Micromechanics models allow the prediction of a composite material's properties by adding their phases' contributions to such properties. The models can be used to obtain the intrinsic properties of the reinforcements because are difficult to obtain experimentally. This paper explores a simplified model to obtain the intrinsic strength of natural fibers. This model allows obtaining the value directly from the experimental strength of a composite and the matrix. Other models like the Kelly and Tyson equation have three unknowns, needing the use of mathematical methods to obtain a solution, and the obtained solution sometimes deviates from the expected values for natural fiber-reinforced composites. The proposed equation has been able to evaluate the intrinsic strength of hemp fibers as polypropylene composites at a mean value of 600 MPa. This value agrees with the literature. The proposed method simplifies the obtention of the intrinsic tensile strengths of natural fiber reinforcements and does not need morphologic properties of such reinforcements to obtain a solution, decreasing the costs in time and equipment in comparison to usual models like Kelly and Tyson's. furthermore, the obtained results are like those obtained with other micromechanics approaches and reveal the same information about the intrinsic tensile strength of the reinforcements and the strength of the interface.

This study presents a novel equation that obtains the intrinsic flexural modulus of a natural fiber from its microfibril angle (MFA) and its crystalline cellulose content, once having estimated both parameters from X-ray diffraction (XRD). The percentage of crystalline cellulose was estimated as the content of cellulose times the crystallinity index. Moreover, the MFA of abaca strands was obtained through an equation relating MFA with the strain at break of the strands and by XRD azimuthal integration, obtaining similar results. Fully bio-based composites, consisting of biopolyethylene reinforced with of abaca strands at 20 to 50 wt% contents, were tested to assess the impact of the natural fibers on the flexural modulus of the composites. The intrinsic flexural modulus was also evaluated by using three micromechanics models (Hirsh equation, Halpin and Tsai equation, and its modification by Nielsen). The values obtained from the application of the new equation, the micromechanics methods, and the literature showed satisfactory agreement.Highlights Evaluation of the flexural modulus of abaca strand reinforced bio-polyethylene composites. Use of micromechanics models to obtain the intrinsic modulus of abaca strands. Formula that correlates the intrinsic flexural modulus of abaca to its crystalline cellulose content and microfibril angle.

This study investigates the enhancement of PLA-based biocomposites using high-yield mechanical stone groundwood (SGW) pulp, with a focus on reinforcing fiber-matrix interactions through silane-coupling fiber modification. Different fractions of SGW (20 and 30 wt%) and (3-glycidyloxypropyl)trimethoxysilane (GPS) as a coupling agent (3, 5, 7, and 10 wt%) were incorporated into the PLA matrix. Thermo-mechanical properties including melt flow index, melt rheology, tensile strength, and Young's modulus were evaluated, along with thermal degradation behavior via TGA and DSC. Non-modified and partially modified SGW fractions (20 and 30 wt%) improved PLA-SGW interface, resulting in increased tensile strength (14 % and 27 % respectively). Biocomposites with 30 wt% SGW modified with 5 and 7 wt% GPS exhibited the highest tensile strength improvement, along with the rest of the properties, attributed to GPS influence on melt flow index and processability. The obtained biocomposites showcased properties comparable to commodity polypropylene composites.

Lignin-containing cellulose nanofibrils (LCNFs) have emerged as a new class of nanocelluloses where the presence of residual lignin is expected to impart additional attributes such as hydrophobicity or UV-absorption. In the present work, LCNFs with a lignin content between 7 and 15 wt% were prepared via a TEMPO-mediated oxidation as chemical pretreatment followed by high-pressure homogenization. The impact of the carboxyl content (CC) on the properties of the resulting LCNF gel, in terms of lignin content, colloidal properties, morphology, crystallinity, and thermal stability, were investigated. It was found that lignin content was significantly decreased at increasing CC. In addition, CC had a positive effect on colloidal stability and water contact angle, as well as resulting in smaller fibrils. This lower size, together with the lower lignin content, resulted in a slightly lower thermal stability. The reinforcing potential of the LCNFs when incorporated into a ductile polymer matrix was also explored by preparing nanocomposite films with different LCNF contents that were mechanically tested under linear and non-linear regimes by dynamic mechanical analysis (DMA) and tensile tests. For comparison purposes, the reinforcing effect of the LCNFs with lignin-free CNFs was also reported based on literature data. It was found that lignin hinders the network-forming capacity of LCNFs, as literature data shows a higher reinforcing potential of lignin-free CNFs. Nonetheless, the tensile strength of the acrylic matrix was enhanced by 10-fold at 10 wt% of LCNF content.

Bio-based polymers, with any of their constituents based on nonrenewable sources, can answer the demands of society and regulations regarding minimizing the environmental impact. The more similar such biocomposites are to oil-based composites, the easier the transition, especially for companies that do not like the uncertainty. A BioPE matrix, with a structure similar to that of a high-density polyethylene (HDPE), was used to obtain abaca-fiber-reinforced composites. The tensile properties of these composites are displayed and compared with commercial glass-fiber-reinforced HDPE. Since the strength of the interface between the reinforcements and the matrix is responsible for the exploitation of the strengthening abilities of the reinforcements, several micromechanical models were used to obtain an estimation of the strength of the interface and the intrinsic tensile strength of the reinforcements. Biocomposites require the use of a coupling agent to strengthen their interface, and once an 8 wt.% of such coupling agent was added to the composites, these materials returned tensile properties in line with commercial glass-fiber-reinforced HDPE composites.

The growing demand for plant fiber-reinforced composites offers new opportunities to compete against glass fiber (GF)-reinforced composites, but their performance must be assessed, revised, and improved as much as possible. This work reports on the production and the flexural strength of composites from polypropylene (PP) and hemp strands (20–50 wt.%), using maleic anhydride-grafted PP (MAPP) as a compatibilizer. A computational assessment of the reaction between cellulose and MAPP suggested the formation of only one ester bond per maleic anhydride unit as the most stable product. We determined the most favorable MAPP dosage to be 0.06 g per gram of fiber. The maximum enhancement in flexural strength that was attained with this proportion of MAPP was 148%, corresponding to the maximum fiber load. The modified rule of mixtures and the assumption of similar coupling factors for tensile and flexural strength allowed us to estimate the intrinsic flexural strength of hemp strands as 953 ± 116 MPa. While falling short of the values for sized GF (2415 MPa), the reinforcement efficiency parameter of the natural fibers (0.209) was found to be higher than that of GF (0.045).

Composites from polypropylene (PP) reinforced with hemp strands (HS) are prepared in the current work with the aim of deepening on the influence of this reinforcement on the impact performance of these specific composites. Despite all the research conducted in this field, the effect of this natural reinforcement on the absorbed energy during crack formation and propagation is not fully tackled in previous research works. From the methodology and samples’ geometry, the results concluded that the quality of the interface has a noticeable role in the impact resistance of these materials. The interface strength, fiber dispersion and fiber pullout are the main contributors to crack formation, whereas fiber pullout is the main one responsible for crack propagation. Maximum values of absorbed energy were found for PP composites comprising 20–30 wt% of HS and 8 wt% of the coupling agent for the un-notched samples, whereas maximum absorbed energy values corresponded to PP composites with 40 wt% of HS and 4 wt% of coupling agent for the notched samples. The water-absorption behavior in different humid environments is also examined. From the kinetic study, the water diffusion followed a Fickean behavior showing low-diffusion coefficients, increasing with fiber content. This systematic investigation represents a contribution to the analysis of the potential of reinforcing conventional polymers with natural materials, as a strategy towards more sustainable development.

Biocomposites from poly-(lactic acid) (PLA) and jute strands were prepared, and their flexural strength was analyzed. Jute strands were submitted to a progressive delignification process and the resulting morphology, composition, and crystallinity index were evaluated. Then, PLA biocomposites comprising 30 wt% of jute strands were produced and characterized under flexural conditions. The delignification processes decreased the lignin content and progressively increased the cellulose content. All this resulted in an enhancement of the composite flexural strength. A modified rule of mixtures, and the relation between tensile and flexural properties were used to determine the intrinsic flexural strength (of the jute strands) and their correlation with their physic-chemical characteristics. Equations correlating the intrinsic flexural strength with the crystallinity index, the cellulose content, and the microfibril angle were proposed. These equations show the impact of these properties over the intrinsic properties of the fibers and can help researchers to select appropriate fibers to obtain accurate properties for the composites. Jute strands show their value as reinforcement by increasing the flexural strength of the matrix by 70% and being less expensive and more environmentally friendly than mineral reinforcements. Together with the profitability and the environmental advantages, the mechanical results suggest that these PLA biocomposites are suitable for specific products of different market sectors.

The cost-effective implementation of nanofibrillated cellulose (CNF) at industrial scale requires optimizing the quality of the nanofibers according to their final application. Therefore, a portfolio of CNFs with different qualities is necessary, as well as further knowledge about how to obtain each of the main qualities. This paper presents the influence of various production techniques on the morphological characteristics and properties of CNFs produced from a mixture of recycled fibers. Five different pretreatments have been investigated: a mechanical pretreatment (PFI refining), two enzymatic hydrolysis strategies, and TEMPO-mediated oxidation under two different NaClO concentrations. For each pretreatment, five high-pressure homogenization (HPH) conditions have been considered. Our results show that the pretreatment determines the yield and the potential of HPH to enhance fibrillation and, therefore, the final CNF properties. These results enable one to select the most effective production method with the highest yield of produced CNFs from recovered paper for the desired CNF quality in diverse applications.

The use of bio-based matrices together with natural fibers as reinforcement is a strategy for obtaining materials with competitive mechanical properties, costs, and environmental impacts. However, bio-based matrices, unknown by the industry, can be a market entry barrier. The use of bio-polyethylene, which has properties similar to polyethylene, can overcome that barrier. In this study, composites reinforced with abaca fibers used as reinforcement for bio-polyethylene and high density polyethylene are prepared and tensile tested. A micromechanics analysis is deployed to measure the contributions of the matrices and reinforcements and to measure the evolution of these contributions regarding AF content and matrix nature. The results show that the mechanical properties of the composites with bio-polyethylene as a matrix were slightly higher than those of the composites with polyethylene as a matrix. It was also found that the contribution of the fibers to the Young's moduli of the composites was susceptible to the percentage of reinforcement and the nature of the matrices. The results show that it is possible to obtain fully bio-based composites with mechanical properties similar to those of partially bio-based polyolefin or even some forms of glass fiber-reinforced polyolefin.

Composite materials containing natural reinforcement fibers, generally called biocomposites, have attracted the interest of both researchers and manufacturers, but the most environmentally advantageous combinations include a bio-based matrix, as well. With this in mind, a poly(lactic acid) (PLA) matrix was reinforced with natural fibers from hemp, both untreated strands (UHSs) and soda-bleached fibers (SBHFs). The preparation of the subsequent fully bio-sourced, discontinuously reinforced composites involved kinetic mixing, intensive single-screw extrusion, milling, and injection molding. Up to a fiber content of 30 wt%, the tensile modulus increased linearly with the volume fraction of the dispersed phase. Differences between SBHFs (up to 7.6 Gpa) and UHSs (up to 6.9 Gpa) were hardly significant (p = 0.1), but SBHF-reinforced composites displayed higher strain at failure. In any case, for the same fiber load (30 wt%), the Young's modulus of PLA/hemp biocomposites was greater than that of glass fiber (GF)-reinforced polypropylene (5.7 GPa), albeit lower than that of PLA/GF (9.8 GPa). Considering all the measurements, the contribution of each phase was analyzed by applying the Hirsch model and the Tsai-Pagano model. As a concluding remark, although the intrinsic tensile modulus of SBHFs was lower than that of GF, the efficiency of those natural fibers as reinforcement (according to the rule of mixtures) was found to be higher.

The compatibility between poly(lactic acid) (PLA) and natural fibers to develop bio-sourced, recyclable, and biodegradable composites remains a commonplace issue. This work highlights that, at least in the case of hemp, pulping and bleaching towards delignified short fibers attained remarkable improvements over untreated hemp strands. This approach differs from usual proposals of chemically modifying hydroxyl groups. Soda-bleached hemp fibers (SBHFs) granted a relatively large bonding surface area and a satisfactory quality of the interphase, even in the absence of any dispersant or compatibilizer. To attain satisfactory dispersion, the matrix and the fibers were subjected to kinetic mixing and to a moderately intensified extrusion process. Then, dog-bone specimens were prepared by injection molding. Up to a fiber content of 30 wt.%, the tensile strength increased linearly with the volume fraction of the dispersed phase. It reached a maximum value of 77.8 MPa, signifying a relative enhancement of about 52%. In comparison, the tensile strength for PLA/hemp strands was 55.7 MPa. Thence, based on the modified rule of mixtures and the Kelly & Tyson modified equation, we analyzed this performance at the level of the constituent materials. The interfacial shear strength (over 28 MPa) and other micromechanical parameters were computed. Overall, this biocomposite was found to outperform a polypropylene/sized glass fiber composite (without coupling agent) in terms of tensile strength, while fulfilling the principles of green chemistry.

The use of dithizone (DTZ) for colorimetric heavy-metal detection is approximately one century old. However, its pending stability issues and the need for simple indicators justify further research. Using cellulose nanofibers, we attained DTZ-containing emulsions with high stability. These emulsions had water (at least 95 wt %) and acetic acid (1-8 mL/L) conforming the continuous phase, while dispersed droplets of diameter <1 μm contained chloroform-solvated DTZ (3 wt %). The solvation cluster was computed by molecular dynamics simulations, suggesting that chloroform slightly reduces the dihedral angle between the two sides of the thiocarbazone chain. Nanocellulose concentrations over 0.2 wt % sufficed to obtain macroscopically homogeneous mixtures with no phase separation. Furthermore, the rate of degradation of DTZ in the nanocellulose-stabilized emulsion did not differ significantly from a DTZ/chloroform solution, outperforming DTZ/toluene and DTZ/acetonitrile. Not only is the emulsion readily and immediately responsive to mercury(II), but it also decreases interferences from other ions and from natural samples. Unexpectedly, neither lead(II) nor cadmium(II) triggered a visual response at trace concentrations. The limit of detection of these emulsions is 15 μM or 3 mg/L, exceeding WHO limits for mercury(II) in drinking water, but they could be effective at raising alarms.

Current knowledge on the properties of different types of cellulose nanofibers (CNFs) is fragmented. Properties variation is very extensive, depending on raw materials, effectiveness of the treatments to extract the cellulose fraction from the lignocellulosic biomass, pretreatments to facilitate cellulose fibrillation and final mechanical process to separate the microfibrils. Literature offers multiple parameters to characterize the CNFs prepared by different routes. However, there is a lack of an extensive guide to compare the CNFs. In this study, we perform a critical comparison of rheological, compositional, and morphological features of CNFs, produced from the most representative types of woody plants, hardwood and softwood, using different types and intensities of pretreatments, including enzymatic, chemical and mechanical ones, and varying the severity of mechanical treatment focusing on the relationship between macroscopic and microscopic parameters. This structured information will be exceedingly useful to select the most appropriate CNF for a certain application based on the most relevant parameters in each case.

The present work shows the feasibility of incorporating lignocellulosic nanofibers (LCNFs) from date palm waste, with diameters in the range of 10 and 30 nm, into polyethylene glycol (PEG)-plasticized polylactic acid (PLA). PLA/PEG/LCNF nanocomposites, with nanocellulose contents ranging from 2 to 10 wt%. were successfully prepared by one-step melt processing using PEG as a carrier to prevent the aggregation of LCNFs. The effect of the LCNFs content on the mechanical properties was assessed by tensile tests and dynamic mechanical analysis (DMA), pointing an enhancement in the tensile strength and Young's modulus by about 250% and 1100%, respectively, at 8% LCNFs content while maintaining a high toughness (around 16 MJ/m3). In addition, the proper dispersion in the form of a 3D-structured network and the good compatibility of LCNFs with the PLA/PEG matrix were confirmed by DMA and melt rheology measurements, as the stiffness in the rubbery state and the storage modulus increased with the content of LCNFs, respectively. The homogenous dispersion of LCNFs within PLA/PEG matrix was further confirmed by scanning electron microscopy (SEM) observation. Finally, from the disintegration tests in composting conditions, both PEG and LCNFs were found to positively contribute to the disintegration of PLA, mainly due to their affinity with water. Given the better sustainability of LCNFs owing to the absence of any chemical to isolate cellulose, along with their dispersibility within PLA matrix, the use of PEG as a carrier to produce PLA-LCNFs composites via melt processing may contribute to further highlight the merits of LCNFs as reinforcement in a biobased polymer matrix to produce composites with enhanced mechanical properties.

Cationic cellulose, despite its long history, has yet to find a place in the paper industry. However, recent research is evaluating the potential of its nanoscale forms. Likewise, the processes of Western manufacturers are optimized for wood pulps, relegating non-wood crops to specific products that, as also proposed by current research, could include nanocellulose. We combined these trends with the existing knowledge of the strong adsorption of poly(diallyldimethylammonium chloride) (polyDADMAC) on cellulosic fibers, which can be deemed a non-covalent kind of cationization. For that, polyDADMAC was first anchored to refined hemp pulps, under conditions that allowed the deprotonation of the primary hydroxyl groups of cellulose. The fiber surface remained positively-charged even after thoroughly washing the samples, owing not only to the small proportions of acidic hemicelluloses and lignin, but also to stable ion-dipole interactions. This non-covalent cationization was found to follow pseudo-second order kinetics, indicating that diffusion through the fiber was the rate-controlling step. PolyDADMAC-containing fibers were then fibrillated by high-pressure homogenization. The surface charge of cationic nanocellulose was greater than that of the starting fibers, as the specific surface area increased. Nonetheless, polyDADMAC caused agglomeration of fibrils to a certain extent. As a drawback, when applied in papermaking, cationic nanocellulose lowered air permeability to a lesser extent than non-cationized nanofibers. As an advantage, the tensile index increased by up to 57% in the absence of any retention agent.

The performance of henequen fibers and polypropylene composites obtained by injection molding with and without coupling agent was evaluated. Henequen fibers are natural non-wood fibers mainly used in textile sector or in thermosetting matrix composites. In this work, henequen fibers have been used as a possible substitute reinforcement material for sized glass fibers. The surface charge density of the materials used was evaluated, as well as the morphology of the fibers inside the material. A significant reduction in the length of the fibers was observed as a consequence of the processing. The use of a 4% coupling agent based on fiber content was found to be effective in achieving significant improvements in the tensile strength of the composites in the reinforcement range studied. The influence of the aspect ratio on the coupling factor was determined, as well as the evaluation of the interface quality. The results obtained demonstrate the great potential of henequen fibers as reinforcement of composite materials, giving rise to strong interfaces with coupling. Finally, the comparison of henequen fiber composites with sized glass fiber composites showed that it is possible to substitute polypropylene composites with 20 wt.% glass fiber for 50 wt.% henequen fibers.

Abstract As cationic cellulose, despite its long history, has yet to find a place in the paper industry, recent research is assessing the potential of its nanoscale forms. We combined this trend with the existing knowledge of the strong adsorption of poly(diallyldimethylammonium chloride) (polyDADMAC) on cellulosic fibers, which can be deemed a non-covalent kind of cationization. For that, polyDADMAC was first anchored to refined kraft pulps from hemp, under conditions that allowed the deprotonation of the hemiacetal groups of cellulose. Conveniently, a highly positively-charged fiber surface remained after thoroughly washing the samples, owing not only to the small proportions of acidic hemicelluloses and lignin, but also to stable ion-dipole interactions. This non-covalent cationization was found to follow pseudo-second order kinetics, indicating that diffusion through the fiber is the rate-controlling step. PolyDADMAC-containing fibers were then fibrillated by high-pressure homogenization. Far from promoting desorption, cationic nanocellulose had greater surface charge than the starting fibers, as the specific surface area increased. Nonetheless, polyDADMAC caused agglomeration of fibrils to a certain extent, resulting in, besides loss of transparency, higher permeability when applied in papermaking by bulk addition. As an advantage, the tensile index increased by up to 57% in the absence of any retention agent.

The current need to develop more sustainable processes and products requires the study of new materials. In the field of plastic materials, the need to develop 100% bio-based materials that meet market requirements is evident. In this sense, the present work aims to explore the potential of rapeseed waste as a reinforcement of a bio-based plastic matrix that does not generate new sub-waste. For this purpose, three types of processing of rapeseed residues have been studied: (i) milling; (ii) mechanical process; (iii) thermomechanical process. In addition, the reinforcing capacity of these materials, together with the need for an optimized coupling agent at 6 wt.%, has been verified. The micromechanics of the materials have been evaluated to determine the development of these fibers in the composite material. The results obtained show remarkable increases in mechanical properties, reaching more than 141% in tensile strength and 128% in flexural strength. There is a remarkable difference in the impact behavior between the materials with milled rapeseed and the fibers obtained by mechanical or thermomechanical processes. It was found that by sustainable design it is possible to achieve a 76.2% reduction in the amount of plastic used to manufacture material with the same mechanical properties.

While the potential of cellulose nanofibers to enhance the mechanical and barrier properties of paper is well-known, there are many uncertainties with respect to how to apply them. In this study, we use not only bulk addition of micro-/nanofibers and bar coating with oxidized nanofibers, but also a combination of these and, as a novel element, electrospray deposition of nanofiber dispersions. Characterization involved testing the strength of uncoated and coated paper sheets, their resistance to air flow, their Bendtsen roughness, and their apparent density, plus visualization of their surface and cross-sections by scanning electron microscopy. As expected, bulk addition to the unrefined pulp was sufficient to attain substantial strengthening, but this enhancement was limited to approximately 124%. Following this, surface addition by bar coating improved air resistance, but not strength, since, as applying nanocellulose at high consistency was technically unfeasible, this was performed several times with detrimental drying stages in between. However, replacing bar coating with electrospraying helped us overcome these apparent limitations, producing enhancements in both barrier and tensile properties. It is concluded that electrosprayed nanofibers, owing to their uniform deposition and favorable interactions, operate as an effective binder between fibers (and/or fines).