Search

The heterogeneous structure of lignocellulosic biomass makes it difficult to dissolve its main components (cellulose, hemicelluloses, and lignin) by solvent action with the aim of further applying the mixture of the biological macromolecules generated in the solvent medium. In the present study, the dissolution efficiency (DE) of lignocellulosic sisal fibers in the lithium chloride/dimethylacetamide solvent system (LiCl/DMAc) was evaluated for further application in the formation of hydrogels. Catalytic amounts of trifluoroacetic acid (TFA) were used in some experiments, which increased the DE from 40% to 90%. The regeneration of the solutions, either previously filtered or not, led to hydrogels based on sisal lignocellulosic biomass. In brief, the properties of the hydrogels were influenced by the content of the lignocellulosic components in the hydrogels, present both in the dissolved fraction and in the incorporated undissolved fraction (when nonfiltered solutions were used). Hydrogels presented water absorption up to 7479% and resorption content in the lyophilized hydrogel up to 2133%. Extracts obtained from preselected hydrogels exhibited cell viability up to 127% compared to the control group when in contact with fibroblast cultures, exhibiting their noncytotoxic properties. This attribute increased the range of possible applications of these hydrogels, ranging from agriculture to biocompatible materials.

Cellulose nanocrystals (CNCs), castor oil (CO), and recycled poly(ethylene terephthalate) (rPET), were used to add value to renewable raw materials and to a recycled polymer produced worldwide, producing mats composed of fibers on the nano- and submicrometric (ultrathin) scales through a sustainable process. Bio-based electrospun mats composed of aligned (rotary collector) and nonaligned (static collector) nanofibers/ultrathin fibers were produced from the electrospinning of solutions prepared from rPET (mixed with CO, CNCs, or CNCs/CO). The contact angle results showed that the CNC mat surfaces composed of nonaligned fibers were hydrophilic, and in contrast, these surfaces were hydrophobic when composed of aligned fibers. Among the mats composed of nonaligned fibers, PET/CO/CNC exhibited storage and Young's moduli approximately eleven and ten times, respectively, better than those of neat rPET. The PET/CO/CNC mat showed both modulus and tensile strength values higher than those of PET/CNC, when characterized in the preferential direction of fiber alignment. Electrospun mats were obtained from environmentally sound raw materials with diversified properties, which were modulated by the type of collector used, as well as whether CO and CNC were mixed with rPET, and have the potential for use in applications such as membrane separation processes and biomedical applications.

Palm oil production generates oil palm mesocarp fiber (OPMF) as the main lignocellulosic waste from the oil/fruit separation process. The plentiful OPMF can be used for diverse applications, such as reinforcement in polymeric matrix composites or to produce glucose for second-generation ethanol. In both applications, surface properties are essential, and the presence of silica bodies is usually harmful. In the present study, three treatments to remove silica bodies were evaluated as follows: hydrothermal (HT), alkali (AT), and sodium citrate solution (ST). Morphological and structural characteristics of untreated and treated fibers were determined using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Many silica bodies attached to the untreated OPMF surface were observed. The treatments partially removed the silica bodies from the surface. AT was superior, with a removal rate of approximately 91% as quantified by microwave-induced plasma optical emission spectrometry. The crystallinity index increased from 27% in the raw fiber to 40% after all treatments because of the removal of non-crystalline regions of cellulose and extracted material. Thermogravimetric analysis revealed no significant differences in the thermal stability of untreated and treated fibers. Elongation at break was the lowest for AT and HT, and the highest for ST. Removing silica bodies from the OPMF surface can benefit applications where surface properties are critical, adding value to the waste. As far as it is known, the approach used in this study is unprecedented.

In this study, sisal cellulose/magnetite-nanoparticle (Fe3O4 NPs; 0.5, 1.4, and 3.0 g L−1) hybrid films (denoted as FCFe0.5, FCFe1.4, and FCFe3.0, respectively) were prepared by casting, using the solvent system LiCl/DMAc. Sisal was chosen as a cellulose source because it is a fast-growing plant, in contrast to the long cycle of woody trees, and Brazil accounts for most of the sisal produced in the world. Fe3O4 NPs were chosen owing to their excellent properties (superparamagnetic behavior at room temperature, high chemical stability, and low toxicity). The synthesized magnetite NPs (coated with oleic acid and oleylamine to prevent agglomeration during synthesis) were spherical with an average diameter of 5.1 ± 0.5 nm (transmission electron microscopy analysis; TEM). X-ray diffraction analysis showed that the NPs were satisfactorily incorporated into the cellulose films (as confirmed by TEM) and that their presence favored the formation of cellulose crystalline domains. FCFe1.4 and FCFe3.0 exhibited higher tensile strengths (14.3 MPa and 12.1 MPa, respectively) than the neat cellulose film (9.9 MPa). The moduli of elasticity of FCFe0.5, FCFe1.4, and FCFe3.0 were 1650, 1500 MPa, and 780 MPa, respectively, lower than that of the cellulose film (1860 MPa), indicating that the incorporation of NPs in the cellulosic matrix decreased the films’ stiffness. Hybrid films exhibited high magnetizations at 300 K, i.e., 23.0 emu g−1 (FCFe0.5), 31.0 emu g−1 (FCFe1.4), and 37.0 emu g−1 (FCFe3.0), as well as no magnetic hysteresis and remanent magnetization (Mr) null, namely, a superparamagnetic behavior at room temperature. The results obtained suggest several applications of hybrid films based on cellulose and magnetite, such as biomedical applications, miniaturized electronic devices, and advanced catalysis. Keywords: Sisal cellulose, Magnetite nanoparticles, Magnetic hybrid films

Cellulose, combined with lignin in some instances, was used to prepare mats made of fibers preferentially oriented in one direction. The aim of this study was evaluating the influence of this polysaccharide on the end properties of the mats when a thermoplastic polymer (in this case recycled polyethylene terephthalate; PET) is used as the primary component of solutions subjected to electrospinning. All of the prepared mats were composed mostly of ultrathin fibers. The mechanical properties were evaluated in the preferred and perpendicular directions of the alignment of the fibers. The storage and elastic moduli, as well as the tensile strength, were higher in the preferred direction. Cellulose led to mats with higher Tg PET values, indicating interactions at the molecular level between the chain segments of both polymers. One of the cellulose mats, (PETC-2), showed a superior alignment index (AI = 0.72 ± 0.03) and a higher average preferred orientation (APO = 88 ± 1°), which, in turn, led to higher mechanical properties, storage modulus, tensile strength, and elastic modulus when evaluated in the preferred direction of fiber alignment (PETC-2 dir), compared to the others. The results reveal that cellulose can be used to tune various properties of mats based on thermoplastics, thereby significantly increasing the range of applications of these materials.

Cellulose nanocrystals (CNC) exhibit remarkable properties such as being lightweight, renewability, nanoscale dimension, raw material availability, and a unique morphology. They have been widely used in film-forming composites, but the literature is scarce concerning bulky-composites (i.e., non-filmogenic). Microcrystalline cellulose (MCC) is widely available and has emerged as an important material for the reinforcement of composites. This investigation focuses on the preparation of non-filmogenic composites prepared from a polyurethane-type matrix, based on modified lignosulfonate and castor oil, reinforced with CNC or MCC, aiming to compare their reinforcing capacity. CNC was obtained through the acid hydrolysis of MCC. Sodium lignosulfonate was chemically modified using glutaraldehyde to increase its reactivity towards isocyanate groups in the synthesis of lignopolyurethane. The results show that adding CNC or MCC led to materials with improved impact strength, flexural properties, and storage modulus compared to pristine lignopolyurethane. With the exception of the flexural modulus, which was higher for the CNC-reinforced composite compared to the MCC-reinforced composite, all other properties were similar. The set of results indicates that CNC and MCC are promising for the reinforcement of polyurethane-type matrices. Bulky materials with good properties and prepared from high renewable raw material contents were obtained, meeting current expectations concerning sustainable development.

Properties of cellulosic materials, such as average molar mass (MMvis), crystallinity index and hemicelluloses content may influence the efficiency of the enzymatic conversion of cellulose to glucose. Studies on the simultaneous influence of these parameters have been scarcely found in the literature. In the present study, the conversion of cellulose to glucose was investigated using cellulosic materials with different MMvis, crystallinity, and hemicelluloses content: microcrystalline cellulose (MCC, MMvis = 22104 g mol−1, CI = 79%, no hemicelluloses detected), sisal pulp (SP, MMvis = 94618 g mol−1, CI = 66%, hemicelluloses content = 2.6%) and filter paper (FP, MMvis = 98530 g mol−1, CI = 63%, hemicelluloses content = 19.2%). During the reactions, aliquots were withdrawn and, in addition to the liquors, the unreacted cellulosic materials were evaluated by MMvis, CI, SEM, length and thickness, which can help further understand the reaction as a whole. The liquors were characterized by high-performance liquid chromatography (HPLC) and Miller's method (or DNS). The highest yield for the conversion of cellulose to glucose was observed for SP (88%), followed by MCC (64%) and FP (52%). The results indicated that the presence of high hemicelluloses content (FP) had a more significant interference effect than high crystallinity (MCC).

Blend solutions of poly(e-caprolactone) (PCL) and N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (QCh) were successfully electrospun. The weight ratio PCL/QCh ranged in the interval 95/5–70/30 while two QCh samples were used, namely QCh1 ( D Q ¯ = 47.3%; D P v ¯ = 2218) and QCh2 ( D Q ¯ = 71.1%; D P v ¯ = 1427). According to the characteristics of QCh derivative and to the QCh content on the resulting PCL/QCh nonwoven, the nanofibers displayed different average diameter (175 nm–415 nm), and the nonwovens exhibited variable porosity (57.0%–81.6%), swelling capacity (175%–425%) and water vapor transmission rate (1600 g m−2 24 h–2500 g m−2 24 h). The surface hydrophilicity of nonwovens increases with increasing QCh content, favoring fibroblast (HDFn) adhesion and spreading. Tensile tests revealed that the nonwovens present a good balance between elasticity and strength under both dry and hydrated state. Results indicate that the PCL/QCh electrospun nonwovens are new nanofibers-based biomaterials potentially useful as wound dressings.

Chemical modification of fiber surfaces can increase wettability of composites reinforced by vegetal fibers and, consequently, the dispersion of the fiber in the matrix and mechanical properties can be improved. Although there are some studies about agents for chemical modifications of vegetal fiber surfaces, there are few data and discussion about the usage of lignin. In the present work, chemical modifications of sugarcane bagasse and sisal fibers using lignin (previously hydroxymethylated) were carried out under different reaction times (15, 30, and 60 min). The composition (holocellulose, hemicelluloses, cellulose, and lignin contents) of the treated and untreated fibers was evaluated. Phenolic composites were prepared using unmodified and modified fibers via compression molding process under temperature. Izod impact, water absorption tests, and scanning electron microscopy were performed to evaluate composite properties. The resin and lignin were characterized by size exclusion chromatography. Results showed that there was a tendency of reducing water absorption for composites prepared from modified fibers. Impact strengths of composites reinforced with sugarcane bagasse with modified fibers were similar to the ones with unmodified fibers (around 20 J/m). However, impact strengths for composites reinforced with modified sisal fibers (around 104 J/m for 15 min of reaction time) were higher than the ones with unmodified fibers (around 95 J/m). Therefore, the usage of lignin as a modifier agent of vegetal fiber surfaces to increase fiber–matrix adhesion for phenolic composites is a strategic alternative for improving products through simple, eco-friendly, and low-cost procedures.

The increased awareness about environmental issues has resulted in developing novel materials and sustainable solutions to reduce the dependence on fossil-based products. Herein, cellulose from sisal was derivatized into carboxylic esters (acetate, Ac; butyrate, Bu; and hexanoate, Hx); the produced materials were “shaped” into mats composed of nano- and ultrathin fibers. Our objective was to assess the effects of cellulose ester degree of substitution (DS), low- and high DS, ca. 0.2 and 2.6; the length of the acyl group and the electrospinning flow rate, 45.5 and 65.5 μL/min on the morphology of the fibrous material obtained therefrom. Cellulose was converted into its carboxylic esters under homogeneous conditions using LiCl/N,N-dimethylacetamide solvent, and acid anhydrides as acylating agents. The obtained cellulose- acetate, Cel-Ac, butyrate, Cel-Bu, and hexanoate, Cel-Hx were dissolved in trifluoracetic acid. The solutions of esters were subjected to electrospinning, under positive voltage of 25 kV, and needle-collector distance of 4 cm. Scanning Electron Microscopy of the electrospun mats showed the formation of ultrathin- (100 nm > diameter

The present investigation addressed the use of treated and untreated sisal fibers (3 cm, 30 wt%, randomly distributed) as a reinforcement in bio-based composites. Sodium lignosulfonate (NaLS) was used to physically treat the sisal fibers and also as a macromonomer to prepare phenolic-type thermosets, namely, the matrices (LCs). The introduction of NaLS moieties on the surface of the fibers and in the chemical structure of the matrix aimed to increase the affinity of the fiber-matrix interface in addition to increasing the bio-sourced character of the final material. Sisal fibers were treated (and subsequently characterized) with aqueous 5 wt% NaLS solutions via heating (70 °C/1 h, SFT1), ultrasound irradiation (1 and 2 h, SFT2 and SFT3, respectively), and room temperature treatment at 24 h followed by ultrasound (1 h, SFT4). Briefly, considering only some properties of the composites, the following results can be highlighted: all the phenolic composites (PC, control samples) exhibited impact and flexural strengths considerably greater than the unreinforced phenolic thermoset (PT). The phenolic composite reinforced with untreated sisal fiber (PC-UF) and PC-SFT4 exhibited an impact strength of approximately 435 Jm −1 , and the others, PC-SFT1 and PC-SFT2, had a tendency to have a greater impact strength, with the exception of PC-SFT3 when compared with PC-UF. Based on the results exhibited by the PC-treated fibers, only LC-SFT1 and LC-SFT2 were prepared among the LC-treated fibers besides LC-UF. The set of PCs exhibited a lower impact strength than their LC composite counterparts. For example, the impact strength of LC-UF was approximately 1000 Jm −1 (compared to approximately 435 Jm −1 for PC-UF). This is a very good result for a thermoset matrix reinforced with natural fibers and clearly shows that the fiber-matrix interaction at the interface was favored when the thermoset was prepared from NaLS, and then, the load received during the impact was more efficiently transferred to the sisal fibers. SEM images showed good adhesion at the fiber-matrix interface of LC-treated fibers due to the similarity of the chemical structure of the matrix and treated sisal fiber. Concerning the assessment of the thermal conductivity (at 10, 25 and 50 °C), only the thermosets (phenolic, PT, lignosulfonate-based, and LT), the composites reinforced with untreated fibers (PC-UF and LC-UF), and PC-SFT2 (due to its high impact strength) were evaluated. The results showed no significant variation in the thermal conductivity as a function of temperature. There was no significant variation in the thermal conductivity of both thermosets (the thermal conductivity of PT and LT at 25 °C, for instance, were 0.30 and 0.28 Wm −1 K −1 , respectively) to their respective composites (at 25 °C, the thermal conductivity was 0.40 and 0.36 Wm −1 K − 1 for PC–UF and PC–SFT2, respectively, and 0.24 Wm −1 K −1 for LC–UF). A tendency towards lower conductivities (at 10, 25 and 50 °C) was observed for LC-UF when compared with PC-UF. Overall, these results meet the current expectations concerning the production of materials prepared from a high percentage of raw materials from renewable sources with good properties.

This study aimed to evaluate the production of cellulases from Aspergillus sp. CBMAI 1198, through solid-state fermentation, and their actions on different cellulosic materials (microcrystalline cellulose, sisal pulp, and filter paper). The influence of pH, temperature, and composition of substrates (sisal pulp and wheat straw), on the filter paper activity (FPase) of the cellulases produced from these substrates, was investigated using a complete central factorial composite design. Low temperature (32 °C), sisal pulp content (25%), and pH (5.0) led to the production of enzymes with higher activity (0.244 UmL−1). The results on the reducing sugars produced by the enzymatic hydrolysis of microcrystalline cellulose, sisal pulp, and filter paper showed that the cellulosic material with a higher content of hemicelluloses and lower crystallinity (filter paper) exhibited the better result (8.04 μmol mL−1). Non-hydrolyzed microcrystalline cellulose, sisal pulp, and filter paper were withdrawn from the medium during the reaction, and changes in their physicochemical properties were monitored assessing changes in molar mass, crystallinity index, surface morphology (scanning electron microscopy), and fiber lengths and thicknesses (MorFi technique). This approach on the properties of non-hydrolyzed fibers differentiates this study from those found in the literature. The results showed that cellulases were successfully produced from Aspergillus sp. and, despite the low yield, these enzymes hydrolyzed cellulosic materials with different properties. The approach of the present study, as well as the set of results obtained, added novelty to the respective area, and are important for the deepening of the investigations.

Brazil has played a leading role in the global cultivation of sugarcane, used in the production of sugar and ethanol, which results in sugarcane bagasse as agrowaste. This agroresidue generates electricity and second-generation ethanol, but the colossal amount available allows for alternative applications. Currently, mechanized harvesting/unburn predominates over manual harvesting/burn. The present study was conducted in this scenario and investigated the use of fibers from unburned sugarcane bagasse (SBU) in bio-based composites. Phenolic thermoset was chosen as a matrix due to its excellent properties. The mechanization/unburn method allows the use of variable length fibers (this study: 1/3/5 cm, 30 wt%). SBU was characterized in detail, highlighting the characterization via inverse gas chromatography (IGC, which provides information regarding the polarity of the groups present on the surface of the fibers). Briefly, the composition of SBU shows no significant differences compared to burnt bagasse (SBB), and IGC showed that SBU has more polar groups on the surface than SBB, which favors intermolecular interactions and then adhesion with the phenolic matrix. Composites reinforced with 3- and 5-cm fibers presented a storage modulus higher than that of the unreinforced thermoset, and the impact strength of all composites was higher than that of the thermoset (up to 45%). This set of results points to applications such as rigid packaging, non-structural parts of buildings and automotive vehicles, which increases the applications of the investigated agrowaste within the circular bioeconomy.

Kraft lignin (KL) and castor oil (CO) were used as polyols in the synthesis of bio-based polyurethanes (PUs) in the absence of both solvents and catalysts at room temperature with simultaneous film formation. KL was purified (PKL), and both KL and PKL were fully characterized. CO was mixed with different percentages of PKL (0%, 10%, 30%, and 50%), as well as with polymeric methyl phenyl diisocyanate. After degassing, the reaction mixture was stirred; when the medium viscosity was suitable for spreading, it was poured onto a glass plate, and the thickness was adjusted using an extender. The storage modulus (E′, 25 °C) and tensile strength of the lignopolyurethane films (LignoPUCOPKL) were higher than those of the control film (PUCO). LignoPUCOPKL30 and LignoPUCOPKL50 did not break under the conditions that the other films broke under. It was noted phase segregation (rigid and flexible domains) for LignoPUCOPKL30 and LignoPUCOPKL50, and the glass transition temperature (Tg) of the flexible domains (96.2 °C and 52.3 °C, respectively) was higher than that of PUCO (8.4 °C). The formed films were also characterized by scanning electron microscopy, thermogravimetric analysis, X-ray diffraction, contact angles, and swelling tests. To our knowledge, the approach of this study is unprecedented.

Polyurethanes are synthesized from polyols, which can be fossil- or plant-sourced. The goal of this study was to investigate how the use of plant-sourced polyols, i.e., the ricinoleic acid triglyceride (the main component of castor oil, CO) and lignosulfonate, impacts the properties of the materials, as well as of their composites reinforced with sisal fibers. To reach this objective, the properties of polyurethanes from plant-sourced polyols were compared with those of their counterparts synthesized using fossil-sourced diethylene glycol (DEG) and polyethylene glycol (PEG). As far as is known, this approach is unheard-of. Polyurethanes and lignopolyurethanes (neat PUs and LigPUs) were synthesized under temperature and compression molding from CO, DEG, and PEG (PUs), and in LigPUs, 30 % of the polyols were replaced by lignosulfonate. Under the same conditions, composites were formed simultaneously with the syntheses after adding sisal fibers (30 % by weight, 3 cm in length) to the reagents. A notable characteristic is the impact strength of the neat PU and PU sisal composites in which PEG (approximately 750 Jm−1and 850 Jm−1, respectively) and CO (unfractured and approximately 850 Jm−1, respectively) were used. Flexural tests showed that the use of CO as a polyol in the synthesis of the neat PUs and LigPUs and composites imparted elastomeric characteristics to the materials. Similar properties were noted when PEG was used as a polyol, except when it was used together with lignosulfonate in the sisal reinforced composite. A high content of renewable raw material was used in the LigPU sisal fiber composites, meeting expectations regarding the sustainability of the processes, as well as the potential to contribute to the development of the bioeconomy. The materials were prepared using renewable reagents largely available, with no solvent or catalyst use, through a simple process, and no byproducts generated. These features favor the scaling-up of the process. Also, the bio-based materials exhibited good and diverse properties, which qualify them for various applications in which polyurethanes obtained only from fossil-sourced raw materials are used.

Electrospun nanofibers obtained from cellulose acetate before (CA) and after (DCA) deacetylation were used as electrolyte membranes in dye-sensitized solar cells. As holders of the active components of the device and compared to the reference system, the CA and DCA membranes increased the average device efficiency by as much as 14%. The membranes enhanced the charge transfer at the counter electrode (assessed by the Ohmic and charge transfer resistance and corresponding Helmholtz capacitance). Simultaneously, the photoelectrode did not interfere with the performance as measured by the short-circuit current density, open circuit voltage, fill factor and conversion efficiency. Long-term stability tests (light soaking) showed that the CA- and DCA-based solar cells sustain operation for at least 500 h. For long term use and/or to serve as a scaffold for other purposes, DCA performs better than CA. The proposed active electrolyte membranes are expected to open the way toward rapid and continuous assembly of dye sensitize solar cells using cellulose esters. Graphical abstract: [Figure not available: see fulltext.].

The goal of this study was to investigate how the use of high concentration of cellulase may impact the properties of the substrate and the reaction medium during the enzymatic hydrolysis of the sisal pulp. Enzyme concentration of 0.9 mL g−1 was considered for hydrolysis of a sisal cellulosic substrate, and the results were compared with previous ones using 0.5 mL g−1 as cellulase concentration. Nonhydrolyzed pulps and the liquors were withdrawn from the reaction medium and characterized by scanning electron microscopy, crystallinity index, average molar mass, length/thickness, and high-performance liquid chromatography (HPLC). The results indicated that the enzyme/substrate ratio impacted crystallinity variations during the reaction and the induction period for exoglucanase action. The concentration of 0.9 mL g−1 led to a glucose yield (98%, an almost quantitative conversion) higher than 0.5 mL g−1 (89%). Aiming to gain information on the post-burst phase (after 15 h), 1 g of sisal pulp was added, and the results demonstrated that the enzymes remained active, which can counterbalance the higher cost due to the use of high enzymes concentrations. This study deepened the understanding of the enzymatic hydrolysis of sisal cellulosic pulp, and the findings may also benefit investigations on other pulps.

Interest in the use of renewable raw materials in the preparation of materials has been growing uninterruptedly in recent decades. The aim of this strategy is to offer alternatives to the use of fossil fuel-based raw materials and to meet the demand for materials that are less detrimental to the environment after disposal. In this context, several studies have been carried out on the use of lignocellulosic biomass and its main components (cellulose, hemicelluloses, and lignin) as raw materials for polymeric materials. Lignocellulosic fibers have a high content of cellulose, but there has been a notable lack of investigations on application of the electrospinning technique for solutions prepared from raw lignocellulosic biomass, even though the presence of cellulose favors the alignment of the fiber chains during electrospinning. In this investigation, ultrathin (submicrometric) and nanoscale aligned fibers were successfully prepared via electrospinning (room temperature) of solutions prepared with different contents of lignocellulosic sisal fibers combined with recycled poly(ethylene terephthalate) (PET) using trifluoroacetic acid (TFA) as solvent. The “macro” fibers were deconstructed by the action of TFA, resulting in solutions containing their constituents, i.e., cellulose, hemicelluloses, and lignin, in addition to PET. The “macro” sisal fibers were reconstructed at the nanometer and submicrometric scale from these solutions. The SEM micrographs of the mats containing the components of sisal showed distinct fiber networks, likely due to differences in the solubility of these components in TFA and in their dielectric constants. The mechanical properties of the mats (dynamic mechanical analysis, DMA, and tensile properties) were evaluated with the samples positioned both in the direction (dir) of and in opposition (op) to the alignment of the nano and ultrathin fibers, which can be considered a novelty in the analysis of this type of material. DMA showed superior values of storage modulus (E’ at 30 °C) for the mats characterized in the preferential direction of fiber alignment. For example, for mats obtained from solutions prepared from a 0.4 ratio of sisal fibers/PET, Sisal/PET0.40dir presented a high E’ value of 765 MPa compared to Sisal/PET0.40op that presented an E’ value of 88.4 MPa. The fiber alignment did not influence the Tg values (from tan δ peak) of electrospun mats with the same compositions, as they presented similar values for this property. The tensile properties of the electrospun mats were significantly impacted by the alignment of the fibers: e.g., Sisal/PET0.40dir presented a high tensile strength value of 15.72 MPa, and Sisal/PET0.40op presented a value of approximately 2.5 MPa. An opposite trend was observed regarding the values of elongation at break for these materials. Other properties of the mats are also discussed; such as the index of fiber alignment, average porosity, and surface contact angle. To our knowledge, this is the first time that the influence of fiber alignment on the properties of electrospun mats based on untreated lignocellulosic biomass combined with a recycled polymer, such as PET, has been evaluated. The mats obtained in this study have potential for diversified applications, such as reinforcement for polymeric matrices in nanocomposites, membranes for filtration, and support for enzymes, wherein the fiber alignment, together with other evaluated properties, can impact their effectiveness in these applications.

The rational valorization of lignin and its derivatives is a challenge in biorefinery because this biopolymer is one of the major source of aromatic moieties. Lignosulfonates are used to a lesser extent than lignin to prepare macromolecular materials. In the current study, sodium lignosulfonate (NaLS), which was either blended or not blended with OH-containing vegetable oil (i.e., castor oil (CO)), was reacted with diphenylmethane diisocyanate (MDI) to prepare polyurethane-type materials, such as lignopolyurethanes (i.e., CO/NaLS/MDI and NaLS/MDI, respectively). NaLS was oxypropylated (LS-Oxy) to increase its reactivity towards MDI. LS-Oxy was characterized and then used after being blended or not blended with CO to prepare lignopolyurethanes CO/LS-Oxy/MDI and LS-Oxy/MDI, respectively. These materials were characterized by infrared spectroscopy, thermogravimetry (TG), and dynamic mechanical thermoanalysis (DMA). The Tg values obtained from DMA (loss modulus peak) indicated that the lignopolyurethanes with an intermediate degree of cross-linking were obtained. In a final set of experiments and due to their potential application, the obtained lignopolyurethanes were reinforced with sisal fibers, and the impact strength, flexural properties and scanning electron microscopy (SEM) images of the materials were obtained. The results indicated that the presence of sisal fibers led to a significant improvement in the impact strength of the lignopolyurethanes, especially in those prepared from LS-Oxy [CO/LS-Oxy/MDI: approximately from 40 J m −1 (without sisal) to 370 J m −1 (with sisal); LS-Oxy/MDI: from 15 J m −1 (without sisal) to 459 J m −1 (with sisal)]. The flexural properties of CO/LS-Oxy/MDI (with or without sisal) corresponded to a less rigid material compared to the other material. The results indicated that the characteristics of the lignopolyurethanes could be tuned by oxypropylation of NaLS and/or blending with CO as well as by the addition of sisal fibers, which enables the production of materials with a wide range of properties.

Biocomposites based on a polymer with good biodegradability, poly(butylene succinate) (PBS), and reinforced with different lignocellulosic fibers (coconut, sugarcane bagasse, curaua, sisal) were prepared through the traditional thermo-pressed molding technique. The fibers were characterized in terms of chemical composition, thermal stability (TGA), cristallinity (XRD) and surface morphology (SEM). The polymer thermal properties were evaluated by TGA and DSC. The composite characteristics were investigated by mechanical tests (Izod impact strength, flexural resistance), thermal stability (TGA), water uptake and SEM micrographs of the fractured surfaces. The results showed that sisal and curaua fibers feature a huge potential as reinforcing agents of PBS due to their superior chemical compatibility with the aliphatic matrix as well as to their surface morphology. Both factors contributed to the formation of a strong interface capable to effectively transfer the load from the matrix to the fibers. Sisal/PBS and curaua/PBS composites also showed greater resistance against water absorption if compared to coconut/PBS and sugarcane bagasse/PBS composites. Novel biocomposites with good properties were produced from fibers and polymer that can obtained from renewable raw materials.

Cellulose nanocrystals (CNC) were prepared from curaua fibers via acid hydrolysis, and used as reinforcing phase for high-density biopolyethylene (HDBPE) or green polyethylene. Castor oil (CO), epoxidized soybean oil (ESO) and epoxidized linseed oil (ELO) were chosen as compatibilizers for this study. Nanocomposites reinforced with CNC (3, 6, and 9 wt %) were processed by extrusion, using CO (3, 6, and 9 wt %) to evaluate its action as CNC dispersing agent in the HDBPE matrix. From the results obtained for these films, the CNC and oil contents were set at 3 wt%. In addition to CO, ELO, and ESO were also used, and besides processing by extrusion, extrusion/hot-pressing process was also considered, in order to compare the two processing techniques. The nanocomposites were characterized by microscopic, thermal, mechanical, and rheological analyses. The presence of oil leads to less opaque films and improved dispersion. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1010–1019

Enzymatic saccharification of sisal cellulosic pulp has been investigated. Brazil leads global production of lignocellulosic sisal fiber, which has high cellulose content, an important property for producing glucose via saccharification. Hence, sisal pulp can be a good alternative for use in biorefineries. Prior to enzymatic hydrolysis, the starting pulp [85 ± 2% α-cellulose, 15 ± 2% hemicelluloses, 1.2 ± 2% insoluble lignin, viscometric average molar mass (MMvis) 19,357 ± 590 g mol−1, crystallinity index (CI) 74%] was pretreated with alkaline aqueous solution (mercerization, 20 g of pulp L−1, 20% NaOH, 50 °C). The changes in the properties of the cellulosic pulp during this pretreatment were analyzed [α-cellulose content, MMvis, CI, pulp fiber dimensions, and scanning electron microscopy (SEM)]. The unmercerized and mercerized (97.4 ± 2% α-cellulose, 2.6 ± 2% hemicelluloses, 0.3 ± 0.1% insoluble lignin, MMvis 94,618 ± 300 g mol−1, CI 68%) pulps were subjected to enzymatic hydrolysis (48 h, commercial cellulase enzymes, 0.5 mL g−1 pulp); during the reactions, aliquots consisting of unreacted pulp and liquor were withdrawn from the medium at certain times and characterized (unreacted pulp: MMvis, CI, fiber dimensions, SEM; liquor: high-performance liquid chromatography). The changes in pulp properties observed during mercerization facilitated access of enzymes to cellulose chains, and the yield of the hydrolysis reaction increased from 50.2 (unmercerized pulp) to 89.0% (mercerized pulp). These initial results for enzymatic hydrolysis of sisal pulp indicate that it represents a good alternative biomass for bioethanol production.

Bio-based films were prepared from LiCl/DMAc solutions containing sisal cellulose esters (acetates, butyrates and hexanoates) with different degrees of substitution (DS 0.7–1.8) and solutions prepared with the cellulose esters and 20 wt% sisal cellulose. A novel approach for characterizing the surface morphology utilized field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and contact angle analysis. XPS and ToF-SIMS were a powerful combination while investigating both the ester group distribution on the surface and effects of cellulose content on the film. The surface coverage by ester aliphatic chains was estimated using XPS measurements. Fibrous structures were observed in the FE-SEM images of the cellulose and bio-based films, most likely because the sisal cellulose chains aggregated during dissolution in LiCl/DMAc. Therefore, the cellulose aggregates remained after the formation of the films and removal of the solvent. The XPS results indicated that the cellulose loading on the longer chain cellulose esters films (DS 1.8) increased the surface coverage by ester aliphatic chains (8.2 % for butyrate and 45 % for hexanoate). However, for the shortest ester chains, the surface coverage decreased (acetate, 42 %). The ToF-SIMS analyses of cellulose acetate and cellulose hexanoate films (DS 1.8) revealed that the cellulose ester groups were evenly distributed across the surface of the films.

High-density biopolyethylene (HDBPE) used as a matrix in composites reinforced by curaua fibers (5, 10, 15 and 20 wt%, 1 cm) was obtained on an industrial scale by polymerization of ethylene derived from sugarcane ethanol. Castor (CO) and canola (CA) oils were used in the preparation of composites (5, 10, 15, and 20 wt%) as a potential compatibilizer of the polar fibers and nonpolar matrix to facilitate the respective processing and to intensify polymer and reinforcement material interface interactions. The composites were characterized by SEM, DSC, TGA, DMA, and flexural and impact strength measurements. The results indicated that the incorporation of oils in various compositions, particularly CO, generally led to improved properties compared to the HDBPE/fiber composite material, indicating the potential of the oil as a compatibilizer at the fiber/matrix interface.

The aim of this study was to evaluate the influence of cellulose and/or lignin on the properties of mats prepared from dissolution (for 48 h or 72 h, solvent: trifluoroacetic acid) of recycled poly (ethylene terephthalate) (PET). Briefly, the presence of cellulose led to a tendency of higher average fiber diameter and average pore area as well as lower average porosity compared to the neat mat (PETref, 242 ± 59 nm, 9.6 ± 1.1 104 nm2 and 19.0 ± 1.1%, respectively). The Tg values for electrospun PET combined with cellulose and/or lignin were higher than that of PETref (92.5 ± 0.1 °C), and the tensile strength increased with the cellulose and/or lignin loading. In addition, the presence of lignin (72 h of dissolution) led to a mat with an elongation at break of 149 ± 9% compared to 14 ± 2% for PETref. The results indicated that the properties of mats based on PET can be tuned by adding cellulose and/or lignin to solutions posteriorly electrospun as well as by varying the dissolution time.

Low average molar mass cellulose has been submitted to carboxymethylation reactions to yield carboxymethylcellulose (CMC) materials with different degrees of substitution (DS) that have been investigated as alternative renewable stabilizing agents for aqueous alumina suspensions to usual synthetic polyelectrolyte additives. The CMC materials were characterized by infrared, X-ray diffraction and 1H nuclear magnetic resonance (NMR) spectroscopies, as well as by size exclusion chromatography (SEC), thermogravimetry (TG) and differential scanning calorimetry (DSC). All CMC materials reported (DS of 0.7, 1.3 and 1.8 as estimated by 1H NMR) proved to be good additives to stabilize aqueous alumina suspensions with high solid concentrations (60%, w/w). Addition of low amounts of CMC (from 0.10% to 0.20%, w/w) produced suspensions with small and uniformly distributed particle sizes, thereby yielding colloids with lower viscosity, negative zeta potential values and longer sedimentation times. The present work demonstrates the viability of substituting synthetic fossil-based polyelectrolytes in traditional industrial activities with renewable cellulosic biomass-based ones.

The use of products and byproducts from the agro-industry and forest biorefinery is essential for the development of value-added and low environmental-impact materials. In this study, polyurethanes were prepared using sodium lignosulfonate (NaLS) and castor oil (CO) as reagents and were used to prepare composites reinforced with lignocellulosic fibers, namely, curaua and coir fibers (30 wt %, 3 cm length, and randomly oriented). The SEM images of fractured surfaces of the composites revealed excellent adhesion at the fiber/matrix interface of both coir and curaua composites, which probably resulted from the favorable interactions between polar groups, as well as amid low polarity domains that are present in both the matrix and the reinforcements. The composites exhibited different impact/flexural and strength/flexural moduli (NaLS/CO/Curaua = 465 Jm−1/44 MPa/2 GPa; NaLS/CO/Coir = 180 Jm−1/25 MPa/1 GPa). The higher tensile strength/aspect ratio of the curaua fibers (485 MPa/259) compared with that of the coir fibers (120 MPa/130) most likely contributes to the enhanced performance of its composite. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Neste trabalho, foram utilizadas fibras de curauá como reforço de matriz termoplástica de biopolietileno de alta densidade. O polietileno foi obtido por polimerização de eteno, gerado do etanol de cana de açúcar. Este polímero é também chamado de biopolietileno (BPEAD), por ser preparado a partir de material oriundo de fonte natural. Desta forma, pretendeu-se contribuir para desenvolver materiais que, dentre outras propriedades, causem menor emissão de CO2 para a atmosfera na sua produção, utilização e substituição, comparativamente a outros materiais. Adicionalmente, polibutadieno líquido hidroxilado (PBHL) foi acrescentado à formulação do compósito, visando a um aumento na resistência à propagação da trinca durante impacto. Os compósitos e as fibras foram caracterizados por várias técnicas, tais como microscopia eletrônica de varredura (MEV), Calorimetria Exploratória Diferencial (DSC), Termogravimetria (TG), além da caracterização dos compósitos quanto à Análise Térmica Dinâmico-Mecânica (DMTA), propriedades mecânicas (impacto e flexão) e absorção de água. A presença das fibras de curauá diminuiu algumas propriedades do BPEAD, como resistência ao impacto. A análise de DMTA mostrou que as fibras geram material mais rígido. Pode-se considerar que a introdução de PBHL na formulação do material foi eficiente, levando a uma resistência ao impacto do compósito BPEAD/PBHL/Fibra maior do que a do compósito BPEAD/Fibra.In this work, curaua fibers were used in the reinforcement of a high-density (HDPE) thermoplastic matrix. The polyethylene used was obtained by polymerization of ethene produced from sugarcane ethanol. This polymer, also called high-density biopolyethylene (HDBPE), was prepared from a natural source material. The aim was to contribute to developing materials which could lead to smaller release of CO2 into the atmosphere in comparison to other materials. Additionally, liquid hydroxylatedpolybutadiene (LHPB) was added to the composite formulation, aiming at improving resistance to crack spreading during impact. The fibers and their composites were characterized by several techniques, such as scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetry (TG). The composites were also characterized by dynamic mechanical thermal analysis (DMTA), mechanical properties (flexural and impact strength), and water absorption. The presence of curaua fibers reduced some of the properties of HDBPE, such as flexural and impact strength. DMTA indicated a more rigid material with the fibers incorporated. The addition of LHPB to the formulation was efficient, leading to greater impact strength for the HDBPE/LHPB/Fiber composite, as compared to the HDBPE/Fiber composite.

Composites of high-density biopolyethylene (HDBPE) obtained from ethylene derived from sugarcane ethanol and curaua fibers were formed by first mixing in an internal mixer followed by thermopressing. Additionally, hydroxyl-terminated polybutadiene (LHPB), which is usually used as an impact modifier, was mainly used in this study as a compatibilizer agent. The fibers, HDBPE and LHPB were also compounded using an inter-meshing twin-screw extruder and, subsequently, injection molded. The presence of the curaua fibers enhanced some of the properties of the HDBPE, such as its flexural strength and storage modulus. SEM images showed that the addition of LHPB improved the adhesion of the fiber/matrix at the interface, which increased the impact strength of the composite. The higher shear experienced during processing probably led to a more homogeneous distribution of fibers, making the composite that was prepared through extruder/injection molding more resistant to impact than the composite processed by the internal mixer/thermopressing.

A tannin–phenolic resin (40 wt% of tannin, characterized by 1 H nuclear magnetic resonance (NMR) and 13 C NMR, Fourier transform infrared, thermogravimetry, differential scanning calorimetry) was used to prepare composites reinforced with sisal fibers (30–70 wt%). Inverse gas chromatography results showed that the sisal fibers and the tannin–phenolic thermoset have close values of the dispersive component and also have predominance of acid sites (acid character) at the surface, confirming the favoring of interaction between the sisal fibers and the tannin–phenolic matrix at the interface. The Izod impact strength increased up to 50 wt% of sisal fibers. This composite also showed high storage modulus, and the lower loss modulus, confirming its good fiber/matrix interface, also observed by SEM images. A composite with good properties was prepared from high content of raw material obtained from renewable sources (40 wt% of tannin substituted the phenol in the preparation of the matrix and 50 wt% of matrix was replaced by sisal fibers).

The present work is inserted into the broad context of the upgrading of lignocellulosic fibers. Sisal was chosen in the present study because more than 50% of the world’s sisal is cultivated in Brazil, it has a short life cycle and its fiber has a high cellulose content. Specifically, in the present study, the subject addressed was the hydrolysis of the sisal pulp, using sulfuric acid as the catalyst. To assess the influence of parameters such as the concentration of the sulfuric acid and the temperature during this process, the pulp was hydrolyzed with various concentrations of sulfuric acid (30–50%) at 70 °C and with 30% acid (v/v) at various temperatures (60–100 °C). During hydrolysis, aliquots were withdrawn from the reaction media, and the solid (non-hydrolyzed pulp) was separated from the liquid (liquor) by filtering each aliquot. The sugar composition of the liquor was analyzed by HPLC, and the non-hydrolyzed pulps were characterized by viscometry (average molar mass), and X-ray diffraction (crystallinity). The results support the following conclusions: acid hydrolysis using 30% H2SO4 at 100 °C can produce sisal microcrystalline cellulose and the conditions that led to the largest glucose yield and lowest decomposition rate were 50% H2SO4 at 70 °C. In summary, the study of sisal pulp hydrolysis using concentrated acid showed that certain conditions are suitable for high recovery of xylose and good yield of glucose. Moreover, the unreacted cellulose can be targeted for different applications in bio-based materials. A kinetic study based on the glucose yield was performed for all reaction conditions using the kinetic model proposed by Saeman. The results showed that the model adjusted to all 30–35% H2SO4 reactions but not to greater concentrations of sulfuric acid. The present study is part of an ongoing research program, and the results reported here will be used as a comparison against the results obtained when using treated sisal pulp as the starting material.

The effects of alkali treatment on the structural characteristics of cotton linters and sisal cellulose samples have been studied. Mercerization results in a decrease in the indices of crystallinity and the degrees of polymerization, and an increase in the α-cellulose contents of the samples. The relevance of the structural properties of cellulose to its dissolution is probed by studying the kinetics of cellulose decrystallization, prior to its solubilization in LiCl/N,N-dimethylacetamide (DMAc). Our data show that the decrystallization rate constants and activation parameters are only slightly dependent on the physico-chemical properties of the starting celluloses. This multi- step reaction is accompanied by a small enthalpy and large, negative, entropy of activation. These results are analyzed in terms of the interactions within the biopolymer chains during decrystallization, as well as those between the two ions of the electrolyte and both DMAc and cellulose.

Cellulose acetates with different degrees of substitution (DS, from 0.6 to 1.9) were prepared from previously mercerized linter cellulose, in a homogeneous medium, using N,N-dimethylacetamide/lithium chloride as a solvent system. The influence of different degrees of substitution on the properties of cellulose acetates was investigated using thermogravimetric analyses (TGA). Quantitative methods were applied to the thermogravimetric curves in order to determine the apparent activation energy (Ea) related to the thermal decomposition of untreated and mercerized celluloses and cellulose acetates. Ea values were calculated using Broido's method and considering dynamic conditions. Ea values of 158 and 187 kJ mol-1 were obtained for untreated and mercerized cellulose, respectively. A previous study showed that C6OH is the most reactive site for acetylation, probably due to the steric hindrance of C2 and C3. The C6OH takes part in the first step of cellulose decomposition, leading to the formation of levoglucosan and, when it is changed to C6OCOCH3, the results indicate that the mechanism of thermal decomposition changes to one with a lower Ea. A linear correlation between Ea and the DS of the acetates prepared in the present work was identified.Acetatos de celulose com graus de substituição, GS, variando entre 0,6 e 1,9, foram preparados previamente a partir de celulose de linter mercerizado, em meio homogêneo, usando N,N-dimetilacetamida/cloreto de lítio como sistema de solvente. A influência de diferentes graus de substituição nas propriedades dos acetatos de celulose foi investigada usando a análise termogravimétrica (TGA). Métodos quantitativos foram aplicados nas curvas termogravimétricas obtidas a fim de determinar a energia de ativação aparente (Ea) relacionado à decomposição térmica de celulose não-tratada e mercerizada e acetatos de celulose. Valores de Ea foram calculados usando o método de Broido e considerando condições dinâmicas. Valores de Ea de 158 e 187 kJ mol-1 foram obtidos para a celulose não-tratada e mercerizada, respectivamente. Em trabalho anterior verificou-se que o C6OH é o sítio mais reativo na acetilação, provavelmente devido ao impedimento estérico de C2 e C3. O C6OH participa da primeira etapa de decomposição da celulose, levando à formação de levoglucosana e, quando se tem a substituição para C6OCOCH3, o resultado indica que o mecanismo de decomposição térmica muda para um com Ea menor. Uma correlação linear entre Ea e o GS dos acetatos preparados no presente trabalho foi identificada.

Tannin–phenolic polymers prepared using tannin, a macromolecule obtained from natural sources, were used in the preparation of composites reinforced with coir fibers. The composites based on tannin–phenolic polymers (50% (w/w) of tannin as substitute of the phenol) were prepared using the coir fibers as reinforcement (30–70% (w/w), 3.0–6.0 cm, randomly distributed). The Izod impact strength of the composites showed an improvement in this property due to the incorporation of coir fibers in the tannin–phenolic matrices. The SEM images showed excellent adhesion at the fiber/matrix interface. The coir fiber had bundles regularly spaced, which enhanced the diffusion of the resin into the fiber. In addition, the high lignin content of this fiber results in a high concentration of aromatic rings, which increased the compatibility with the matrix. The values of the diffusion coefficient of water, determined using Fick's laws, show that there was no correlation between the fiber percentage and the water diffusion. The DMTA curves showed that the storage moduli of the composites reinforced with coir fibers were considerably higher than that of the thermoset, and the increase in the proportion of fibers led to a proportional increase in the storage moduli of these materials. The biobased composites obtained have potential for non-structural applications, such as in the internal parts of automotives vehicles. To our knowledge, this is the first study on this kind of biobased composites.

Glioxal pode ser obtido a partir de biomassa (como da oxidação de lipídeos) e não é tóxico ou volátil, tendo sido por isso utilizado no presente trabalho como substituto de formaldeído na preparação de resina fenólica do tipo novolaca, sendo usado como catalisador o ácido oxálico, que também pode ser obtido de fontes renováveis. A resina glioxal-fenol foi utilizada na preparação de compósitos reforçados com celulose microcristalina (CM, 30, 50 e 70% em massa), uma celulose com elevada área superficial. As imagens de microscopia eletrônica de varredura (MEV) das superfícies fraturadas demonstraram que os compósitos apresentaram boa interface reforço/matriz, consequência da elevada área superficial da CM e presença de grupos polares (hidroxilas) tanto na matriz como na celulose, o que permitiu a formação de ligações hidrogênio, favorecendo a compatibilidade entre ambas. A análise térmica dinâmico-mecânica (DMTA) demonstrou que todos os compósitos apresentaram elevado módulo de armazenamento à temperatura ambiente. Além disso, o compósito reforçado com 30% de CM apresentou baixa absorção de água, comparável à do termorrígido fenólico, que é utilizado em escala industrial. Os resultados demonstraram que compósitos com boas propriedades podem ser preparados usando elevada proporção de materiais obtidos de biomassa.Glyoxal, which can be obtained from biomass (as by lipids oxidation), is non-toxic and non-volatile. It was used as a substitute of formaldehyde, which does not have these properties, in the synthesis of a novolac-type phenolic resin, using oxalic acid as a catalyst, which can also be obtained from renewable sources. The glyoxal-phenol resin was used in the preparation of composites reinforced with microcrystalline cellulose (MCC 30, 50, and 70% w/w). Scanning electron microscopy (SEM) images of the fractured surfaces showed that the composites presented a good reinforcement/matrix interface. This can be attributed to the high surface area of the MCC and also to the presence of polar groups (hydroxyl) in both cellulose and matrix, which allowed the formation of hydrogen bonds, leading to a good adhesion between the components present at the interface. Dynamic mechanical thermoanalysis (DMTA) showed that all of the obtained composites have high storage modulus at room temperature. Moreover, the composite reinforced with 30% of MCC showed the lowest water absorption, almost the same as that of the phenolic thermoset, which is used in industrial applications. The results showed that composites with good properties can be prepared using high proportions of materials obtained from biomass.

In this work, composites based on a phenolic matrix and untreated- and treated sisal fibers were prepared. The treated sisal fibers used were those reacted with NaOH 2% solution and esterified using benzophenonetetracarboxylic dianhydride (BTDA). These treated fibers were modified with the objective of improving the adhesion of the fiber-matrix interface, which in turn influences the properties of the composites. BTDA was chosen as the esterifying agent to take advantage of the possibility of introducing the polar and aromatic groups that are also present in the matrix structure into the surface of the fiber, which could then intensify the interactions occurring in the fiber-matrix interface. The fibers were then analyzed by SEM and FTIR to ascertain their chemical composition. The results showed that the fibers had been successfully modified. The composites (reinforced with 15%, w/w of 3.0 cm length sisal fiber randomly distributed) were characterized by SEM, impact strength, and water absorption capacity. In the tests conducted, the response of the composites was affected both by properties of the matrix and the fibers, besides the interfacial properties of the fiber-matrix. Overall, the results showed that the fiber treatment resulted in a composite that was less hygroscopic although with somewhat lower impact strength, when compared with the composite reinforced with untreated sisal fibers.

The aim of the present work was to investigate the toughening of phenolic thermoset and its composites reinforced with sisal fibers, using hydroxyl-terminated polybutadiene rubber (HTPB) as both impact modifier and coupling agent. Substantial increase in the impact strength of the thermoset was achieved by the addition 10% of HTPB. Scanning electron microscopy (SEM) images of the material with 15% HTPB content revealed the formation of some rubber aggregates that reduced the efficiency of the toughening mechanism. In composites, the toughening effect was observed only when 2.5% of HTPB was added. The rubber aggregates were found located mainly at the matrix–fiber interface suggesting that HTPB could be used as coupling agent between the sisal fibers and the phenolic matrix. A composite reinforced with sisal fibers pre-impregnated with HTPB was then prepared; its SEM images showed the formation of a thin coating of HTPB on the surface of the fibers. The ability of HTBP as coupling agent between sisal fibers and phenolic matrix was then investigated by preparing a composite reinforced with sisal fibers pre-treated with HTPB. As revealed by its SEM images, the HTPB pre-treatment of the fibers resulted on the formation of a thin coating of HTPB on the surface of the fibers, which provided better compatibility between the fibers and the matrix at their interface, resulting in a material with low water absorption capacity and no loss of impact strength.

The (bio)degradation of polyolefins can be accelerated by modifying the level of crystallinity or by incorporation of carbonyl groups by adding pro-oxidants to masterbatches or through exposure to ultraviolet irradiation. In this work, we sought to improve the degradation of PP by adding cobalt, calcium or magnesium stearate to Ecoflex ® , PP or Ecoflex ® /PP blends. The effect of the pro-oxidants on biodegradability was assessed by examining the mechanical properties and fluidity of the polymers. PP had higher values for tensile strength at break and Young's modulus than Ecoflex ® , and the latter had little influence on the properties of PP in Ecoflex ® /PP blends. However, the presence of pro-oxidants (except for calcium) reduced these properties. All of the pro-oxidants enhanced the fluidity of PP, a phenomenon that facilitated polymer degradation at high temperatures.

Thermoset phenolic composites reinforced with sisal fibers were prepared to optimize the cure step. In the present study, processing parameters such as pressure, temperature, and time interval were varied to control the vaporization of the water generated as a byproduct during the crosslinking reaction. These molecules can vaporize forming voids, which in turn affect the final material properties. The set of results on impact strength revealed that the application of higher pressure before the gel point of the phenolic matrix produced composites with better properties. The SEM images showed that the cure cycle corresponding to the application of higher values of molding pressure at the gel point of the phenolic resin led to the reduction of voids in the matrix. In addition, the increase in the molding pressure during the cure step increased the resin interdiffusion. Better filling of the fiber channels decreased the possibility of water molecules diffusing through the internal spaces of the fibers. These molecules then diffused mainly through the bulk of the thermoset matrix, which led to a decrease in the water diffusion coefficient (D) at all three temperatures (25, 55 and 70 °C) considered in the experiments.

The objective of this work was the preparation and characterization of poly(2,5-benzimidazole) (ABPBI) as electrolyte membrane for fuel cells applications at intermediate temperatures (130-200°). The ABPBI membranes were prepared by casting and then doped in phosphoric acid baths of different concentrations. The characterization included thermogravimetric analyses, elemental analyses and size exclusion chromatography. ABPBI membrane-electrode assemblies (MEAs) were tested in H2/O2 fuel cells.

Curaua fibers were treated with ionized air to improve the fiber/phenolic matrix adhesion. The treatment with ionized air did not change the thermal stability of the fibers. The impact strength increased with increase in the fiber treatment time. SEM micrographs of the fibers showed that the ionized air treatment led to separation of the fiber bundles. Treatment for 12h also caused a partial degradation of the fibers, which prompted the matrix to transfer the load to a poorer reinforcing agent during impact, thereby decreasing the impact strength of the related composite. The composites reinforced with fibers treated with ionized air absorbed less water than those reinforced with untreated fibers.

Sisal fibers have been chemically modified by reaction with lignins, extracted from sugarcane bagasse and Pinus-type wood and then hydroxymethylated, to increase adhesion in resol-type phenolic thermoset matrices. Inverse gas chromatography (IGC) results showed that acidic sites predominate for unmodified/modified sisal fibers and for phenolic thermoset, indicating that the phenolic matrix has properties that favor the interaction with sisal fibers. The IGC results also showed that the phenolic thermoset has a dispersive component closer to those of the modified fibers suggesting that thermoset interactions with the less polar modified fibers are favored. Surface SEM images of the modified fibers showed that the fiber bundle deaggregation increased after the treatment, making the interfibrillar structure less dense in comparison with that of unmodified fibers, which increased the contact area and encouraged microbial biodegradation in simulated soil. Water diffusion was observed to be faster for composites reinforced with modified fibers, since the phenolic resin penetrated better into modified fibers, thereby blocking water passage through their channels. Overall, composites' properties showed that modified fibers promote a significant reduction in the hydrophilic character, and consequently of the reinforced composite without a major effect on impact strength and with increased storage modulus.

Resol type resins were prepared in alkaline conditions (potassium hydroxide or potassium carbonate) using furfural obtained by acid hydrolysis of abundant renewable resources from agricultural and forestry waste residues. The structures of the resins were fully determined by 1H, 13C, and 2D NMR spectrometries with the help of four models compounds synthesized specially for this study. MALDI-Tof mass spectrometry experiments indicated that a majority of linear oligomers and a minority of cyclic ones constituted them. Composites were prepared with furfural–phenol resins and sisal fibers. These fibers were chosen mainly because they came from natural lignocellulosic material and they presented excellent mechanical properties. Thermal analyses (dTG and DSC) and electron microscopy images indicated that the composites displayed excellent adhesion between resin and fibers. Impact strength measurement showed that mild conditions were more suitable to prepare thermosets. Nevertheless, mild conditions induced a high-diffusion coefficient for water absorption by composites. Composites with good properties could be prepared using high proportion of materials obtained from biomass without formaldehyde. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008