ABSTRACT
The use of biobased materials in additive manufacturing is a promising long-term strategy for advancing the polymer industry toward a circular economy and reducing the environmental impact. In commercial 3D printing formulations, there is still a scarcity of efficient biobased polymer resins. This research proposes vegetable oils as biobased components to formulate the stereolithography (SLA) resin. Application of nanocellulose filler, prepared from agricultural waste, remarkably improves the printed material's performance properties. The strong bonding of nanofibrillated celluloses' (NFCs') matrix helps develop a strong interface and produce a polymer nanocomposite with enhanced thermal properties and dynamical mechanical characteristics. The ultra-low NFC content of 0.1-1.0 wt% (0.07-0.71 vol%) was examined in printed samples, with the lowest concentration yielding some of the most promising results. The developed SLA resins showed good printability, and the printing accuracy was not decreased by adding NFC. At the same time, an increase in the resin viscosity with higher filler loading was observed. Resins maintained high transparency in the 500-700 nm spectral region. The glass transition temperature for the 0.71 vol% composition increased by 28°C when compared to the nonreinforced composition. The nanocomposite's stiffness has increased fivefold for the 0.71 vol% composition. The thermal stability of printed compositions was retained after cellulose incorporation, and thermal conductivity was increased by 11%. Strong interfacial interactions were observed between the cellulose and the polymer in the form of hydrogen bonding between hydroxyl and ester groups, which were confirmed by Fourier-transform infrared spectroscopy. This research demonstrates a great potential to use acrylated vegetable oils and nanocellulose fillers as a feedstock to produce high-performance resins for sustainable SLA 3D printing.
ABSTRACT
In response to rising concerns over the environmental and human health ramifications of polymers derived from petroleum, particularly in the food packaging industry, research has pivoted towards more sustainable materials. Poly(butylene succinate) (PBS), selected as the polymer matrix, stands out as one of the most promising bio-based and biodegradable polymers suitable for film blowing and lamination. A layered spray-coating technique was employed to apply 1, 5, 10, and 20 layers of nanofibrillated cellulose (NFC) between blown PBS films, creating a three-layer laminate structure. NFC sourced from minimally processed hemp stalk waste highlights the potential for minimizing environmental impact. The water vapor transmission rate (WVTR) of these films, a critical parameter for food packaging, was assessed in a controlled environment at 38 °C and 90% relative humidity over a period of two months. The integration of a single NFC layer, constituting 0.35% of the composite's weight, was observed to significantly reduce the WVTR by up to 5.5-fold. It was noted that higher NFC layer counts above 10 reduced the adhesion within the laminate layers. Morphological assessments showed that the number of structural defects increased with a higher count of NFC layers. As the count of NFC layers increased, the optical transparency of the laminates dropped from approximately 65% to 25% in the visible light spectrum. Notably, by weight percent, NFC proved to be an effective barrier even without chemical modification. The developed laminates stand out as a viable, green option for food packaging, offering a sustainable and renewable solution.
ABSTRACT
Liquid crystal (LC) based magnetic materials consisting of LC hosts doped with functional magnetic nanoparticles enable optical switching of the mesogens at moderate magnetic field strengths and thereby open the pathway for the design of novel smart devices. A promising route for the fabrication of stable ferronematic phases is the attachment of a covalently bound LC polymer shell onto the surface of nanoparticles. With this approach, ferronematic phases based on magnetically blocked particles and the commercial LC 4-cyano-4'-pentylbiphenyl (5CB) liquid crystal were shown to have a sufficient magnetic sensitivity, but the mechanism of the magneto-nematic coupling is unidentified. To get deeper insight into the coupling modes present in these systems, we prepared ferronematic materials based on superparamagnetic particles, which respond to external fields with internal magnetic realignment instead of mechanical rotation. This aims at clarifying whether the hard coupling of the magnetization to the particle's orientation (magnetic blocking) is a necessary component of the magnetization-nematic director coupling mechanism. We herein report the fabrication of a ferronematic phase consisting of surface-functionalized superparamagnetic Fe3O4 particles and 5CB. We characterize the phase behavior and investigate the magneto-optical properties of the new ferronematic phase and compare it to the ferronematic system containing magnetically blocked CoFe2O4 particles to get information about the origin of the magneto-nematic coupling.
ABSTRACT
There is an opportunity to use nanocellulose as an efficient renewable reinforcing filler for polymer composites. There have been many investigations to prove the reinforcement concept of different nanocellulose sources for thermoplastic and thermoset polymers. The present comparative study highlighted the beneficial effects of selecting cellulose nanofibers (CNFs) and nanocrystals (CNCs) on the exploitation properties of vegetable oil-based thermoset composite materials-thermal, thermomechanical, and structural characteristics. The proposed UV-light-curable resin consists of an acrylated epoxidized soybean oil polymer matrix and two different nanocellulose reinforcements. High loadings of up to 30 wt% of CNFs and CNCs in irradiation-cured vegetable oil-based thermoset composites were reported. Infrared spectroscopy analysis indicated developed hydrogen-bonding interactions between the nanocellulose and polymer matrix. CNCs yielded a homogeneous nanocrystal dispersion, while CNFs revealed a nanofiber agglomeration in the polymer matrix, as shown by scanning electron microscopy. Thermal degradation showed that nanocellulose reduced the maximum degradation temperature by 5 °C for the 30 wt% CNC and CNF nanocomposites. Above the glass transition temperature at 80 °C, the storage modulus values increased 6-fold and 2-fold for the 30 wt% CNC and CNF nanocomposites, respectively. In addition, the achieved reinforcement efficiency factor r value for CNCs was 8.7, which was significantly higher than that of CNFs of 2.2. The obtained nanocomposites with enhanced properties show great potential for applications such as UV-light-processed coatings, adhesives, and additive manufacturing inks.
ABSTRACT
Typical resins for UV-assisted additive manufacturing (AM) are prepared from petroleum-based materials and therefore do not contribute to the growing AM industry trend of converting to sustainable bio-based materials. To satisfy society and industry's demand for sustainability, renewable feedstocks must be explored; unfortunately, there are not many options that are applicable to photopolymerization. Nevertheless, some vegetable oils can be modified to be suitable for UV-assisted AM technologies. In this work, extended study, through FTIR and photorheology measurements, of the UV-curing of epoxidized acrylate from soybean oil (AESO)-based formulations has been performed to better understand the photopolymerization process. The study demonstrates that the addition of appropriate functional comonomers like trimethylolpropane triacrylate (TMPTA) and the adjusting of the concentration of photoinitiator from 1% to 7% decrease the needed UV-irradiation time by up to 25%. Under optimized conditions, the optimal curing time was about 4 s, leading to a double bond conversion rate (DBC%) up to 80% and higher crosslinking density determined by the Flory-Rehner empirical approach. Thermal and mechanical properties were also investigated via TGA and DMA measurements that showed significant improvements of mechanical performances for all formulations. The properties were improved further upon the addition of the reactive diluents. After the thorough investigations, the prepared vegetable oil-based resin ink formulations containing reactive diluents were deemed suitable inks for UV-assisted AM, giving their appropriate viscosity. The validation was done by printing different objects with complex structures using a laser based stereolithography apparatus (SLA) printer.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
