of the final materials has also been performed. N₂ adsorption isotherms, NH₃ thermal desorption, X-ray fluorescence, X-ray diffraction, ²⁷Al NMR and thermogravimetry of each material have been determined in order to establish the influence of the procedure used for template elimination on the physicochemical and textural properties of the material. Moreover, the ability of the different catalysts prepared for reducing the toxicity of the mainstream smoke evolved when cigarettes are smoked has been checked too. The results obtained show that the final properties of the catalyst depend noticeably on the experimental conditions used in the template extraction process (i.e., the solvent selected, the solvent:catalyst ratio, the temperature, the contact time and the number of successive extraction steps). Thus, the adequate selection of such conditions permits a material to be obtained with properties very similar to that of the calcined MCM-41 material. As a conclusion, the material showing the best properties, among the catalysts studied in this work, produces a mean reduction of the yield of the different compounds analyzed in the gases and in the condensed products retained in the filters and in the traps of around 35%, 75% and 45%, respectively, which are slightly higher than the values corresponding to the calcined MCM-41 used as reference (i.e., 25%, 56% and 40%, respectively). These reductions results in an increase of the amount of ashes of around 2 mg/cigarette due to the presence of the catalyst.     

Morphology and thermal behavior of poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/poly(butylene adipate‐co‐terephthalate)/clay nanocomposites

Biopolymers are gaining increasing interest because of decline of mineral oil reserves, increasing waste problem, and increasing consciousness of society for environmental problems. However, competitiveness of biopolymers compared with conventional plastics is still limited due to partly insufficient properties and high prices. This study investigates the influence of blending of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) with poly(butylene adipate‐co‐terephthalate) (PBAT) as well as the influence of addition of functionalized montmorillonite (OMMT) to the blends on morphology and thermal behavior. Dispersion state and morphology of the nanocomposites are studied by X‐ray diffraction as well as scanning electron microscopy. Thermal stability is studied by thermogravimetric analysis and crystallization behavior is studied by differential scanning calorimetry and polarized optical microscopy. With respect to the morphology for the blends it can be seen that the immiscible biopolymers PHBV and PBAT are distributed in interlocking zones. There is a good dispersion and homogeneous distribution of OMMT within the biopolymer blends. The addition of 50% or more PBAT to PHBV as well as the insertion of OMMT enhances thermal stability of PHBV. In the blends, the addition of PBAT retards crystallization of PHBV. The OMMT acts as nucleating agent leading in total to more but less perfect crystals in the blends, and the crystallization slows further due to constraint in the movement of polymer chains. These results contribute to the understanding of the structure–properties relationship of bionanocomposite materials for packaging applications. POLYM. COMPOS., 36:2051–2058, 2015. © 2014 Society of Plastics Engineer     

Precise and traceable (13)C/(12)C isotope amount ratios by multicollector ICPMS

A new method for the measurement of SI traceable carbon isotope amount ratios using a multicollector inductively coupled mass spectrometer (MC-ICPMS) is reported for the first time. Carbon (13)C/(12)C isotope amount ratios have been measured for four reference materials with carbon isotope amount ratios ranging from 0.010659 (delta(13)C(VPDB) = -46.6 per thousand) to 0.011601 (delta(13)C(VPDB) = +37 per thousand). Internal normalization by measuring boron (11)B/(10)B isotope amount ratios has been used to correct for the effects of instrumental mass bias. Absolute (13)C/(12)C ratios have been measured and corrected for instrumental mass bias and full uncertainty budgets have been calculated using the Kragten approach. Corrected (13)C/(12)C ratios for NIST RM8545 (Lithium Carbonate LSVEC), NIST RM8573 (L-Glutamic Acid USGS40), NIST RM8542 (IAEA-CH6 Sucrose) and NIST RM8574 (L-Glutamic Acid USGS41) differed from reference values by 0.06-0.20%. Excellent linear correlation (R = 0.9997) was obtained between corrected carbon isotope amount ratios and expected carbon isotope amount ratios of the four chosen NIST RMs. The method has proved to be linear within this range (from (13)C/(12)C = 0.010659 to (13)C/(12)C =0.011601), and therefore, it is suitable for the measurement of carbon isotope amount ratios within the natural range of variation of organic carbon compounds, carbonates, elemental carbon, carbon monoxide, and carbon dioxide. In addition, a CO2 gas sample previously characterized in-house by conventional dual inlet isotope ratio mass spectrometry has been analyzed and excellent agreement has been found between the carbon isotope amount ratio value measured by MC-ICPMS and the IRMS measurements. Absolute values for carbon isotope amount ratios traceable to the SI are given for each NIST RM, and the combined uncertainty budget (including instrumental error and each parameter contributing to Russell expression for mass bias correction) has been found to be < 0.1% for the four materials. The advantage of the method versus conventional gas source isotope ratio mass spectrometry measurements is that carbon isotope amount ratios are measured as C(+) instead of CO2(+), and therefore, an oxygen (17)O correction due to the presence of (12)C(17)O(16)O(+) is not required. Organic compounds in solution can be measured without previous derivatization, combustion steps, or both, thus making the process simple. The novel methodology opens new avenues for the measurement of absolute carbon isotope amount ratios in a wide range of samples.     

Combined electrochromic and plasmonic optical responses in conducting polymer/metal nanoparticle films

Poly(3,4-ethylenedioxithiophene)/poly(styrene sulphonate) (PEDOT/PSS) aqueous dispersions were mixed with aqueous gold nanoparticle and aqueous silver nanoparticle colloids. PEDOT/gold nanoparticles (Au NP) and PEDOT/silver nanoparticles (Ag NP) films were obtained by solvent casting the corresponding aqueous solutions. The nanocomposite films showed the optical characteristics associated with both the surface plasmon absorption resonance of the metal nanoparticles and the excitation of the bipolaron band of the conducting polymer. As an interesting application we demonstrate the use of metal nanoparticles to tune the color of PEDOT based electrochromic films from blue to violet in the case of Au NP or green in the case of Ag NP.     

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/clay nanocomposites for replacement of mineral oil based materials

Due to the short‐running of mineral oil and the increasing waste problem, biopolymers become more and more important. However, they still suffer from disadvantages, and in many cases, their properties are still insufficient to replace mineral oil based plastics. In this study, the biobased and biodegradable polymer poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) is reinforced by different clay types and their effect on the properties profile is investigated. Natural as well as organomodified montmorillonite and bentonite are dispersed by melt mixing within the PHBV matrix. Thermal stability, crystallization behavior, and dynamic mechanical properties as well as the materials morphology is analyzed. Dispersion state of the nanoclay is found to be crucial for the improvement of the material performance and well dispersed organomodified clays reveal to simultaneously improve different properties of PHBV matrix. POLYM. COMPOS., 34:1033–1040, 2013. © 2013 Society of Plastics Engineers     

Extensional viscosity measurements and characterization of poly (vinyl chloride‐co‐vinyl acetate) plastisols and foams

The foaming of PVC‐VA [Poly (vinyl chloride‐co‐vinyl acetate)] plastisols is a complex combination of processes involving the simultaneous curing of the paste with the evolution of gases caused by the decomposition of the chemical blowing agent. The extensional viscosity is a fundamental characteristic of the material, responsible for the behavior of the system when undergoing the extensional stress produced by the released gases. Nevertheless, such changes have not been considered to the same extent as the complex viscosity evolution or the thermal processes suffered by PVC‐VA plastisols. The objective of the present work is to study the extensional viscosity of the PVC‐VA plastisols prepared with three plasticizers of similar structure, but with different curing and rheological behavior in order to investigate its influence on the quality of the foams obtained. Extensional viscosity measurements under forced prestretch conditions revealed that depending on the structure and consequently on the compatibility of the plasticizer used, each plastisol develops its properties and structure accordingly. DINCH plasticizer (Diisononyl cyclohexane‐1,2‐dicarboxylate presenting alicyclic ring) seems to be the less compatible compared with the other two studied (both presenting aromatic rings) according to its behavior during the curing and foaming processes and may not be able to withstand the pressure evolved by the released gases during the foaming process yielding foams of poorer quality. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013