Micro and nano cellular amorphous polymers (PMMA, PS) in supercritical CO2 assisted by nanostructured CO2-philic block copolymers - One step foaming process

Microcellular foaming of commodity amorphous polymers, poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) was studied in supercritical CO₂ via a batch one-step process in the presence of block copolymers able to change their foaming behaviour and therefore the porous structures. Triblock (styrene-co-butadiene-co-methylmethacrylate SBM, methylmethacrylate-co-butylacrylate-co-methylmethacrylate MAM) terpolymers were blended to PS or PMMA by extrusion. They showed advantages compared to classical PS-PMMA polymer blends in terms of cell size control and reduction of cell size. Foaming is carried out on bulk injection molded samples which were saturated under high pressures of CO₂ (300 bars) at different temperatures (25° C to 80 °C) and different depressurization rates (pressure drop rates from 150 bar/min to 12 bar/min). Very distinct cellular structures and densities were controlled by varying either the copolymer type or the foaming conditions (T,P). Cell sizes ranged from 0.2 μm to 200 μm, and densities from 0.30 g/cm³ to 1 g/cm³ in the polymers considered. Particularly, when triblock copolymers were able to self organize (nanostructuring) in a polymer matrix, they became phase separated at a nanometer level, presenting nanostructured polymers matrixes. To conclude the study, a possible nanostructuring mechanism is suggested based on the interplay between rubbery and highly CO₂-philic blocks/rigid and less CO₂-philic blocks. It is demonstrated that block copolymer additives are a good pathway towards micro and ultra microcellular supercritical CO₂ foaming of amorphous polymers.     

Synthesis and Surface-Active Properties of Uronic Amide Derivatives,Surfactants from Renewable Organic Raw Materials

Short chemical syntheses were developed to produce a new set of surfactants from uronic acids derived from widely available raw materials. Three different strategies were used to synthesize uronic amide derivatives, the structures of which were totally characterized by spectrometric methods (IR, MS, ¹H-RMN and ¹³C-RMN). The best one, using an acid chloride as the synthetic intermediate, furnished the expected amides as a mixture of anomers in 46–58% global yield. Surface-active properties (CMC, γ_cmc, Γ_max, A _min) of homologous series of uronic acid N-alkylamides from C8 to C18 were also assessed. In general, these sugar-based surfactants exhibited good surface-activities, and appeared as valuable nonionic surfactants compared to octylphenol 9–10 ethylene oxide condensate, the most well-known nonionic surfactant. Increasing the alkyl chain length influenced the CMC values for both glucuronic and galacturonic N-alkylamide derivatives. The galacturonic N-alkylamides decreased γ_cmc at slower values than their counterpart’s glucuronic N-alkylamides.     

Towards continuous sustainable processes for enzymatic synthesis of biodiesel in hydrophobic ionic liquids/supercritical carbon dioxide biphasic systems

The excellent suitability of immobilized Candida antarctica lipase B (Novozym 435) catalyst to carry out the synthesis of methyl oleate (biodiesel) by methanolysis of triolein in ILs based on imidazolium cations with large alkyl side chain (from C₁₂ to C₁₈) has been demonstrated at 60 and 85 °C. The phase behaviour of IL/triolein/methanol and IL/methyl oleate mixtures were studied at different concentrations and temperatures, the best results (up to 98.6% biodiesel yield after 6 h) being obtained for ILs able to provide monophasic reaction systems, i.e. 1-methyl-3-octadecylimidazolium bis(trifluoromethylsulfonyl)imide). A continuous enzymatic reactor, based on biocatalysts particles coated with hydrophobic ILs, for biodiesel synthesis in supercritical carbon dioxide was studied at 60 °C and 180 bar. The operational stability of the immobilized lipase was improved by its coating with ILs, i.e. 1-methyl-3-octadecylimidazolium hexafluorophosphate, leading to a two-phase systems with respect to the biodiesel product, which showed an excellent catalytic behaviour in continuous operation under supercritical conditions (up to 82% biodiesel yield after 12 cycles of 4 h).     

Coating carbon nanotubes with a polystyrene-based polymer protects against pulmonary toxicity

Background  

carbon nanotubes (CNT) can have adverse effects on health. Therefore, minimizing the risk associated with CNT exposure is of crucial importance. The aim of this work was to evaluate if coating multi-walled CNT (MWCNT) with polymers could modify their toxicity, thus representing a useful strategy to decrease adverse health effects of CNT. We used industrially-produced MWCNT uncoated (NT1) or coated (50/50 wt%) with acid-based (NT2) or polystyrene-based (NT3) polymer, and exposed murine macrophages (RAW 264.7 cell line) or Balb/c mice by intratracheal administration. Biological experiments were performed both in vitro and in vivo, examining time- and dose-dependent effects of CNT, in terms of cytotoxicity, expression of genes and proteins related to oxidative stress, inflammation and tissue remodeling, cell and lung tissue morphology (optical and transmission electron microscopy), and bronchoalveolar lavage fluid content analysis.     

Effect of processing procedures and conditions on structural,morphological, and rheological properties of polyethylene/polyamide/nanoclay blends

The article deals with the effect of processing procedures and conditions on structural, morphological, and rheological properties of ternary blends composed of polyethylene (PE), polyamide (PA)‐12, and organically modified montmorillonite nanoclay with selective affinity. Samples were prepared from PE/PA and PA/PE blends, either by simultaneous mixing or from a polymer/clay masterbatch, using two processing conditions. The results have shown the existence of a weight fraction threshold, above which no significant processing effect was observed. Below this weight fraction threshold, the results tend to underline the significant role of two parameters that depend on processing procedures and/or conditions: the contact time between PE and PA phases and the contact time between clay and PA. Clay structure, blend morphology, and rheological properties were all shown to depend on these two parameters, and also on the nature of the matrix (PE or PA), because of the selective affinity of clay toward polymer phases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of pressure on the structure and electrical conductivity of cardanol–furfural–polyaniline blends

Pressure‐sensitive polymers that simultaneously present reasonable electrical conducting properties, useful thermosetting behavior, and softness are hard to develop. To combine these properties into a single material, a cardanol‐based phenolic resin was prepared and blended in situ with polyaniline (PAni). The final polymer blend was composed of a soft solid material that could not be dissolved in ordinary solvents. Samples were characterized through X‐ray scattering, Fourier transform infrared (FTIR) spectroscopy, and electrical conductivity and pressure sensitivity measurements. FTIR results indicate that the insertion of PAni into the blends did not change the chemical nature of the resin. According to wide‐angle X‐ray scattering results, PAni was dispersed homogeneously in the final polymer samples; this improved the sensitivity of the electrical conductivity to pressure variations, as confirmed through electromechanical tests. Pressure sensitivity and electromechanical analyses indicated that the produced blends could be used as pressure‐sensing materials. Among the tested materials, the blends containing 5 wt % PAni·H₂SO₄ presented the largest compression sensitivity values. Finally, it was shown for the first time through XRD analyses under pressure that PAni chains were considerably disturbed by compressive stresses. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Processing and properties of transparent hydroxyapatite and β tricalcium phosphate obtained by HIP process

Stoichiometric β-tricalcium phosphate (β-TCP) and hydroxyapatite (HA) powders were synthesized by chemical precipitation of aqueous solutions of diammonium phosphate and calcium nitrate. After a calcination treatment and a milling step, the powders were shaped by slip casting. The sintering temperature effect on the relative density and the average grain size was investigated. By natural sintering at 1200 and 1120 °C, densities of 98% and 99% were obtained for HA and TCP, respectively. After determination of minimum temperatures to obtain only closed porosity and a pre-sintering at these temperatures, hot isostatic pressing (HIP) treatment was carried out. Transparent or translucent samples were obtained, indicating a relative density very close to the theoretical value (>99.9%). Mechanical properties (three-point bending strength, fracture toughness, Young's modulus and Vickers hardness) were measured on both materials with similar grain size (～ 1 μm). Bending strengths of 181 and 105 MPa were measured for TCP and HA, respectively.     

Simulation of Superheated Steam Drying from Coupling Models

Modeling of the transfer between a porous medium and its surroundings is commonly made using transfer coefficients that are theoretically well known only under boundary layer hypothesis. The resolution of Navier–Stokes equations in the surroundings of the product in order to get information about the boundary conditions avoids the classical use of these transfer coefficients. In this article, a modeling and a simulation of superheated steam drying of a rectangular piece of porous medium is proposed using a coupling method between a porous medium code and a CFD software. In some cases of superheated steam drying, even if a thermal boundary layer exists, a mass boundary layer cannot be defined. Moreover, boiling occurs during the process. An analysis of the interfacial transfer coupled with the analysis of the temperature, moisture content, and pressure profiles inside the porous medium is proposed.     

From Drying to Thermo-Hydro-Rheology—A Thirty-Year-Long Unfinished Maze

By 1976, chemical and mechanical engineering had produced a tremendous effort to understand drying in physical terms, mainly for consolidated bodies. In spite of an obvious interest aroused by the food processing industry, very little had been done on saturated deformable media. This article relates how a succession of nineteen Ph.D. students tried to enforce into practical and fundamental drying the relatively few laws we have at our disposal in continuum mechanics. Practical problems suggested by industry alternated with more theoretical work in an unplanned manner: it was my duty and my pleasure to ensure that all treatments echoed correctly with a certain harmony.     

Preparation of chitosan‐based adhesives and assessment of their mechanical properties

The aim of this study is to develop chitosan‐based adhesives and to characterize their shear strength. The desirable features of such adhesives are biodegradability, biocompatibility, non‐toxicity, and anti‐microbial properties. Various eco‐friendly polyanionic polysaccharides, acids, and plasticizers, in single or multiple formulations, were associated with chitosan. The resulting crosslinked polymers were glued on some chemically treated aluminum adherends. The shear strength of these formulations was measured with the “double lap‐joint” bonding method, as it features a low‐peeling effect. The shear strength of 40.8 MPa obtained for formulations containing chitosan and glycerol plasticizer was the most significant finding in this study. This value is equivalent to that obtained with a synthetic adhesive used in industry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013