Effects of Alkali Treatment on the Properties of Short Flax Fiber–Poly(Lactic Acid) Eco-Composites

In this study, the influence of alkali (NaOH) treatment on the mechanical, thermal and morphological properties of eco-composites of short flax fiber/poly(lactic acid) (PLA) was investigated. SEM analysis conducted on alkali treated flax fibers showed that the packed structure of the fibrils was deformed by the removal non-cellulosic materials. The fibrils were separated from each other and the surface roughness of the alkali treated flax fibers was improved. The mechanical tests indicated that the modulus of the untreated fiber/PLA composites was higher than that of PLA; on the other hand the modulus of alkali treated flax fiber/PLA was lower than PLA. Thermal properties of the PLA in the treated flax fiber composites were also affected. T_g values of treated flax fiber composites were lowered by nearly 10 °C for 10% NaOH treatment and 15 °C for 30% NaOH treatment. A bimodal melting behavior was observed for treated fiber composites different than both of neat PLA and untreated fiber composites. Furthermore, wide angle X-ray diffraction analysis showed that the crystalline structure of cellulose of flax fibers changed from cellulose-I structure to cellulose-II.     

Preparation and Fundamental Characterization of Cellulose Nanocrystal from Oil Palm Fronds Biomass

The objective of this work was to isolate cellulose nanocrystal (CNC) from oil palm fronds (Elaeis guineensis) and its subsequent characterization. Isolation involves sodium hydroxide/anthraquinone pulping with mechanical refining followed by total chlorine free bleaching (includes oxygen delignification, hydrogen peroxide oxidation and peracetic acid treatment) before acid hydrolysis. Bleaching significantly decreased kappa number and increased α-cellulose percentage of fibers as confirmed by Technical Association of the Pulp and Paper Industry standards. Transmission electron microscopy (TEM), X-ray diffraction, Fourier transform infrared spectroscopy and thermogravimetric analysis revealed that acid hydrolysis along with bleaching improved crystallinity index and thermal stability of the extracted nanocrystals. It was observed that CNC maintained its cellulose 1 polymorph despite hydrolysis treatment. Mean diameter as observed by TEM and average fiber aspect ratio of obtained CNC was 7.44 ± 0.17 nm and 16.53 ± 3.52, respectively making it suitable as a reinforcing material for nanocomposite.     

Preparation of Cellulose Nanocrystals Using an Ionic Liquid

In this paper cellulose nanocrystals were prepared by treating microcrystalline cellulose with 1-butyl-3-methylimidazolium hydrogen sulphate ionic liquid. Cellulose nanocrystals, after separation from ionic liquid, were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Field emission scanning electron microscopy (FESEM) Transmission Electron Microscope (TEM) and Thermogravimetric analysis. XRD results showed no changes in type of cellulose after the treatment with ionic liquid, however, high crystallinity index was observed in the ionic liquid treated sample. Cellulose nanocrystals, having length around 50–300 nm and diameter around 14–22 nm were observed in the ionic liquid treated sample under FESEM and TEM, and similar patterns of peaks as that of microcrystalline cellulose were observed for cellulose nanocrystals in the FTIR spectra. The thermal stability of the cellulose nanocrystals was measured low as compare to microcrystalline cellulose.     

The Effect of Extraction Conditions on the Chemical Characteristics of Pectin from Opuntia ficus indica Cladode Flour

Pectin from the cladode flour of Opuntia ficus indica was extracted at different ethylenediaminetetraacetate concentrations (10 or 20 %), temperatures (40 or 80 °C), pH values (2 or 11), and times (10, 20, 30 40, 50 or 60 min). The effects of the extraction conditions on the yield, purity, and chemical composition of pectin were assessed. The highest pectin yield was observed for pectin obtained under alkaline conditions and 20 % of EDTA. However, pectin produced from alkaline extractions had a lower content of GalA than pectin produced from acid extractions. Higher temperatures favored the extraction of pectin under acid conditions, but these conditions diminished the arabinose content of pectins in a time-dependent manner. The tested extraction conditions caused only slight changes in the molecular weight of the extracted pectin as a function of time.     

Recovery of biomass cellulose from waste sewage sludge

In our previous work, the primary sludge from wastewater treatment plants was shown to contain a considerable amount of cellulose (about 20%, based on suspended solids) owing to the discharge of toilet paper. For the purpose of using the cellulose as a biomass resource, this study examined a simple method for its recovery. When fibrous cellulose was suspended in 0.3% sulfuric acid and autoclaved at 130°C for 60 min, 85%–88% of the initial solids remained without dissolving. Under these conditions, an activated sludge sample not containing cellulose was strongly hydrolyzed and only 7% of the initial solids remained. The prescribed amounts of cellulose added to the activated sludge sample were quantitatively recovered by the autoclaving treatment. In the treatment of primary sludge containing >20% cellulose, residual solids with relatively high levels of cellulose (>69%) could be obtained. The results indicate that the method proposed here could recover cellulose practically from waste sewage sludge for biomass utilization. Received: July 17, 2000 / Accepted: July 4, 2001     

A Comparative Study of Pectin Extracted from Passion Fruit Rind Flours

Brazil is the world’s main producer of passion fruit. Previous reports show that passion fruit rinds, an industrial waste, contain large amounts of pectin. Pectin is a dietary fiber that is widely used in the food industry as a gelling agent and stabilizer. In this study, the quality and characteristics of pectin extracted from yellow passion fruit rind flour was investigated. Pectin was extracted from both commercially available and prepared passion fruit peels using nitric acid. Once extracted, the pectin was evaluated for its molecular characteristics and chemical composition as well as for the apparent and reduced viscosity of the gel. Prepared (blanched) rind flour yielded 203.4 g kg⁻¹ of pectin, which contained a uronic acid content of 681 mg g⁻¹, a degree of esterification of 80, a degree of methylation of 80, a reduced viscosity of 6.8 dL g⁻¹ and an apparent viscosity of 13.4 cP. The results suggest a clear influence of the raw material on it’s the resultant characteristics of the pectin. In addition, our results show that therheological properties and molar characteristics of pectin were negatively affected when the rind flours were subjected to high temperatures. Pectin methyl esterase activity was detected in the freeze-dried, unblanched raw material. Extensive efforts have been directed towards minimizing waste and the reported results show that high quality pectin can be obtained from passion fruit rinds, an industrial waste product of passion fruit processing.     

Recovery of materials from waste printed circuit boards by vacuum pyrolysis and vacuum centrifugal separation

In this research, a two-step process consisting of vacuum pyrolysis and vacuum centrifugal separation was employed to treat waste printed circuit boards (WPCBs). Firstly, WPCBs were pyrolysed under vacuum condition at 600 °C for 30 min in a lab-scale reactor. Then, the obtained pyrolysis residue was heated under vacuum until the solder was melted, and then the molten solder was separated from the pyrolysis residue by the centrifugal force. The results of vacuum pyrolysis showed that the type-A of WPCBs (the base plates of which was made from cellulose paper reinforced phenolic resin) pyrolysed to form an average of 67.97 wt.% residue, 27.73 wt.% oil, and 4.30 wt.% gas; and pyrolysis of the type-B of WPCBs (the base plates of which was made from glass fiber reinforced epoxy resin) led to an average mass balance of 72.20 wt.% residue, 21.45 wt.% oil, and 6.35 wt.% gas. The results of vacuum centrifugal separation showed that the separation of solder was complete when the pyrolysis residue was heated at 400 °C, and the rotating drum was rotated at 1200 rpm for 10 min. The pyrolysis oil and gas can be used as fuel or chemical feedstock after treatment. The pyrolysis residue after solder separation contained various metals, glass fibers and other inorganic materials, which could be recycled for further processing. The recovered solder can be reused directly and it can also be a good resource of lead and tin for refining.     

Experimental co-digestion of corn stalk and vermicompost to improve biogas production

Anaerobic co-digestion of corn stalk and vermicompost (VC) as well as mono-digestion of corn stalk were investigated. Batch mono-digestion experiments were performed at 35 ± 1 °C and initial total solid loading (TSL) ranged from 1.2% to 6.0%. Batch co-digestion experiments were performed at 35 ± 1 °C and initial TSL of 6% with VC proportions ranged from 20% to 80% of total solid (TS). For mono-digestion of corn stalk, a maximum methane yield of 217.60 ± 13.87 mL/g TS_added was obtained at initial TSL of 4.8%, and acidification was found at initial TSL of 6.0% with the lowest pH value of 5.10 on day 4. Co-digestion improved the methane yields by 4.42–58.61% via enhancing volatile fatty acids (VFAs) concentration and pH value compared with mono-digestion of corn stalk. The maximum biogas yield of 410.30 ± 11.01 mL/g TS_added and methane yield of 259.35 ± 13.85 mL/g TS_added were obtained for 40% VC addition. Structure analysis by X-ray diffractometry (XRD) showed that the lowest crystallinity of 35.04 of digested corn stalk was obtained from co-digestion with 40% VC, which decreased 29.4% compared to 49.6 obtained from un-treated corn stalk. It is concluded that co-digestion with VC is beneficial for improving biodigestibility and methane yield from corn stalk.     

Synthesis of Polyurethane and Characterization of its Composites Based on Alfa Cellulose Fibers

Polyurethane (PU) based on polycaprolactone (PCL) and 4,4′ diphenyl methylene diisocyanate (MDI) was synthesized using a two-step method. The PU obtained was then blended with various amounts of cellulose extracted from alfa stems to prepare composite materials. The influence of cellulose on the thermal and mechanical properties of different composites was demonstrated by means of several characterization techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM)…     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

Characterization and Properties of Hydrophilic Cellulose Acetate Propionate Derivative

The chemical modification of Acrylamidomethyl Cellulose Acetate Propionate (AMCAP) was carried out by radical addition of acrylic acid. The structural modification was confirmed with the aid of FTIR, MS and NMR techniques. Thermal properties of hydrophilic cellulose derivative (AMCAP–H₂O₂) such as glass transition (T_g 153 °C) and thermal stability (372.7 °C) were determined by DSC and TGA techniques, respectively. These thermal properties confirmed the introduction of carboxylic groups into AMCAP structure, which causes an impact in their properties. The AMCAP–H₂O₂ shows minor contact angle compared to AMCAP, giving a more hydrophilic characteristic, due to acrylic acid addition into the side chains of AMCAP polymer.     

Measurement of carbon storage in landfills from the biogenic carbon content of excavated waste samples

Landfills are an anaerobic ecosystem and represent the major disposal alternative for municipal solid waste (MSW) in the U.S. While some fraction of the biogenic carbon, primarily cellulose (Cel) and hemicellulose (H), is converted to carbon dioxide and methane, lignin (L) is essentially recalcitrant. The biogenic carbon that is not mineralized is stored within the landfill. This carbon storage represents a significant component of a landfill carbon balance. The fraction of biogenic carbon that is not reactive in the landfill environment and therefore stored was derived for samples of excavated waste by measurement of the total organic carbon, its biogenic fraction, and the remaining methane potential. The average biogenic carbon content of the excavated samples was 64.6 ± 18.0% (average ± standard deviation), while the average carbon storage factor was 0.09 ± 0.06 g biogenic-C stored per g dry sample or 0.66 ± 0.16 g biogenic-C stored per g biogenic C_.     

Extraction of Cellulose Nanocrystals from Phormium tenax Fibres

Cellulose nanocrystals with an acicular structure ranged from 100 to 200 nm in length and 15 nm in width were extracted from Phormium tenax leaf fibres by acid hydrolysis. A two-step procedure for the extraction of nano-sized cellulose was studied and the obtained nanocrystals were characterized using morphological investigations (optical, scanning electron and atomic force microscopy), as well as physico-chemical characterization by Wide Angle X-ray Scattering, infrared spectroscopy and thermogravimetric analysis. A study of birefringence properties was also performed. The first chemical treatment leads to the production of holocellulose by the gradual removal of lignin, while the subsequent sulphuric acid hydrolysis process allows obtaining cellulose nanocrystals in an aqueous suspension. The results reported support the repeatability and the effectiveness of the procedure performed. Moreover, the high cellulose content of P. tenax fibre and their declining market interest, suggest the interest of this investigation and the possibility to use natural fibres for the production of a reinforcement phase to involve in the nanocomposite approach for industrial applications.     

Development of Thixotropic Coatings Using Dimerized Soybean Oil Fatty Acids: The Case of Polyamide of 1,2-Phenylene Diamine

Soybean oil (SBO) was dimerized and the crude dimer acid product reacted with 1,2-phenylene diamine at 210 ± 5 °C under inert atmosphere to obtain fatty polyamide (FPA). The FPA was used to modify a commercial alkyd resin by reacting a mixture of the alkyd resin with 5 wt% of FPA at 120 °C for 80 min under inert atmosphere. The FTIR spectrum of the FPA modified resin showed evidence of higher degree of H-bonding than was found for the unmodified alkyd. White gloss coatings of 15, 20, 25, and 30% solids were formulated from the modified and unmodified resins and examined for performance with respect to: leveling, sag resistance, drying time, pigment settling, skinning tendency and film hardness. Results showed that the unmodified alkyd coatings exhibited good leveling but poor sag resistance at all solid contents. In contrast, FPA modified alkyd coatings combined good leveling with high sag resistance indicating their thixotropic nature. A strong tendency to pigment settling was observed for unmodified alkyd coatings but was not observed in the FPA modified alkyd coatings. The modified alkyd coatings showed skinning while the unmodified alkyd coatings did not skin. A 30% solids coating formulation of the FPA modified resin showed shorter surface dry time but longer hard dry time than the unmodified alkyd resin coating.     

Biodegradable Polymers from 5-Hydroxylevulinic Acid: 1. Synthesis and Characterization of Poly(5-hydroxylevulinic acid)

As an attempt to synthesize new biodegradable polymers from renewable cellulose resources, melt polycondensation of 5-hydroxylevulinic acid (5-HLA) was reported for the first time. The resulting product, poly(5-hydroxylevulinic acid) (PHLA), was synthesized and characterized with GPC, FTIR, ¹H NMR and DSC. The in vitro degradation behaviors in phosphate-buffered saline (PBS) and in deionized water (DW) were also examined. The molecular weight of PHLA is not high (several 1,000s), but it possesses unordinary high glass transition temperature (as high as 120 °C). This is very different from existing aliphatic polyesters that usually have T _gs lower than 60 °C. The high T _g is attributed to the formation of inter- and/or intramolecular hydrogen bonds due to a characteristic keto–enol tautomerism equilibrium in the polymer structure. PHLA readily degraded hydrolytically in aqueous media.     

Preparation of Alginic Acid and Metal Alginate from Algae and their Comparative Study

Alginic acid and metal alginates are prepared from fresh algae using extraction method. A FTIR spectrum indicates that alginic acid is converted into the metal alginate. Comparing calcium and cobalt alginates, asymmetric stretching of free carboxyl group of calcium alginate at 1630 cm⁻¹ is shifted to 1585 cm⁻¹ in cobalt alginate, due to the change of charge density, radius and atomic weight of the cation, creating a new environment around the carbonyl group. The strong exothermic peak of alginic acid in DSC thermogram indicates the decomposition of biopolymer, whereas strong exothermic peak of metal alginate in DSC thermogram attributed to the decomposition of biopolymer and formation of respective carbonate. Based on DSC study, the decomposition of cobalt alginate occurs at higher temperature comparing to those of sodium and calcium alginate, which may conclude into the higher stability of cobalt alginate. TGA results reveal that, cobalt alginate is more stable than calcium and sodium alginate at 300 °C temperature. Surface morphology (at same magnification), as well as porosity (%) and pore size distribution results change with metals present in different metal alginates.     

Improved quartz furnace method for chlorine and sulfur determination in municipal solid waste

 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO _x , whereas plastics contained 1.1 mg S/g with 55.1% SO _x formation. Received: March 20, 2002 / Accepted: October 13, 2002     

Isolation and Characterization of Nanocrystalline Cellulose from Totally Chlorine Free Oil Palm Empty Fruit Bunch Pulp

Nanocrystalline cellulose (NCC) was isolated from a totally chlorine free (TCF) bleached oil palm empty fruit bunch (OPEFB) pulp via acid hydrolysis using a 58 % sulfuric acid concentration and ultrasonic treatment. The effects of acid concentration and hydrolysis time were investigated. Characterization of OPEFB–NCC was carried out using TEM, FTIR, ¹³C-NMR, XRD, zeta potential and TGA. The optimal hydrolysis time was 80 min as indicated by the leveling off of the OPEFB–NCC dimensions (length 150 nm and diameter 6.5 nm) with no significant loss of crystallinity at this point. The presence of a shoulder peak at 1231 cm^?1 (assigned to a sulfate group) in the FTIR spectrum of NCC is indicative of a successful esterification. This is further corroborated by the ¹³C-NMR analysis whereby the distinct C4 amorphous and crystalline peaks present in OPEFB–TCF pulp had almost disappeared and the cluster of signals for C2, C3, C5, and a well separated signal of C6 had merged into one single peak in the OPEFB–NCC sample. These observations allude to most of the amorphous region having been removed and to the strong possibility of sulfonation having not only occurred on the C6, but also on C2 and C3. OPEFB–NCC isolated over shorter hydrolysis time was more thermally stable; however, the char fraction decreases with hydrolysis time despite having a higher zeta potential. The results of this investigation demonstrate that NCC can be produced from pulp made by chlorine free environmentally benign processes with ensuing savings in energy and chemicals.     

Finished leather waste chromium acid extraction and anaerobic biodegradation of the products

Due to the amounts of chromium in the leachate resulting from leather leaching tests, chromium sulfate tanned leather wastes are very often considered hazardous wastes. To overcome this problem, one option could be recovering the chromium and, consequently, lowering its content in the leather scrap. With this objective, chromium leather scrap was leached with sulfuric acid solutions at low temperature also aiming at maximizing chromium removal with minimum attack of the leather matrix. The effects of leather scrap dimension, sulfuric acid and sodium sulfate concentration in the solutions, as well as extraction time and temperature on chromium recovery were studied, and, additionally, organic matrix degradation was evaluated. The best conditions found for chromium recovery were leather scrap conditioning using 25 mL of concentrated H₂SO₄/L solution at 293 or 313 K during 3 or 6 days. Under such conditions, 30–60 ± 5% of chromium was recovered and as low as 3–6 ± 1% of the leather total organic carbon (TOC) was dissolved. Using such treatment, the leather scrap area and volume are reduced and the residue is a more brittle material showing enhanced anaerobic biodegradability. Although good recovery results were achieved, due to the fact that the amount of chromium in eluate exceeded the threshold value this waste was still hazardous. Thus, it needs to be methodically washed in order to remove all the chromium de-linked from collagen.