Thermal and FT-IR Characterization of Gigantochloa levis and Gigantochloa scortechinii Bamboo, a Naturally Occurring Polymeric Composite

This research presents, thermal (TGA, Kinetics, DSC) analysis and FT-IR characterization of two bamboo species viz. Gigantochloa levis and Gigantochloa scortechinii at different position and locations (Internode and node). The internodes and nodes of Gigantochloa levis and Gigantochloa scortechinii exhibited similar thermal stability, observed up to 200 °C. The decomposition of cellulose and hemicelluloses component of the bamboo species occurred between 220 and 390 °C, while the degradation of lignin was observed above 400 °C. The kinetic studies revealed that Gigantochloa levis is more sensitive to degradation as compared to Gigantochloa scortechinii. The FT-IR studies were carried to assign the functional groups available at different positions and locations.     

Cellulose Fiber Isolation and Characterization from Sweet Blue Lupin Hull and Canola Straw

In this study, cellulose fibers were removed from crop by-products using a combination of sodium hydroxide treatment followed by acidified sodium chlorite treatment. The objective was to obtain high recovery of cellulose by optimizing treatment conditions with sodium hydroxide (5–20%, 25–75 °C and 2–10 h) followed by acidified sodium chlorite (1.7%, 75 °C for 2–6 h) to remove maximum lignin and hemicellulose, as well as to investigate the effect of lignin content of the starting materials on the treatment efficiency. Samples were characterized for their chemical composition, crystallinity, thermal behavior and morphology to evaluate the effects of treatments on the fibers’ structure. The optimum sodium hydroxide treatment conditions for maximum cellulose recovery was at 15% NaOH concentration, 99 °C and 6 h. Subsequent acidified sodium chlorite treatment at 75 °C was found to be effective in removing both hemicellulose and lignin, resulting in higher recovery of cellulose in lupin hull (~?95%) and canola straw (~?93%). The resultant cellulose fibers of both crop by-products had increased crystallinity without changing cellulose I structure (~?68–73%). Improved thermal stabilities were observed with increased onset of degradation temperatures up to 307–318 °C. Morphological investigations validated the effectiveness of treatments, revealing disrupted cell wall matrix and increased surface area due to the removal of non-cellulosics. The results suggest that the optimized combination of sodium hydroxide and acidified sodium chlorite treatments could be effectively used for the isolation of cellulose fibers from sweet blue lupin hull and canola straw, which find a great number of uses in a wide range of industrial applications.     

Pyrolysis of jute dust: effect of reaction parameters and analysis of products

Biowastes are becoming potential feedstocks for direct utilization or conversion to solid, liquid and gaseous fuels via various thermochemical routes. In this regard, jute dust which is a major agro-industrial waste in jute mills was pyrolysed in a fixed-bed reactor with an aim to study the product distribution and their characterization and to identify the optimum condition for bio-oil yield. The investigated process variables were temperature (400–700 °C), heating rate (10 and 40 °C/min) and nitrogen gas flow rate (50–250 ml/min). The yield of bio-oil is found to be maximum at 500 °C with a heating rate of 40 °C/min. However, further increase in temperature leads to decrease in bio-oil yield. Chemical compositions of the bio-oils were investigated using chromatographic and spectroscopic techniques such as ¹H NMR, FTIR and GC–MS. The heating value of the bio-oil is 26.71 MJ/kg. The study shows that jute dust have potential for conversion to bio-oil through the process of pyrolysis to supplement the petro-derived liquid fuel for heating and transportation applications after upgrading. The biochar produced as a co-product of jute dust pyrolysis can be a potential soil amendment with multiple benefits including increased soil fertility and C-sequestration.     

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.     

Styrene/Lignin-Based Polymeric Composites Obtained Through a Sequential Mass-Suspension Polymerization Process

A modified sequential mass-suspension polymerization was employed to ensure adequate dispersion of lignin into the monomeric phase. Due to its complex macromolecular structure and low compatibility with styrene, eucalyptus wood-extracted lignin, via a modified Kraft method, was esterified with methacrylic anhydride to ensure organic phase homogeneity into the reaction medium. Infrared spectroscopy showed a decrease in the hydroxyl band, a characteristic of natural lignin (3200–3400 cm^?1) and an increase in the characteristic ester band (1720–1740 cm^?1) whereas nuclear magnetic resonance measurements exhibited intense peaks in the range from 1.7 to 2.05 ppm (–CH₃) and 5.4 to 6.2 ppm (=CH₂), related to methacrylic anhydride. Comparatively, the esterified lignin also displayed an increase of its glass transition temperature for 98?°C, related to natural lignin, whose T _g was determined to be equal to 91?°C. Styrene/lignin-based polymers exhibited higher average molar masses in comparison to the values observed for polystyrene synthesized with similar amounts of benzoyl peroxide, due to the ability of lignin to act as a free-radical scavenger. Composites obtained with styrene and natural or esterified lignin were successfully synthesized, presenting regular morphology and proper lignin dispersion. Based on a very simple polymerization system, it is possible to enhance the final properties of polystyrene through the incorporation of lignin, which represents an important platform for developing attractive polymeric materials from renewable resources.     

Lignin Functionalized by Thermally Curable Propargyl Groups as Heat-Resistant Polymeric Material

Lignin was chemically functionalized via Williamson etherification reaction with propargyl bromide to prepare a thermosetting bio-resin, propargyllignin. The optimum reaction conditions were found at 70?°C for 4?h under the catalysis of sodium hydroxide in the ethanol solution. The propargllignin resin had highly improved processing capability, evidenced by good solubility, low melting point (<100?°C) and thermal curability. Upon heating, propargyllignin resin solidified with an exotherm around 180?C280?°C peaking at 240?°C, implying its thermal cure reaction via ethynyl polymerization. Compared with lignin feedstock, the propargyllignin resin showed much higher thermal properties: an onset decomposition temperature of 410?°C and a residue yield of 58?% at 800?°C (for lignin, onset decomposition temperature of 250?°C and residue yield of 34?%). Different from the lignin feedstock, propargyllignin was readily applied as curable thermosetting resin for composite matrix, and exhibited high mechanical and thermal properties.     

Laccase-Assisted Grafting of Acrylic Acid onto Lignin for its Recovery from Wastewater

The acrylic acid (AA) in the wastewater from paint manufacturing could be recovered by grafting to lignosulfonate in the presence of laccase and tert-butyl hydroperoxide (t-BHP). The low concentration of t-BHP did not inhibit the laccase activity, but improved the radical formation on lignin by laccase reaction, then initiated AA polymerization on lignin. The results showed laccase took a significant role for AA grafting to lignin. 94 % of AA could be polymerized on lignin by laccase/t-BHP, while only 32 % of AA was grafted on lignin with the same condition without laccase. The ratio of lignin to acrylic acid also affected AA recovery, and higher concentration of acrylic acid led to high recovery rate of AA. In this reaction system, the suitable range of temperature was 30–40 °C for the chemo-enzymatic reaction. The AA grafted on lignin could be precipitated by calcium ion and recovered.     

Color analysis of combustion ashes of seawater-soaked wood: estimation of salt concentration

The color of wood ash is normally white, but black color ash was observed when seawater-soaked wood was combusted. In order to check the conditions for generation of black ash, we examined both ashing temperatures from 500 to 800 °C and seawater salt densities for wood soaking. As seawater salt densities rose, the ash color got black at ashing temperatures of 500 and 700 °C. The colors of the ash were analyzed by a spectrophotometer, and color space L* a* b* was measured. The L* value and wood ash yield showed a negative correlation when the ashing temperature was at 600 °C. Salt concentration in wood (SC) was practicably estimated from the L* value (R ² = 0.51) by the approximation formula [SC (%) = 11.82e^?0.038L*]. By scanning electron microscope (SEM) observation, black ash of 600 °C was fully covered by translucent material. It was composed of Na, Mg and Cl by energy dispersive X-ray spectroscopy analysis, and seemed to be crystallized seawater salt. Washed black ash was also observed by SEM, translucent seawater salt was removed and the wood tissue was observed. Black ash was found to be carbonized wood tissue residue, and it was generated when seawater salt exists with a woody biomass.     

Influence of zinc chloride addition on the chemical structure of bio-oil obtained during co-pyrolysis of wood/synthetic polymer blends

The chemical structure of liquid products of the pinewood sawdust (W) co-pyrolysis with polystyrene (PS) and polypropylene (PP) with and without the zinc chloride as an additive was investigated. The pyrolysis process was carried out at 450 °C with the heating rate of 5 °C/min. The yield of liquid products of pyrolysis was in the range of 37–91 wt% and their form was liquid or semi-solid depending on the composition of the wood/polymer blend. The zinc chloride addition to wood/polymer blends has influenced the range of samples decomposition as well as the chemical structure of resulted bio-oils. All bio-oils from wood/polypropylene blends were two-phase (liquid and solid). Contrarily, all bio-oils obtained from biopolymer/polypropylene blends with zinc chloride added were yellow liquids. All analyses proved that the structure and the quality of bio-oil strongly depend on both the composition of the blend and the presence of ZnCl₂ as an additive. The FT-IR analyses of oils showed that oxygen-containing groups and hydrocarbons content highly depend on the composition of biomass/synthetic polymer mixture. The fractionation of bio-oils by column chromatography with four different solvents was followed by GC–MS analysis. Results confirmed the significant removal and/or transformation of oxygen-containing organic compounds due to the zinc chloride presence during pyrolysis process.     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

Residual organic fluorinated compounds from thermal treatment of PFOA,PFHxA and PFOS adsorbed onto granular activated carbon (GAC)

Perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS) adsorbed onto granular activated carbon (GAC) were thermally treated in N₂ gas stream. The purpose was to assess the fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) during thermal regeneration of GAC, which had been used for water treatment. Mineralized F, residual PFASs including short-chained species, and volatile organic fluorine (VOF) were determined. In a temperature condition of 700 °C, VOF were 13.2, 4.8, and 5.9 % as for PFOA, PFHxA, and PFOS. However, the VOF decreased to 0.1 %, if the GAC and off-gas were kept at 1000 °C. No PFASs remained in GAC at 700–1000 °C; at the same time, short-chained PFASs were slightly detected in the aqueous trapping of off-gas at 800 and 900 °C conditions. The destruction of PFASs on GAC could be perfect if the temperature is higher than 700 °C; however, the process is competitive against volatile escape from GAC. Destruction in gaseous phase needs a temperature as high as 1000 °C. Destruction of PFASs on the surface of GAC, volatile escape from the site, and thermolysis in gas phase should be considered, as to thermal regeneration of GAC.     

Microwave Assisted Short-Time Alkaline Extraction of Birch Xylan

Efficacy of microwave energy for the extraction of xylan from birch wood as an alternative to conventional method of extraction was investigated. Effect of irradiation time and microwave power input on the solubilization of wood and yield of extracted xylan was studied. The maximum yield of xylan obtained at the higher power level was significantly lesser compared to the lower power level indicating the molecular degradation of the polymer. The highest yield of xylan (60 % of the original xylan) was obtained at the lowest power level studied, 110 W, for an irradiation time of 10 min. Comparison with conventional extraction showed that 10 min of microwave extraction provided a similar wood dissolution to that at 90 °C for 1.5 h, but with a higher yield of xylan. Characterization of the precipitated xylan indicated that the extracted xylan contained 68–88 % of xylose with the major chemical structure consisting of a linear backbone of (1-4) β-d-xylopyransoyl residues. Molecular mass of the extracted xylan indicated that the xylan extracted using microwave contained 60–70 % of high molecular weight fraction, and about 30–40 % of low molecular weight fraction, whereas xylan extracted using conventional method showed a reverse trend. Molecular mass of non-aggregated xylan was reported to be 6,000 Da (in terms of dextran equivalents). Crystallinity of wood fibers increased irrespective of the method of extraction indicating no degradation of the strength of the fibers occurred during the extraction.     

Synthesis and Properties of Polyesters from Waste Grapeseed Oil: Comparison with Soybean and Rapeseed Oils

The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917^®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. T _g’s of the polyesters ranged from ?36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher T _g polymers (?17 to 17 °C) than soybean (?25 to 6 °C) and rapeseed (?36 to ?27 °C). Grapeseed oil showed similar properties to soybean oil in terms of T _g, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.     

A Novel and Formaldehyde-Free Preparation Method for Lignin Amine and Its Enhancement for Soy Protein Adhesive

In this work, a novel two-step process to prepare primary lignin amine was developed. The lignin used in this study was obtained from the residue of cellulosic sugar fermentation for bioethanol (referred as “lignin”). The lignin was initially oxidized through Fenton oxidation. The oxidized lignin was further converted to lignin amine by reductive amination. Ammonia was used in the second step leading to give the highly active primary lignin amine. The oxidation and reduction exhibited relatively high yields of 80.0 and 91.2 % respectively. For comparison, lignin was partially depolymerized via mild hydrogenolysis and then the partial depolymerized lignin was also converted to lignin amine using the same method. The obtained lignin amines were characterized in detail using elemental analysis, proton nuclear magnetic resonance (¹H NMR), and Fourier transform infrared spectroscopy (FTIR). Further, modification of soy protein adhesive by lignin amine was exemplified in wood bonding, and the results indicated that addition of lignin amine greatly increased water resistance of soy protein adhesives.     

Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials

Lignin represents a vastly under-utilized natural polymer co-generated during papermaking and biomass fractionation. Different types of lignin exist, and these differ with regard to isolation protocol and plant resource (i.e., wood type or agricultural harvesting residue). The incorporation of lignin into polymeric systems has been demonstrated, and this depends on solubility and reactivity characteristics. Several industrial utilization examples are presented for sulfur-free, water-insoluble lignins. These include materials for automotive brakes, wood panel products, biodispersants, polyurethane foams, and epoxy resins for printed circuit boards.     

Determination of In Situ Esterification Parameters of Citric Acid-Glycerol Based Polymers for Wood Impregnation

The development of wood treatments is of increasing industrial importance. A novel technique for improving the properties of lodgepole pine and white pine through modification of the microstructure is described. The present investigation is devoted to the synthesis and determination of in situ parameters of citric acid and glycerol based polymers for wood impregnation. This solvent free approach is environmentally friendly and achieved through an esterification condensation reaction under acidic conditions. Crude glycerol and citric acid reactants were cross-linked via a curing process at 160?°C creating a polymer with only water as the byproduct. The ester bonds and crosslinking levels were controlled using different catalysts and citric acid contents and related to the reaction time and temperature. The nature of bonding within the polymers and at the wood cell walls was determined by FT-IR analysis. The thermal properties such as glass transition temperature (T_g) were studied using TGA/DSC and the effect of citric acid content and catalyst type determined. Dimensional stability of impregnated wood samples improved above 50% for each sample with HCl and p-TSA catalysts compared to control samples. FTIR spectra were studied to show the presence of the ester linkages of the polymer in situ at the wood cell walls. Bonding between the polymer and wood macromolecules were observed by scanning electron microscopy and interpreted as evidence of chemical bonds at the wood cells. When prepared using a catalyst, the polymer was intimately incorporated into wood structure significantly improving the substrate dimensional stability. Enhanced stability makes this approach of particular interest for exterior wood products especially as a green renewable option for the wood industry.     

Novel Bioactive Chiral Poly(amide–imide)s Containing Different Amino Acids Linkages: Studies on Synthesis, Characterization and Biodegradability

In this paper chiral bioactive poly(amide–imide)s (PAI)s were synthesized from four different diacids containing chiral amino acids with 4,4′-methylene bis(3-chloro 2,6-diethylaniline) as a diamine via direct polycondensation reaction in a system of tetra-n-butylammonium bromide and triphenyl phosphite as a condensing agent. The structures of these polymers were confirmed by FT-IR, ¹H-NMR, specific rotation, elemental and thermogravimetric analysis (TGA) techniques. TGA showed that the 10 % weight loss temperature in a nitrogen atmosphere was more than 378 °C, which indicates that the resulting PAIs have a good thermal stability. The biodegradability of the monomers and prepared polymers was investigated in culture media and soil burial test for assessment of the susceptibility of these compounds to microbial degradation. The results showed that the synthesized monomers and theirs derived polymers are biologically active and nontoxic to microbial growth.     

Recovery of Kraft Lignin from OPEFB and Using for Lignin–Agarose Hydrogel

Lignins from the spent pulping liquor were normally acquired as waste product of pulp and paper mills. The possibilities of utilizing kraft lignin have yet been developed for commercial innovation. The objectives of this research are to recovery and utilization of lignin from black liquor of oil palm empty fruit bunches (OPEFBs). Kraft lignins from the OPEFBs black liquor were recovered by acidification procedure. They were precipitated at pH 4, 3, and 2 in order that determine the optimum pH for isolation. It can be clearly seen that the best condition of lignin precipitation was at pH 3. It offered the highest yield and purity. The kraft lignin and agarose were utilized as the crude material for the production of lignin–agarose hydrogel. Lignin–agarose hydrogel could be prepared by using epichlorohydrin as the cross-linking agent. The cross-linking occurrence was recognized by FTIR. Physical and chemical properties of hydrogel were investigated. Gel strength of lignin–agarose hydrogel was characterized by texture personal analysis. The results demonstrated that the gel strength increased with increasing of lignin and epichlorohydrin (ECH) in agarose solutions. 5% lignin, 5% agarose and 10 mL ECH contributed the best gel formation and the great mechanical properties. The effect of cross-linking condition on the gel properties, for example, gel hardness and fracturability, was examined.     

Effect of pretreatment techniques on food waste solubilization and biogas production during thermophilic batch anaerobic digestion

The purpose of this study was to optimize the alkaline, ultrasonication, and thermal pretreatment in order to enhance the solubilization of food waste (FW) for the production of volatile fatty acids, hydrogen, and methane in thermophilic batch anaerobic digestion. Initially, the effect of pretreatment techniques in the acidogenic phase was studied, and the optimal combinations of different conditions were determined. It was found that each pretreatment technique affected food waste solubilization differently. Alkaline pretreatment increased hydrogen yield in the acidogenic sludge by four times over control. COD solubilization was increased by 47 % when FW pre-heated at 130 °C for 60 min. Ultrasonication at 20 kHz and 45 min reduced processing time to 38 h from the 60–80 h needed in normal operation. Response surface methodology (RSM) was used to optimize a combination of alkaline, ultrasonication, and thermal pretreatment. Optimized conditions were applied to methanogenic single-stage thermophilic AD process, and their impact on biogas production was monitored. Results showed that FW heated at 130 °C for 50 min geminates biogas production compared to control experiment. In conclusion, a short thermal pretreatment regime could significant affect biogas production in single-stage thermophilic AD.     

Potential utilization of burned wood in manufacture of medium density fiberboard

The potential utilization of burned wood in the manufacture of medium density fiberboard (MDF) was investigated. For this aim, the MDF panels were made of various mixtures of burned pine wood (Pinus sylvestris L.), unburned beech (Fagus orientalis L.) and oak (Ouercus robur L.) woods under commercial conditions in an MDF company. The mixture ratio of the unburned beech and oak woods to the burned pine wood were 50/50 wt%. The mixing ratios of burned wood chips with unburned wood chips were 0:100, 25:75, 50:50, 75:25 and 100:0, %, respectively. A commercial urea–formaldehyde resin was used as a binder. The physical properties measured in the investigation included density and thickness swelling, while the mechanical properties examined were bending strength, modulus elasticity, internal bond, screw holding ability perpendicular to the plane of panel, and janka hardness perpendicular to the plane of the panel. Surface roughness and color of the panels were also measured. The results indicated that all the panels met the mechanical properties of general-purpose MDF requirements of EN 622-5. The surface roughness of the MDF panels containing burned wood decreased with increasing burned wood content but remained higher than the control panels. The dimensional stability of the MDF panels decreased with the incorporation of burned wood fibers as compared with the control MDF panels.