Biobased Resin for Sustainable Stereolithography: 3D Printed Vegetable Oil Acrylate Reinforced with Ultra-Low Content of Nanocellulose for Fossil Resin Substitution.

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.

Biodegradable Poly(butylene succinate) Laminate with Nanocellulose Interphase Layer for High-Barrier Packaging Film Application.

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.

Elaboration of Nanostructured Levan-Based Colloid System as a Biological Alternative with Antimicrobial Activity for Applications in the Management of Pathogenic Microorganisms.

Considering the documented health benefits of bacterial exopolysaccharides (EPSs), specifically of bacterial levan (BL), including its intrinsic antimicrobial activity against certain pathogenic species, the current study concentrated on the development of active pharmaceutical ingredients (APIs) in the form of colloid systems (CoSs) containing silver nanoparticles (AgNPs) employing in-house biosynthesized BL as a reducing and capping agent. The established protocol of fermentation conditions implicating two species of lactic acid bacteria (LAB), i.e., Streptococcus salivarius K12 and Leuconostoc mesenteroides DSM 20343, ensured a yield of up to 25.7 and 13.7 g L-1 of BL within 72 h, respectively. An analytical approach accomplished by Fourier-transform infrared (FT-IR) spectroscopy allowed for the verification of structural features attributed to biosynthesized BL. Furthermore, scanning electron microscopy (SEM) revealed the crystalline morphology of biosynthesized BL with a smooth and glossy surface and highly porous structure. Molecular weight (Mw) estimated by multi-detector size-exclusion chromatography (SEC) indicated that BL biosynthesized using S. salivarius K12 has an impressively high Mw, corresponding to 15.435 × 104 kilodaltons (kDa). In turn, BL isolated from L. mesenteroides DSM 20343 was found to have an Mw of only 26.6 kDa. Polydispersity index estimation (PD = Mw/Mn) of produced BL displayed a monodispersed molecule isolated from S. salivarius K12, corresponding to 1.08, while this was 2.17 for L. mesenteroides DSM 20343 isolate. The presence of fructose as the main backbone and, to a lesser extent, glucose and galactose as side chain molecules in EPS hydrolysates was supported by HPLC-RID detection. In producing CoS-BL@AgNPs within green biosynthesis, the presence of nanostructured objects with a size distribution from 12.67 ± 5.56 nm to 46.97 ± 20.23 was confirmed by SEM and energy-dispersive X-ray spectroscopy (EDX). The prominent inhibitory potency of elaborated CoS-BL@AgNPs against both reference test cultures, i.e., Pseudomonas aeruginosa, Escherichia coli, Enterobacter aerogenes, and Staphylococcus aureus and those of clinical origin with multi-drug resistance (MDR), was confirmed by disc and well diffusion tests and supported by the values of the minimum inhibitory and bactericidal concentrations. CoS-BL@AgNPs can be treated as APIs suitable for designing new antimicrobial agents and modifying therapies in controlling MDR pathogens.

Sustainable hemp-based bioplastics with tunable properties via reversible thermal crosslinking of cellulose.

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.

Pectin from Fruit- and Berry-Juice Production by-Products: Determination of Physicochemical, Antioxidant and Rheological Properties.

Plums (Prunus domestica); red currants (Ribes rubrum); black currants (Ribes nigrum); gooseberries (Ribes uva-crispa); sour cherries (Prunus cerasus); pumpkins (Cuccurbita spp.) are sources for valuable fruit- and berry-juice and cider production. This process leaves a large number of by-products (BP) in the form of pomace, which accounts for up to 80% of the raw material. This by-product represents a rich source of biologically active compounds, especially in the form of different pectic polysaccharides. The pectin extracted from commercial fruits such as citric fruits and apples has high medicinal properties, can be used as edible films and coatings, and is also useful in texture improvement and gel production in the food industry. However, many under-utilized fruits have received little attention regarding the extraction and characterization of their high/value pectin from their by-products. Moreover, the commercial extraction process involving strong acids and high temperature to obtain high-purity pectin leads to the loss of many bioactive components, and these lost components are often compensated for by the addition of synthetic antioxidants and colorants. The aim of the research is to extract pectin from juice production by-products with hot-water extraction using weak organic (0.1 N) citric acid, thus minimizing the impact on the environment. The yield of pectin (PY = 4.47-17.8% DM), galacturonic acid content (47.22-83.57 g 100-1), ash content (1.42-2.88 g 100 g-1), degree of esterification (DE = 45.16-64.06%), methoxyl content (ME = 4.27-8.13%), the total content of phenolic compounds (TPC = 2.076-4.668 µg mg-1, GAE) and the antiradical scavenging activity of the pectin samples (DPPH method (0.56-37.29%)) were determined. Free and total phenolic acids were quantified by saponification using high-pressure liquid chromatography (HPLC). The pectin contained phenolic acids-benzoic (0.25-0.92 µg mg-1), gallic (0.14-0.57 µg mg-1), coumaric (0.04 µg mg-1), and caffeic (0.03 µg mg-1). The pectin extracts from by-products showed glucose and galactose (3.89-21.72 g 100 g-1) as the main neutral sugar monosaccharides. Pectin analysis was performed using FT-IR, and the rheological properties of the pectin gels were determined. The quality of the obtained pectin from the fruit and berry by-products in terms of their high biological activity and high content of glucuronic acids indicated that the products have the potential to be used as natural ingredients in various food products and in pharmaceutical products.

Poly(Butylene Succinate) Hybrid Multi-Walled Carbon Nanotube/Iron Oxide Nanocomposites: Electromagnetic Shielding and Thermal Properties.

To address the ever-increasing electromagnetic interference (EMI) pollution, a hybrid filler approach for novel composites was chosen, with a focus on EMI absorbance. Carbon nanofiller loading was limited to 0.6 vol.% in order to create a sustainable and affordable solution. Multiwall carbon nanotubes (MWCNT) and iron oxide (Fe3O4) nanoparticles were mixed in nine ratios from 0.1 to 0.6 vol.% and 8.0 to 12.0 vol.%, respectively. With the addition of surfactant, excellent particle dispersion was achieved (examined with SEM micrographs) in a bio-based and biodegradable poly(butylene succinate) (PBS) matrix. Hybrid design synergy was assessed for EMI shielding using dielectric spectroscopy in the microwave region and transmittance in the terahertz range. The shielding effectiveness (20-52 dB) was dominated by very high absorption at 30 GHz, while in the 0.1 to 1.0 THz range, transmittance was reduced by up to 6 orders of magnitude. Frequency-independent AC electrical conductivity (from 10-2 to 107 Hz) was reached upon adding 0.6 vol.% MWCNT and 10 vol.% Fe3O4, with a value of around 3.1 × 10-2 S/m. Electrical and thermal conductivity were mainly affected by the content of MWCNT filler. The thermal conductivity scaled with the filler content and reached the highest value of 0.309 W/(mK) at 25 °C with the loading of 0.6 vol.% MWCNT and 12 vol.% Fe3O4. The surface resistivity showed an incremental decrease with an increase in MWCNT loading and was almost unaffected by an increase in iron oxide loading. Thermal conductivity was almost independent of temperature in the measured range of 25 to 45 °C. The nanocomposites serve as biodegradable alternatives to commodity plastic-based materials and are promising in the field of electromagnetic applications, especially for EMI shielding.

Multilayered Composites with Carbon Nanotubes for Electromagnetic Shielding Application.

Bulk polylactic acid (PLA)/multiwall carbon nanotube (MWCNT) composites were prepared and investigated in wide frequency ranges (20 Hz-1 MHz and 24-40 GHz). It was determined that the percolation threshold in bulk PLA/MWCNT composites is close to 0.2 vol.% MWCNT. However, the best microwave dielectric properties and absorption were observed in composites with 3.0-5.0 vol.% MWCNT. Therefore, for future investigations, we selected layered (laminate) polymeric structures with gradual changes in MWCNT concentration from 0.2 to 8.0 vol.% MWCNT. Two approaches to laminate structure designs were examined and compared: a five-layer composite and a nine-layer composite that included four pure PLA middle layers. The addition of MWCNT enhanced the elastic modulus by up to 1.4-fold and tensile strength by up to 1.2-fold, with the best performance achieved at 5.0 vol.% loading. High microwave shielding was observed for these layered PLA/MWCNT structures with a gradient change in MWCNT concentration (up to 26 dB in both transmission and absorption coefficients) in the broad frequency range (from 24 to 40 GHz). Obtained structures are highly anisotropic, and the absorption coefficient is 2-5 dB higher in the direction of MWCNT concentration increase; however, the transmission coefficient is the same in both directions. The properties of microwave absorption are mainly unaffected by the additional polymeric layers. The absorption of the layered structure is greater than the absorption of single-layer composites with an optimal MWCNT concentration of the same thickness. The proposed laminate structure design is promising in the field of efficient electromagnetic shielding.

Comparison of Carbon-Nanoparticle-Filled Poly(Butylene Succinate-co-Adipate) Nanocomposites for Electromagnetic Applications.

Electrostatic dissipative (ESD), anti-static (AS), and electromagnetic interference (EMI) shielding materials are commonly based on commodity fossil-fuel-based plastics. This, in turn, contributes to ever-growing non-biodegradable plastic pollution. Graphene nanoplatelets (GN), multi-walled carbon nanotubes (MWCNT), nanostructured carbon black (NCB), and amorphous carbon black (CB) were utilized as nanofillers to prepare bio-based and biodegradable poly(butylene succinate-co-adipate) (PBSA) nanocomposites. Solvent-cast composites were prepared with 1.1 to 30.0 vol.% nanoparticle loading. The literature mainly focuses on relatively low loadings; therefore, for this research, filler loadings were increased up to 30 vol.% but the maximum loading for NCB and CB loadings only reached 17.4 vol.% due to a lack of dimensional stability at higher loadings. The composites were characterized using tensile testing, volumetric and surface conductivity measurements, thermal conductivity measurements, dielectric spectroscopy in the microwave region, and transmittance in the terahertz range. Tensile tests showed excellent carbon filler compatibility and enhanced tensile strength for loadings up to 5 vol.% (up to 20 vol.% for MWCNT). The highest thermal conductivity values were reached for the MWCNT filler, with the 30.0 vol.% filled composite reaching 0.756 W/mK (262% increase over PBSA). All fillers were able to produce composites that yielded volume conductivities above 10-10 S/m. Composites with MWCNT, GN, and NCB inclusions above the percolation threshold are suitable for EMI applications in the microwave and THz frequency range.

The Impact of Atmospheric Parameters on the Dielectric Permittivity Values of SikaBlock®-M150 and Other Rigid Polyurethane Foams Measured with a Capacitive One-Side Access Sensor.

A shortage of research on the impact of atmospheric parameters on the measured dielectric permittivity values of rigid polyurethane (PU) foams was identified. Therefore, the impact of temperature, pressure, and relative humidity of air in the test room on the measured values of dielectric permittivity of rigid PU foams of different densities as well as monolithic polyurethane was investigated in a year-long experimental research study with a capacitive one-side access sensor. It was shown that relative humidity has the highest correlation with the dielectric permittivity values of rigid PU materials. The detected values of parameters were linked to the water vapour mass in ambient air and its correlation with permittivity of the investigated materials was determined. The warm-up drift and warm-up time of the spectrometer were estimated experimentally. A novel methodology was demonstrated to determine the true permittivity spectrum of rigid PU foams without any involvement of the environmental chamber, desiccators, or saturated salt/water solutions. A relative increase in the measured dielectric permittivity value was estimated numerically for the entire density range of rigid PU foams, i.e., 33-1280 kg/m3 (including monolithic PU).

Bacterial cellulose production by Novacetimonas hansenii MSCL 1646 on apple juice.

Biomaterials and biopolymers, such as bacterial cellulose (BC), are becoming increasingly important as sustainable materials with a wide range of potential applications. However, BC industrial production is associated with several difficulties such as low BC production yields and high production costs; therefore, cheap alternative growth media, e.g. apple juice are being studied intensively. The aim of this study is to evaluate BC synthesis under static conditions on apple juice medium (AJM). The optimal concentration of apple juice in unsupplemented AJM for Novacetimonas hansenii MSCL 1646 was shown by its dilution 1:6 with water, which resulted in 0.89 ± 0.01 g/L of dry BC weight after 10 cultivation days. Low BC synthesis can be associated with insufficient N concentration in apple juice; therefore, different organic and inorganic N sources were evaluated in combination with AJM, and beef extract (5 g/L) was found to be the most suitable. Further, AJM optimisation experiment showed the optimal apple juice and beef extract concentrations as 1:2 and 15 g/L respectively, which resulted in 17.27 ± 0.07 g/L of dry BC weight, which is significantly higher than in standard Hestrin-Schramm (HS) medium (4.07 ± 0.02 g/L). Analysis of mechanical and physical properties showed that use of AJM results in changes in BC properties compared with the standard HS medium. Results of the study indicate that apple juice is an effective and cheap C source that in combination with appropriate N source leads to high BC synthesis and makes it suitable for industrial BC production. KEY POINTS: • Low quality apples can be used as raw material for BC production; • Beef extract improves BC synthesis in apple juice medium; • Use of apple juice and beef extract affect mechanical properties of BC.

Data on FTIR, photo-DSC and dynamic DSC of triethylene glycol dimethacrylate and N-vinylpyrrolidone copolymerization in the presence of ionic liquids.

Here we show the effect of the ionic liquid nature, its content and monomer/crosslinker ratio on the copolymerization of N-vinylpyrrolidone (NVP) with triethylene glycol dimethacrylate (TEGDMA) induced by UV or heat irradiation. For the first time, kinetics curves of photopolymerization NVP with TEGDMA in the presence of ionic liquids are obtained. The ionic liquids EmimBF4, BmimBF4, OmimBF4 and EmimTFSI with different cation and anion structures and lengths of the alkyl radical were varied in photopolymer compositions. To understand the influence of ionic liquids on the polymerization kinetics, photo-DSC, dynamic DSC, and FTIR were performed. Parameters obtained from photo-DSC curves allowed to develop the methodology for the stereolithography of ionogels. The presented data constitutes the complete dataset useful for 3D-printing of ionogels with high accuracy, which is reported in the main article.

Sustainable Wax Coatings Made from Pine Needle Extraction Waste for Nanopaper Hydrophobization.

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.

Hydrothermal Ageing Effect on Reinforcement Efficiency of Nanofibrillated Cellulose/Biobased Poly(butylene succinate) Composites.

Nanofibrillated cellulose (NFC) is a sustainable functional nanomaterial known for its high strength, stiffness, and biocompatibility. It has become a key building block for the next-generation of lightweight, advanced materials for applications such as consumer products, biomedical, energy storage, coatings, construction, and automotive. Tunable and predictable durability under environmental impact is required for high performance applications. Bio-based poly (butylene succinate) (PBS) composites containing up to 50% NFC content were designed and aged in distilled water or at high relative humidity (RH98%). PBS/NFC composites are characterized by up to 10-fold increased water absorption capacity and diffusivity and the data are correlated with model calculations. Aged samples exhibited decreased crystallinity and melting temperature. Incorporation of NFC into PBS showed up to a 2.6-fold enhancement of the elastic modulus, although accompanied by a loss of strength by 40% and 8-fold reduction in the strain at failure of maximally loaded composites. Hydrothermal ageing had almost no influence on the tensile characteristics of PBS; however, there were considerable degradation effects in PBS/NFC composites. Altered reinforcement efficiency is manifested through a 3.7-fold decreased effective elastic moduli of NFC determined by applying the Halpin-Tsai model and a proportional reduction of the storage moduli of composites. The adhesion efficiency in composites was reduced by hydrothermal ageing, as measured Puckanszky's adhesion parameter for the strength, which decreased from 3 to 0.8. For the loss factor, Kubat's adhesion parameter was increased by an order. PBS filled with 20 wt.% NFC is identified as the most efficient composition, for which negative environmental degradation effects are counterbalanced with the positive reinforcement effect. The PBS matrix can be used to protect the NFC network from water.

Lignin and Xylan as Interface Engineering Additives for Improved Environmental Durability of Sustainable Cellulose Nanopapers.

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.

Durability of Biodegradable Polymer Nanocomposites.

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.

Cellulose Nanocrystals vs. Cellulose Nanofibers: A Comparative Study of Reinforcing Effects in UV-Cured Vegetable Oil Nanocomposites.

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.

Polytetrafluoroethylene Films in Rigid Polyurethane Foams' Dielectric Permittivity Measurements with a One-Side Access Capacitive Sensor.

As a non-metallic composite material, widely applied in industry, rigid polyurethane (PUR) foams require knowledge of their dielectric properties. In experimental determination of PUR foams' dielectric properties protection of one-side capacitive sensor's active area from adverse effects caused by the PUR foams' test objects has to be ensured. In the given study, the impact of polytetrafluoroethylene (PTFE) films, thickness 0.20 mm and 0.04 mm, in covering or simulated coating the active area of one-side access capacitive sensor' electrodes on the experimentally determined true dielectric permittivity spectra of rigid PUR foams is estimated. Penetration depth of the low frequency excitation field into PTFE and PUR foams is determined experimentally. Experiments are made in order to evaluate the difference between measurements on single PUR foams' samples and on complex samples "PUR foams + PTFE film" with two calibration modes. A modification factor and a small modification criterion are defined and values of modifications are estimated in numerical calculations. Conclusions about possible practical applications of PTFE films in dielectric permittivity measurements of rigid PUR foams with one-side access capacitive sensor are made.

UV-Light Curing of 3D Printing Inks from Vegetable Oils for Stereolithography.

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.

Spent coffee waste as a renewable source for the production of sustainable poly(butylene succinate) biocomposites from a circular economy perspective.

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.

On the Heuristic Procedure to Determine Processing Parameters in Additive Manufacturing Based on Materials Extrusion.

We present a heuristic procedure for determining key processing parameters (PPs) in materials-extrusion-based additive manufacturing processes. The concept relies on a design-of-experiment approach and consists of eleven "test objects" to determine the optimal combinations of key PPs values, starting with the PPs for printing the first layer and progressing to more complex geometric features, e.g., "bridges". In each of the test objects, several combinations of the known PPs' values are used, and only the values resulting in the best printed-part quality are selected for the following tests. The concept is intrinsically insensitive to different artefacts of the additive manufacturing machine (e.g., discrepancies between the nominal and actual nozzle diameters, and improper calibration of the feeding screws) and the optimal values of key PPs for manufacturing defect-free parts under the actual processing conditions can be determined. We validated the proposed procedure for two common commercial polymer feedstock materials, and we show that, by using the proposed procedure, it is possible to reduce the optimization time down to several hours, as well as to reduce the amount of consumed feedstock material. Tensile tests revealed a strong effect of amorphous and semi-crystalline nature of the polymer on the results of optimization. To the best of our knowledge, this is the first attempt to describe a systematic approach for optimizing PPs for materials extrusion-based additive manufacturing processes without relying on statistical data analysis or virtual simulations. The concept was implemented as a web-tool 3DOptimizer®.