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Modern bioplastics and biocomposites frequently contain non-biodegradable or non-sustainable components and require complex recycling routes. Sustainable materials require integrating bio-based, cheap, widely available, recycled, or waste components. In order to incorporate these concepts, we selected hemp stalk waste, the industrial byproducts glycerol and xylan (hemicellulose), and citric acid as key components. Hemp stalks were processed into cast papers using only mechanical processes and no chemical modifications or pre-treatments. Cast papers were impregnated with a crosslinking mixture of glycerol, xylan, citric acid, and the plasticizer polyethylene glycol (PEG). Thermal crosslinking was performed as a single-step reaction by curing materials at 140 °C. All prepared bioplastics were washed in water for 48 h and extensively tested for water resistance and water absorption. A recycling route with depolymerization (for pulp recovery) in sodium hydroxide is demonstrated. A comprehensive analysis of crosslinking reaction is provided via FTIR and rheology, supplemented by structure analysis via SEM. A 7-fold reduction in water uptake was achieved compared to cast hemp paper. Obtained bioplastics, after washing in water, show elastic modulus up to 2.9 GPa, tensile strength up to 70 MPa, and elongation up to 4.3 %. As a result of component ratio variation, bioplastics achieve a high tuneability of properties ranging from brittle to ductile. Dielectric analysis indicates that bioplastics have the potential for application in electric insulation. A three-layer laminate is demonstrated as a concept for potential application as an adhesive for bio-based composites.
Assuntos
Cannabis , Celulose , Celulose/química , Xilanos , Glicerol/química , Biopolímeros , Água/químicaRESUMO
We combine renewable and waste materials to produce hydrophobic membranes in the present work. Cellulose nanopaper prepared from paper waste was used as a structural component for the membrane. The pine wax was reclaimed from pine needle extraction waste and can be regarded as a byproduct. The dip-coating and spray-coating methods were comprehensively compared. In addition, the solubility of wax in different solvents is reported, and the concentration impact on coating quality is presented as the change in the contact angle value. The sensile drop method was used for wetting measurements. Spray-coating yielded the highest contact angle with an average of 114°, while dip-coating reached an average value of 107°. Scanning electron microscopy (SEM) was used for an in-depth comparison of surface morphology. It was observed that coating methods yield significantly different microstructures on the surface of cellulose fibers. The wax is characterized by nuclear magnetic resonance (NMR) spectroscopy and differential scanning calorimetry (DSC). Pine wax has a melting temperature of around 80 °C and excellent thermal stability in oxygen, with a degradation peak above 290 °C. Fourier transform infrared spectroscopy (FTIR) was used to identify characteristic groups of components and show the changes on coated nanopaper. Overall, the results of this work yield important insight into wax-coated cellulose nanopapers and a comparison of spray- and dip-coating methods. The prepared materials have a potential application as membranes and packaging materials.
RESUMO
Cellulose materials and products are frequently affected by environmental factors such as light, temperature, and humidity. Simulated UV irradiation, heat, and moisture exposure were comprehensively used to characterize changes in cellulose nanopaper (NP) tensile properties. For the preparation of NP, high-purity cellulose from old, unused filter paper waste was used. Lignin and xylan were used as sustainable green interface engineering modifiers for NP due to their structural compatibility, low price, nontoxic nature, and abundance as a by-product of biomass processing, as well as their ability to protect cellulose fibers from UV irradiation. Nanofibrillated cellulose (NFC) suspension was obtained by microfluidizing cellulose suspension, and NP was produced by casting films from water suspensions. The use of filler from 1 to 30 wt% significantly altered NP properties. All nanopapers were tested for their sensitivity to water humidity, which reduced mechanical properties from 10 to 40% depending on the saturation level. Xylan addition showed a significant increase in the specific elastic modulus and specific strength by 1.4- and 2.8-fold, respectively. Xylan-containing NPs had remarkable resistance to UV irradiation, retaining 50 to 90% of their initial properties. Lignin-modified NPs resulted in a decreased mechanical performance due to the particle structure of the filler and the agglomeration process, but it was compensated by good property retention and enhanced elongation. The UV oxidation process of the NP interface was studied with UV-Vis and FTIR spectroscopy, which showed that the degradation of lignin and xylan preserves a cellulose fiber structure. Scanning electron microscopy images revealed the structural formation of the interface and supplemented understanding of UV aging impact on the surface and penetration depth in the cross-section. The ability to overcome premature aging in environmental factors can significantly benefit the wide adaption of NP in food packaging and functional applications.
Assuntos
Celulose/química , Lignina/química , Nanoestruturas/química , Xilanos/química , Teste de Materiais , Nanoestruturas/efeitos da radiaçãoRESUMO
Biodegradable polymers (BP) are often regarded as the materials of the future, which address the rising environmental concerns. The advancement of biorefineries and sustainable technologies has yielded various BP with excellent properties comparable to commodity plastics. Water resistance, high dimensional stability, processability and excellent physicochemical properties limit the reviewed materials to biodegradable polyesters and modified compositions of starch and cellulose, both known for their abundance and relatively low price. The addition of different nanofillers and preparation of polymer nanocomposites can effectively improve BP with controlled functional properties and change the rate of degradation. The lack of data on the durability of biodegradable polymer nanocomposites (BPN) has been the motivation for the current review that summarizes recent literature data on environmental ageing of BPN and the role of nanofillers, their basic engineering properties and potential applications. Various durability tests discussed thermal ageing, photo-oxidative ageing, water absorption, hygrothermal ageing and creep testing. It was discussed that incorporating nanofillers into BP could attenuate the loss of mechanical properties and improve durability. Although, in the case of poor dispersion, the addition of the nanofillers can lead to even faster degradation, depending on the structural integrity and the state of interfacial adhesion. Selected models that describe the durability performance of BPN were considered in the review. These can be applied as a practical tool to design BPN with tailored property degradationand durability.
RESUMO
Turning waste products into useable resources is a necessity for the sustainable future of our planet. Such is the case with popular beverage coffee that produces solid waste in the form of spent coffee grounds (SCG). There is an opportunity to use SCG material as a cheap, sustainable, and biodegradable polymer filler that is received as waste from espresso machines. There have been relatively many studies that prove the concept of various agricultural and forestry waste, which can be integrated into modern green materials. Building upon this concept, we have selected a promising polyester poly(butylene succinate) (PBS) as a matrix owing to its bio-based and biodegradable nature. High loadings of SCG from 20 to 60 wt% were tested for optimal composition performance. Tensile, dynamic mechanical, thermal, and structural properties of the composites were examined, while their biodegradation in composting conditions was also analyzed. SCG filler showed different performance from various cellulose fiber-based composites, and properties significantly varied depending on loading. Compared to neat PBS, biodegradation occurred twice as fast for composite materials with high SGC loadings.
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Biodegradable polymer composites from renewable resources are the next-generation of wood-like materials and are crucial for the development of various industries to meet sustainability goals. Functional applications like packaging, medicine, automotive, construction and sustainable housing are just some that would greatly benefit. Some of the existing industries, like wood plastic composites, already encompass given examples but are dominated by fossil-based polymers that are unsustainable. Thus, there is a background to bring a new perspective approach for the combination of microcrystalline cellulose (MCC) and nanofibrillated cellulose (NFC) fillers in bio-based poly (butylene succinate) matrix (PBS). MCC, NFC and MCC/NFC filler total loading at 40 wt % was used to obtain more insights for wood-like composite applications. The ability to tailor the biodegradable characteristics and the mechanical properties of PBS composites is indispensable for extended applications. Five compositions have been prepared with MCC and NFC fillers using melt blending approach. Young's modulus in tensile test mode and storage modulus at 20 °C in thermo-mechanical analysis have increased about two-fold. Thermal degradation temperature was increased by approximately 60 °C compared to MCC and NFC. Additionally, to estimate the compatibility of the components and morphology of the composite's SEM analysis was performed for fractured surfaces. The contact angle measurements testified the developed matrix interphase. Differential scanning calorimetry evidenced the trans-crystallization of the polymer after filler incorporation; the crystallization temperature shifted to the higher temperature region. The MCC has a stronger effect on the crystallinity degree than NFC filler. PBS disintegrated under composting conditions in a period of 75 days. The NFC/MCC addition facilitated the specimens' decomposition rate up to 60 days.
RESUMO
We report the manufacturing and characterization of poly (butylene succinate) (PBS) and micro cellulose (MCC) woody-like composites. These composites can be applied as a sustainable woody-like composite alternative to conventional fossil polymer-based wood-plastic composites (WPC). The PBS/MCC composites were prepared by using a melt blending of 70 wt% of MCC processed from bleached softwood. MCC was modified to enhance dispersion and compatibility by way of carbodiimide (CDI), polyhydroxy amides (PHA), alkyl ester (EST), (3-Aminopropyl) trimethoxysilane (APTMS), maleic acid anhydride (MAH), and polymeric diphenylmethane diisocyanate (PMDI). The addition of filler into PBS led to a 4.5-fold improvement of Young's modulus E for the MCC composite, in comparison to neat PBS. The 1.6-fold increase of E was obtained for CDI modified composition in comparison to the unmodified MCC composite. At room temperature, the storage modulus E' was found to improve by almost 4-fold for the APTMS composite. The EST composite showed a pronounced enhancement in viscoelasticity properties due to the introduction of flexible long alkyl chains in comparison to other compositions. The glass transition temperature was directly affected by the composition and its value was -15 °C for PBS, -30 °C for EST, and -10 °C for MAH composites. FTIR indicated the generation of strong bonding between the polymer and cellulose components in the composite. Scanning electron microscopy analysis evidenced the agglomeration of the MCC in the PBS/MCC composites. PMDI, APTMS, and CDI composites were characterized by the uniform dispersion of MCC particles and a decrease of polymer crystallinity. MCC chemical modification induced the enhancement of the thermal stability of MCC composites.