Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

Comparative Study of Xylan Extracted by Sodium and Potassium Hydroxides (NaOH and KOH) from Bagasse Pulp: Characterization and Morphological Properties

Xylan is the second most abundant polysaccharide and the predominant hemicellulose component of soda bagasse pulp. The present endeavor focuses on increasing the value addition to underutilized agro-industrial residue such as bagasse. For this purpose, xylan was isolated by two conventional alkali extraction methods i.e. NaOH and KOH. The recovery rate and sugar composition of different reaction times and alkali consumptions were monitored with advanced method such as High Performance Liquid Chromatography (HPLC). The Fourier Transform Infrared Spectroscopy (FTIR) and Wide Angle X-ray spectroscopy (WAXS) were respectively employed to characterize the functional groups and Crystallinity Index (CrI) changes during the extraction process. It was explored that highest xylan recovery rates were obtained with 6% of NaOH at 120 min and 6% KOH at 45 min. The xylan morphology via WAXS was found that its structure to be amorphous. HPLC results also showed KOH had higher effectiveness than NaOH in terms of extracted xylan purity. Highest XGRs (Xylose to Glucose Ratios) were also achieved by KOH processes. Hence, this study contributes to the adequate utilization of agricultural residues, with promising potential for applications in the production of certain novel materials and chemical conversion industries.     

Synthesis of CS/PVA Biodegradable Composite Nanofibers as a Microporous Material with Well Controllable Procedure Through Electrospinning

In this study, we have showed a facile route for fabrication of a novel microporous material based on chitosan (CS) and poly(vinyl alcohol) (PVA) biodegradable nanofibers that have high specific surface area, considerable porosity, and small diameter. Scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface area analysis, and CHNS/O elemental analyser were applied to characterize the fabricated CS/PVA composite nanofibers. Moreover, the influences of spinning conditions including concentration, voltage, electrospinning distance, and flow rate, on size distribution and pore diameter of the final product were systematically studied using 2^k?1 factorial design experiments, and the response surface optimization was used for determining the best synthesis parameter. The results obtained from 2^K?1 factorial design experiments showed that electrospinning parameters influenced the size distribution and pore diameter of the CS/PVA microporous material. Based on the response surface methodology, the CS/PVA product could be obtained with a high microporous diameter of 1.8 nm and a small diameter distribution of 15.0 nm under optimized conditions. The obtained results showed that the fabricated samples could be utilized in different applications.     

Selective organic compounds degradation under controlling composting conditions

Organic matter stabilization resulted from the decrease of cellulose, xylan, arabinan, acetyl groups, glucuronic acids, galacturonic acids (easily biodegradable fractions) and the increase of lignin (resistant compound) and humic substances coming from the initial wastes have been studied. A central composite experimental design was used to investigate the influence of environmental composting parameters (moisture, aeration and particle size) on organic matter evolution. The organic matter evolution was clearly influenced by the studied composting parameters. All results were concordant, with an increase of humic substances and lignin and a decrease of the rest of the cellulose and hemicellulose compounds. Lower cellulose, xylan, acetyl groups and glucuronic acids contents (higher degradation) have been observed under low particle size (1 cm) and higher moisture content (70%). However lower lignin and higher humic substances under medium (3 cm) to low particle size and low moisture content (40%) have been found.     

Cardanol Polymerization Under Acid Conditions By Addition And Condensation Reactions

Cashew nut shell liquid (CNSL) is a byproduct of the cashew nut industry and consists predominantly of phenolic compounds that have an side chain with different degrees of unsaturation. Cardanol, one of these components, is biodegradable and widely available. Studies have revealed several polymerization reactions involving cardanol. However, the mechanisms and detailed structures of polymerization reactions have not been explored, although the final product shows different applications. In this work, we evaluated the mechanism and the products structure of the reaction of cardanol with: (i) boron trifluoride diethyl etherate (BF₃O(CH₂CH₃)₂), and (ii) formaldehyde. The characterizations were performed by FTIR, ¹H NMR, SEC and TGA. The results show that the reaction of cardanol with aldehyde produces the expected like-comb structure with a long hydrocarbon pendent chain. Nevertheless, the reaction of cardanol with BF₃O(CH₂CH₃)₂ can exhibits a more complex structure since it was identified aromatic ring linkages, besides the expected polymerization through C=C.     

Morphological and Thermal Characterization of Linseed-Oil Based Polymers from Cationic and Thermal Polymerization

Linseed oil-based polymers have been synthesized via cationic and thermal polymerization and characterized through various techniques, such as SEM, DMA, DSC and TGA. The morphology of the polymer samples after extraction reveals the smooth structure of the polymer matrix. With an increase in oil content, the morphology is observed to be more loosely bound. With an increase in linseed oil content in the samples, the room temperature storage modulus (E′) varies from 10.4 × 10⁷ to 1.8 × 10⁷ Pa. The glass transition temperatures measured through DMA of the cationic samples ranges from 70 to −6 °C and the crosslink densities range from 18.4 × 10³ to 3.4 × 10³ mol/m³. The glass transition temperatures of the thermal samples range from 106 to −4 °C and the crosslink densities range from 7.7 × 10³ to 2.4 × 10³ mol/m³. The TGA results show three stages of degradation of the polymer samples and it is also revealed that these polymers are stable up to 200 °C, showing negligible decomposition.     

Structural Features and Water Interactions of Etherified Xylan Thin Films

In this paper, the model film approach was used to investigate the structural features and humidity induced changes of the etherified xylan derivatives by using surface sensitive methods. Two routes to modify the birch xylan to generate either cross-linking xylan or more hydrophobic xylan were mastered via allylation and butylation, respectively. Thin nanometer scale model films were prepared by spin-coating and the films were further treated by UV-radical treatment and heat. The structural changes and wetting behaviour of the films before and after the post-treatment procedures were studied using atomic force microscopy and water contact angle measurements. In addition, the water vapour uptake of the xylan derivative films was monitored using quartz crystal microbalance with dissipation (QCM-D) equipped with the humidity module. With the QCM-D, the mass uptake due to the water vapour binding was defined. Simultaneously the changes in the viscoelastic properties of the films when subjected to different relative humidity conditions were determined. We show that the water sensitivity and wetting behaviour of the water soluble xylan derivatives can be altered by cross-linking the film structure and through the molecular rearrangements. Cross-linking and the conformational rearrangements of the allylated xylan reduced the water vapour uptake ability approximately 80?%. Butylated xylan as being a more hydrophobic derivative showed lower ability to uptake water vapour when compared to more hydrophilic xylan derivative. This ability was even further reduced after the post-treatments mainly due to the reassembly of the hydrophobic groups.     

Evolution of organic matter during composting of different organic wastes assessed by CPMAS 13C NMR spectroscopy

In this paper, the evolution of organic matter (OM) during composting of different mixtures of various organic wastes was assessed by means of chemical analyses and CPMAS ¹³C NMR spectroscopy measured during composting. The trends of temperatures and C/N ratios supported the correct evolution of the processes. The CPMAS ¹³C NMR spectra of all composting substrates indicated a reduction in carbohydrates and an increase in aromatic, phenolic, carboxylic and carbonylic C which suggested a preference by microorganisms for easily degradable C molecules. The presence of hardly degradable pine needles in one of the substrates accounted for the lowest increase in alkyl C and the lowest reduction in carbohydrates and carboxyl C as opposite to another substrate characterized by the presence of a highly degradable material such as spent yeast from beer production, which showed the highest increase of the alkyl C/O-alkyl C ratio. The highest increase of COOH deriving by the oxidative degradation of cellulose was shown by a substrate composed by about 50% of plant residues. The smallest increases in alkyl C/O-alkyl C ratio and in polysaccharides were associated to the degradation of proteins and lipids which are major components of sewage sludge. Results obtained were related to the different composition of fresh organic substrates and provided evidence of different OM evolution patterns as a function of the initial substrate composition.     

Lyotropic Liquid Crystal Phases in Cellulose Acetate Phthalate/Hydroxypropyl Cellulose Blends

Cellulose and some of its derivatives form liquid crystalline solutions in a variety of solvents. The present work investigates cellulose acetate phthalate/hydroxypropyl cellulose blends in N,N-dimethylacetamide, in function of concentration and composition, by rheology, considering dynamic viscometry and oscillatory shear tests. The effects of composition, concentration, shear rate, and oscillatory deformation on the rheological functions determines the orientation or mobility of the chain segments in the shear field. Atomic force microscopy and polarized light microscopy studies on corresponding films show that specific interactions, such as the hydrogen bonds between cellulose acetate phthalate and the liquid crystalline component—hydroxypropyl cellulose, stabilizes the morphology, leading to the emergence of different formations typical for lyotropic liquid crystal phases. These studies contribute to a better knowledge of the specific interactions that generate and modify the liquid crystalline properties of cellulose derivatives, required by the applications in electronic domains.     

Decomposition of forest products buried in landfills

The objective of this study was to investigate the decomposition of selected wood and paper products in landfills. The decomposition of these products under anaerobic landfill conditions results in the generation of biogenic carbon dioxide and methane, while the un-decomposed portion represents a biogenic carbon sink. Information on the decomposition of these municipal waste components is used to estimate national methane emissions inventories, for attribution of carbon storage credits, and to assess the life-cycle greenhouse gas impacts of wood and paper products. Hardwood (HW), softwood (SW), plywood (PW), oriented strand board (OSB), particleboard (PB), medium-density fiberboard (MDF), newsprint (NP), corrugated container (CC) and copy paper (CP) were buried in landfills operated with leachate recirculation, and were excavated after approximately 1.5 and 2.5 yr. Samples were analyzed for cellulose (C), hemicellulose (H), lignin (L), volatile solids (VS), and organic carbon (OC). A holocellulose decomposition index (HOD) and carbon storage factor (CSF) were calculated to evaluate the extent of solids decomposition and carbon storage. Samples of OSB made from HW exhibited cellulose plus hemicellulose (C + H) loss of up to 38%, while loss for the other wood types was 0–10% in most samples. The C + H loss was up to 81%, 95% and 96% for NP, CP and CC, respectively. The CSFs for wood and paper samples ranged from 0.34 to 0.47 and 0.02 to 0.27 g OC g^?1 dry material, respectively. These results, in general, correlated well with an earlier laboratory-scale study, though NP and CC decomposition measured in this study were higher than previously reported.     

Treatment of chromium plating process effluents with ion exchange resins.

The surface treatment industry deals with various heavy metals, including the elements Cr, Zn, Ni, Cd, and Cu. Conventional treatments of effluents generate class I solid residue. The aim of this investigation was to study the viability of ion exchange as an alternative process for treatment of rinse water and to determine the efficacy of two ion exchange systems, System 1: "strong" cationic resin-"strong" anionic resin and System 2: "strong" cationic resin-"weak" anionic resin. Commercial resins and solutions taken from rinse tanks of chromium plating companies were used in this investigation. A two-column system, one for the cationic resin and another for the anionic resin, both with 150 ml capacity was mounted. The solution was percolated at a rate of 10 ml/min. The following solutions were used for regeneration of the resins: 2% H2SO4 for the cationic and 4% NaOH for the anionic. The percolated solutions revealed chromium contents of less than 0.25 mg/l, independent of the system used. The "strong" cationic resin-"weak" anionic resin gave excellent regeneration results. The "strong" cationic-"strong" anionic resin presented problems during regeneration, and did not release the retained ions after percolation of 2000 ml of 4% NaOH solution. It is concluded that for this type of treatment, the system composed of "strong" cationic resin and "weak" anionic resin is more appropriate.     

Qualitative and Quantitative Analysis of Lignin Produced from Beech Wood by Different Conditions of the Organosolv Process

Lignins in general have been extensively studied, while beech wood lignin in particular is rarely researched. In the present work, Organosolv isolated lignin from beech wood (OBL) has been characterized. The isolation was done by two methods: (a) by using sulfuric acid at 170 °C and a reaction time of 120 min and (b) at a temperature of 180 °C for 240 min. A range of analytical methods were applied including elemental analysis, FT-IR, UV–Vis, ³¹P NMR, SEC, Pyrolysis-GC/MS and HPLC to gain information about establish the purity, structure, molecular weight, thermal behavior and to determine carbohydrate residues according to the NREL protocol. FT-IR and UV–Vis spectra of OBL revealed expected typical absorptions for lignins. NREL analysis presented a carbohydrate-free lignin fraction which has not been achieved to date. TGA and DSC are used to study the thermal behavior of the isolated lignins and showed a relatively low glass transition temperatures (T_g: 123 °C) and decomposition temperatures of 348 and 381 °C. The pyrograms generated from the pyrolysis–GC/MS at 550 °C consisted mainly of fragments of syringyl, guaiacyl and hydroxyphenyl units, thereby confirming the results of the NMR analysis. Our findings support Organolsolv as an efficient method to isolate pure lignin fractions from beech wood with practical value in industry.     

Thermal Degradation and Kinetics of Alginate Polyurethane Hybrid Material Prepared from Alginic Acid as a Polyol

Alginate polyurethane hybrid materials are prepared by varying mole ratio of 2, 4-TDI as a di-isocyanate and alginic acid as a polyol in presence of dimethyl sulfoxide (DMSO) as a solvent. FT-IR and ¹³C one-dimensional (1D) solid state NMR (SSNMR) spectroscopy indicates that alginic acid is converted into alginate-polyurethane hybrid material via urethane linkage. Surface morphology of alginate-polyurethane hybrids changes by varying alginic acid: TDI ratio. The peak at near 221 °C in DSC thermogram of alginic acid (Alg) is shifted to higher temperature in alginate-polyurethane hybrid (Algpu1 and Algpu2). TGA study shows that alginate-polyurethane hybrid prepared using alginic acid: TDI = 1:1 (Algpu2) is more stable than alginic acid: TDI = 1:0.5 (Algpu1) at 300 °C. Kinetic analysis was performed to fit with TGA data, where the entire degradation process has been considered as three consecutive 1st order reactions. This study shows that thermal stability of alginate-polyurethane hybrid material was increased by adjusting mole ratio of 2, 4-TDI and alginic acid.     

Effect of Hydrothermal Polylactic Acid Degradation on Polymer Molecular Weight and Surface Properties

In the present work, polylactic acid, PLA, samples were degraded by hydrothermal treatment, and then their molecular weights, crystallinity, surface charges and compositions, were determined, respectively, by using viscometry, ¹H NMR, Differential Scanning Calorimetry (DSC), microelectrophoresis and Infra Red spectroscopy methods. The viscometry and ¹H NMR data indicate that the molecular weight, of the polymer, decreases after the hydrothermal treatment. However, the crystalline fractions of the PLA samples, as obtained from the DSC and X-ray data, were not altered after the hydrothermal treatment. Furthermore, the zeta potential data, as determined by microelectrophoresis, show for both non-degraded and degraded PLA, an increase of the polymer surface charge density with the pH of the aqueous phase. However, at acidic pH values, the surface charge density for the degraded PLA was higher as compared to the non degraded one. These differences in surface charge densities of the PLA samples were confirmed by Infrared study, according to which the spectra of degraded polymer show the appearance of carboxyl groups occurring at 1,600 cm⁻¹ at the polymer surface.     

Transport and Immobilization of 2,4,6 15N-Trinitrotoluene in Soil Microcosms Subjected to Long Term Incubation Under Aerobic Conditions

¹⁵N-labeling and solid-state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy was applied to study the immobilization of 2,4,6 trinitrotoluene (TNT) into soil organic matter (SOM). Uncontaminated soil from the Ap horizon of a Luvisol was mixed with ¹⁵N-TNT (enrichment: 99 atm%) and laid over an unspiked layer of the same material. The latter covered soil from the Bt horizon. The microcosms were aerobically incubated under laboratory conditions for up to 11 months. After 1 week, within the total microcosm approximately 90% of the added ¹⁵N (¹⁵N_add) were recovered, mostly in the top layer (87%). After 11 months, this amount decreased to 71%, indicating losses due to denitration or transamination. Within two months, half of ¹⁵N_add had been immobilized in the residues not extractable with organic solvents and water. The amount of the sequestered ¹⁵N_add remained fairly constant until the end of the experiment pointing towards a high stability of TNT-SOM associates. Solid-state ¹⁵N NMR revealed their formation by covalent binding, most tentatively as amides. Complete reduction of TNT to triaminotoluene (TAT) was not prerequisite. The most pronounced downwards movement of ¹⁵N-TNT occurred during the first two months. The major part of it, however, experienced quick immobilization, leaving approximately 10% of ¹⁵N_add recovered in the leachate at the end of the experiment. Calculations indicated contributions of inorganic ¹⁵N_add. Approximately 25% of its organic ¹⁵N_add originated from condensed N, suggesting that in soils the transport of partly reduced TNT is in close association with the organic matter of the soil solution to which they are covalently bound.     

Effects of UV/Photo-Initiator Treatments on Enhancement of Crystallinity of Polylactide Films and Their Physicochemical Properties

Effects of UV/photo-initiator treatments on crystal formation and properties of polylactide (PLLA) films are investigated. Camphorquinone and riboflavin photo-initiator solutions in methanol are employed in the treatment of amorphous quenched PLLA films. Results from FTIR, ATR-FTIR, DSC, XRD, and SEM show evidence of crystalline domain formation dispersed throughout the film. ¹H NMR and GPC results suggest that the molecular weights of the polymer slightly decrease after the treatment. This indicates that the treatment leads to a diffusion of the photo-initiators molecules through the film matrix, resulting in a low degree of PLLA chain scissions, and formation of carboxylic acid and hydroxyl polar end groups. This, in turn, induces PLLA crystallization, which imposes profound effects on surface wettability and physical and mechanical properties of the samples. The process can be applied in optimizing properties of PLLA films with shorter treatment times, compared to other methods, which is suitable for use in various fields; especially those that require specific characteristics like biomedical, packaging and environmental applications.     

A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.     

Tween 20 and Its Major Free Fatty Acids as Carbon Substrates for the Production of Polyhydroxyalkanoates in Pseudomonas aeruginosa ATCC 27853

The ability of Pseudomonas aeruginosa ATCC 27853 to grow and synthesize polyhydroxyalkanoates (PHAs) using Tween 20 as the sole carbon source was investigated. Tween 20 could support cell growth and PHA production. The polymer produced from Tween 20 was compared with those produced from its major free fatty acids components: lauric (C₁₂), myristic (C₁₄), and palmitic (C₁₆) acids. Gas-chromatographic analysis of methanolyzed samples and ¹³C-Nuclear Magnetic Resonance (NMR) showed that the PHAs obtained are composed of even carbon atoms 3-hydroxyalkanoates ranging from C₆ to C₁₄, with C₈ and C₁₀ as the predominant components. The nature of the carbon sources used had little influence on the composition, but was found to be important in determining the average molecular weight, shorter chain fatty acids yielding higher molecular weight products. Fast Atom Bombardment-Mass Spectrometry (FAB-MS) of partially pyrolyzed samples, coupled to statistical analysis, showed that these PHAs are random copolymers.     

Polyols and Rigid Polyurethane Foams from Cashew Nut Shell Liquid

Cashew nut shell liquid (CNSL) is a natural aromatic oil consisting of a mixture of phenolic structures with a carboxyl group in ortho position and substituted in meta position with a hydrocarbon chain of 15 carbon atoms. The major component of CNSL is anacardic acid (90?%), which is easily decarboxylated to cardanol by distillation. The present work describes the synthesis of new biobased Mannich polyols for rigid polyurethane foams in two steps: synthesis of Mannich bases by reacting phenolic ring of cardanol with N-(2-hydroxyethyl)-1,3-oxazolidine followed by alkoxylation reactions. The polyols were characterized by wet methods (hydroxyl numbers, viscosity, acid value, density, water content, iodine value etc.), spectroscopic methods (FT-IR, ¹H NMR and ¹³C NMR) and by Gel Permeation Chromatography. The Mannich polyols from cardanol are excellent replacements for petrochemical derived Mannich polyols based on nonyl phenol. Cardanol-based polyols were used successfully for the preparation of rigid polyurethane foams of good physical?Cmechanical and fireproofing properties.     

Thermo-Chemical Decomposition Study of Polyurethane Elastomer Through Glycerolysis Route with Using Crude and Refined Glycerine as a Transesterification Agent

Due to the increasing amount of polyurethane waste, chemical recycling of these materials is a topic of growing interest for many researchers. The primary purpose of polyurethane feedstock recycling is to recover the starting polyol. In this study glycerolysis using glycerine from two sources and two purity grades is proposed as a method of chemical recycling. The main effort of this paper focuses on the employment of commercial glycerine of analytical grade and waste glycerine without purification derived from the biodiesel production, as a decomposing agent for polyurethane recycling. In this study, the influence of polyurethane to glycerine mass ratio (PU/GL) and the type of decomposing agent on the chemical structure by FTIR, ¹H NMR and GPC was examined. FTIR analysis of the glycerolysates showed absorption peaks similar to the virgin polyol. Those results are in compliance with GPC chromatograms, which showed for all samples, well-defined peak at ca. 13 min of retention time. The molecular weight of glycerolysates was ranging from 800 to 1300 g mol^?1 depending on PU/GL mass ratio. The novel decomposition agent, namely waste glycerine derived from biodiesel production was successfully used in glycerolysis process.