Low Crystallinity Research Articles

Building Ultrastrong, Tough and Biodegradable Thermoplastic Elastomers from Multiblock Copolyesters Via a “Reserve‐Release” Crystallization Strategy

AbstractSimultaneously attaining high strength and toughness has been a significant challenge in designing thermoplastic elastomers, especially biodegradable ones. In this context, we present a class of biodegradable elastomers based on multiblock copolyesters that afford extraordinary strength, toughness, and low‐strain resilience despite expedient chemical synthesis and sample processing. With the incorporation of the semi‐crystalline soft block and the judicious selection of block periodicity, the thermoplastic materials feature low quiescent crystallinity (“reserve”) albeit with vast potential for strain‐induced crystallization (“release”), resulting in their significantly enhanced ultimate strength and energy‐dissipating capabilities. Moreover, a breadth of mechanical responses of the materials – from reinforced elastomers to shape‐memory materials to toughened thermoplastics – can be achieved by orthogonal variation of segment lengths and ratios. This work and the “reserve‐release” crystallization strategy herein highlight the double crystalline multiblock chain architecture as a potential avenue towards reconciling the strength‐toughness trade‐off in thermoplastic elastomers and can possibly be extended to other biodegradable building blocks to deliver functional materials with diverse mechanical performances.

Building Ultrastrong, Tough and Biodegradable Thermoplastic Elastomers from Multiblock Copolyesters Via a "Reserve-Release" Crystallization Strategy.

Simultaneously attaining high strength and toughness has been a significant challenge in designing thermoplastic elastomers, especially biodegradable ones. In this context, we present a class of biodegradable elastomers based on multiblock copolyesters that afford extraordinary strength, toughness, and low-strain resilience despite expedient chemical synthesis and sample processing. With the incorporation of the semi-crystalline soft block and the judicious selection of block periodicity, the thermoplastic materials feature low quiescent crystallinity ("reserve") albeit with vast potential for strain-induced crystallization ("release"), resulting in their significantly enhanced ultimate strength and energy-dissipating capabilities. Moreover, a breadth of mechanical responses of the materials - from reinforced elastomers to shape-memory materials to toughened thermoplastics - can be achieved by orthogonal variation of segment lengths and ratios. This work and the "reserve-release" crystallization strategy herein highlight the double crystalline multiblock chain architecture as a potential avenue towards reconciling the strength-toughness trade-off in thermoplastic elastomers and can possibly be extended to other biodegradable building blocks to deliver functional materials with diverse mechanical performances.

Differences in physicochemical properties and proteomics analysis of spray- and freeze-dried milk powders from bovine, goat, and horse sources

Milk powder, a nutrient-rich dairy product, lacks comprehensive information summarizing its specific properties when produced by spray- and freeze-dried technologies from different sources. Therefore, this study investigated the differences in physicochemical properties, microstructure, and proteome of spray- and freeze-dried milk powders from bovine, goat, and horse sources. The results revealed that spray-dried milk powder exhibited a smaller particle size, lower air content within the powder particles, inferior reconstitution properties, and lower lactose crystallinity compared with freeze-dried milk powder. Additionally, among the studied varieties, horse milk powder showed the lowest flowability but the most effective reconstitution properties. Proteomic analysis indicated that freeze-dried milk powder exhibited higher levels of immune-related proteins, including complement C3, C7, and complement factor B, and antimicrobial enzymes such as lysozyme and lactoperoxidase compared with spray-dried milk powder. Furthermore, specific milk powders contained more immune-related proteins such as serum amyloid A, myeloid antimicrobial peptide-28, polymeric immunoglobulin receptor, and mucin-1 compared with bovine milk powder. These findings contribute to a deeper understanding of the differences in the physical-chemical properties and potential biological functions of spray- and freeze-dried milk powders from various sources, which may help in further optimizing specific milk powder processing technologies.

Effect of synthesis temperature on the properties and photocatalytic performance of peroxo-titanate nanotubes prepared by bottom-up synthesis method

The alkaline treatment synthesis of titania/titanate nanotubes (TNTs) requires highly concentrated alkaline solutions (≥ 10 mol/L), which pose environmental and productivity limitations. In contrast, a bottom-up synthesis method for peroxo-titanate nanotubes (PTNTs) has been developed. This method offers two advantages: it can synthesize materials using low-concentration alkaline solutions (1.5 mol/L) and produce photocatalytic materials that are responsive to visible light. In general, the higher the crystallinity of a catalyst, the better its properties. However, PTNTs synthesized at temperatures close to their boiling point (around 100 °C) exhibit low crystallinity. This study hypothesizes a hydrothermal synthesis method at higher temperatures will enhance the crystallinity and photocatalytic performance of PTNTs, synthesizing them at temperatures ranging from 120 to 200 °C using a method capable of exceeding the boiling point. Higher synthesis temperatures resulted in improved morphological and crystallographic properties of the PTNTs. However, the formation of peroxo-bonding, crucial for visible light responsiveness, decreased. Nevertheless, peroxo-bonding formation was still achievable at the highest temperature of 200 °C, and the sample exhibited the best Rhodamine B (Rh B) photodegradation performance under visible light due to its enhanced specific surface area and crystallinity. This study highlights the novelty and environmental significance of hydrothermally synthesized PTNTs as superior photocatalysts by optimizing the synthesis temperature while using lower concentration alkaline solutions.

Synthesis, Characterization, Density Functional Theory Study, Antibacterial Activity and Molecular Docking of Zeolitic Imidazolate Framework‐8

ABSTRACTIn this study, Zeolitic Imidazolate Framework‐8 (ZIF‐8) nanomaterials were synthesized using a co‐precipitation one‐pot method that uses ethanol, methanol, and water as solvents for the precursors (2‐methylimidazole and Zinc nitrate hexahydrate), resulting in yields of 66.77%, 73.14%, and 68.12%, respectively. The as‐synthesized ZIF‐8 nanomaterials were thoroughly characterized by X‐ray diffraction analysis, transmission electron microscopy, ultraviolet–visible spectroscopy, and Fourier‐transform infrared spectroscopy. The X‐ray diffraction analysis showed that the crystallite size of ethanol‐based ZIF‐8 (24.76 ± 1.67 nm) was smaller than those synthesized in water (26.92 ± 1.89 nm) and methanol (31.39 ± 1.03 nm). However, methanol‐based ZIF‐8 exhibited lower crystallinity (85.93%) than water‐based ZIF‐8 (91.48%) and ethanol‐based ZIF‐8 (92.71%). Zeta potential studies revealed that ethanol‐based ZIF‐8 had a larger surface charge (+37 mV) than water‐based ZIF‐8 (+35 mV) or methanol‐based ZIF‐8 (+24 mV). Transmission electron microscopy analysis confirmed particle sizes of 54.35 ± 2.11 nm for ethanol‐based ZIF‐8, 57.91 ± 2.26 nm for water‐based ZIF‐8, and 63.25 ± 4.12 nm for methanol‐based ZIF‐8. Thermogravimetric analysis indicated thermal stability up to 800 °C, with mass losses of 55.98% for ethanol‐ZIF‐8, 50.12% for water‐based ZIF‐8, and 65.36% for methanol‐based ZIF‐8 by 600 °C. In antibacterial studies, water‐based ZIF‐8 exhibited the largest zone of growth inhibition (17.30 ± 0.26 mm) against Escherichia coli compared to ethanol‐based ZIF‐8 (15.57 ± 0.32 mm) and methanol‐based ZIF‐8 (14.70 ± 0.20 mm). Pearson's correlation study revealed that zeta potential, crystallinity, and antibacterial activity are positively related. Furthermore, water‐based ZIF‐8, with a minimum inhibitory concentration of 50 μg/100 μL, confirmed evident cell membrane disruption. Molecular docking experiments revealed ZIF‐8's significant binding affinity for the E. coli protein 5AZC, supporting its robust antibacterial activity.

Regulation of protonation in aramid nanofiber films for improved mechanical properties

Abstract Aramid nanofibers (ANFs) are a strong and heat resistant nanomaterial that can be isolated from commercial poly(p-phenylene terephthalamide) (PPTA) fibers. These nanofibers allow bottom-up self-assembly to form macroscale structures in various form factors through a simple reprotonation process. However, the mechanical properties of these reassembled ANF structures often fall short of those of PPTA fibers, mainly due to insufficient packing, non-uniform microstructures, and low crystallinity. In this study, we present ANF films with improved mechanical properties prepared by a repeated spin-coating technique combined with a reprotonation process using deionized water and formic acid at concentrations ranging from 20 to 60 wt.%. Extensive analyses were performed on the resulting ANF films to evaluate their surface and cross-sectional morphologies, chemical bonds and compositions, thermal stabilities, and mechanical properties. The fabricated ANF films exhibited remarkable performance, with an elastic modulus of 6.7 GPa, tensile strength of 680 MPa, and toughness of 7.7 MJ m−³, while maintaining the inherent thermal stability of PPTA fibers. These properties significantly exceed those of previously reported ANF films, broadening the potential applications for ANF films in various fields.

Single-crystalline High-κ GdOCl dielectric for two-dimensional field-effect transistors

Two-dimensional (2D) dielectrics, integrated with high-mobility semiconductors, show great promise to overcome the scaling limits in miniaturized integrated circuits. However, the 2D dielectrics explored to date still face the challenges of low crystallinity, diminished dielectric constant, and the lack of effective synthesis methods. Here, we report the controllable synthesis of ultra-thin gadolinium oxychloride (GdOCl) nanosheets via a chloride hydrate-assisted chemical vapor deposition (CVD) method. The resultant GdOCl nanosheets display good dielectric properties, including a high dielectric constant (high-κ) of 15.3, robust breakdown field strengths (Ebd) exceeding 9.9 MV/cm, and minimal gate leakage currents of approximately 10−6 A/cm2. The top-gated GdOCl/MoS2 field-effect transistors (FETs) exhibit commendable switch characteristics, a negligible hysteresis of ~5 mV and a subthreshold swing down to 67.9 mV dec−1. The GdOCl/MoS2 FETs can also be employed to construct functional logic gates. Our study underscores the significant potential of the 2D GdOCl dielectric for innovative high-speed operated nanoelectronic devices.

Spatial heterogeneity of sediments on a topographically diverse descending plate at convergent margins: An example from the outer slope of the Mariana Trench

Unraveling deep ocean sediment composition and its controlling mechanisms is crucial to understanding the interplay between the Earth's surface and the deep Earth. Convergent margins are generally featured by various seafloor landforms, but how submarine topography affects sediment accumulation processes remains poorly understood. Here we focus on submarine surface sediments from the outer slope of the Mariana Trench (covering water depths of 1218–6310 m) and combine microscopic observation, clay mineralogy, and elemental geochemistry to characterize sediment composition and to reveal physical, chemical, and biological sedimentary processes at topographically diverse convergent margins. Smear slide observations indicate that foraminifera shells dominate in shallow areas, while pelagic clays and diatom oozes prevail in trench and slope areas. Clay minerals primarily consist of illite (26–98 %) with low crystallinity index values and diverse chemical index values, followed by chlorite (0–45 %) and kaolinite (0–29 %). Smectite (0–61 %, 46 of 70 samples have smectite contents <5 %) of the samples from the outer slope area is low but appears dominant close to the trench. Bulk element compositions are mainly affected by the relative calcareous, siliceous, and lithogenous components that dissolved or accumulated inconsistently as submarine topographic feature changes. Our results imply that submarine topography and sediment provenance lead to significant heterogeneity of sediment composition at topographically diverse convergent margins. The submarine topographic relief, together with associated bathymetry and deep-sea circulation primarily controls carbonate deposition on the Caroline Plateau, and influences the sinking particles (including diatom shells and arc volcanic-sourced materials) accumulation in the trench basin. Continent-derived aeolian dust introduces illite-rich detritus, while localized volcanism potentially contributes to smectite-rich sediment in certain topographic provinces. We propose that the deep sea sedimentation processes in the Mariana convergent system are more diverse and complex than those at the margins with relatively plain topographic characteristics (e.g., the Japan Trench). The significant heterogeneity on descending plates along convergent margins may lead to various subduction behaviors. These findings contribute to a better understanding of deep ocean sediment source-to-sink systems and have implications for Earth's material cycle and multi-sphere interaction studies.

Enhancing the Stereocomplex Crystallization of PLLA/PDLA Symmetric Blend by Controlling the Degree of Molecular Chain Entanglement

In order to enhance the content of stereocomplex crystals (SC) in poly L-lactic acid (PLLA)/poly D-lactic acid (PDLA) symmetric blend, thereby improving the defects of low crystallinity and poor heat resistance of polylactic acid (PLA)-based materials, the samples with different entanglement degrees were prepared by freezing extration method. The critical overlap concentration of the blend system was quantitatively obtained using an Ubbelohde viscometer. Based on this concentration, samples with a series of concentration gradient were prepared to control the different degrees of molecular chain entanglement inside. The results indicated that the chain disentanglement could greatly increase the content of SC in the blend, whether in the precipitation crystallization or the melt crystallization process. Especially after the isothermal crystallization for 30min at 130oC, the L/D-0.1 sample with the highest degree of disentanglement almost only formed SC, accounting for 95.2% of the total crystallinity. Samples with lower entanglement degree had more crystal nuclei and faster growth rate of formed spherulites. For completely entangled sample L/D-50, the crystal nucleus of homo-crystalls (HC) could be considered as SC. Besides, the Vicat softening temperature (VST) of L/D-0.1 sample increased from 79.9oC of L/D-50 sample to 103.8oC with an obvious increase of 24.9oC. All these results provide new ideas for improving the performance of PLA-based materials and show promising development prospects of green and sustainable polymers.

Compatibilization of Post‐Consumer Recycled Polypropylene/Polyethylene Binary Blends

ABSTRACTThis work investigates the compatibilization of post‐consumer recycled binary blends of polypropylene/polyethylene (PP/PE), with either high‐density PE (HDPE) or linear low‐density PE (LLDPE). Ethylene‐octene elastomer copolymers from the olefin block copolymers (OBC) family, Dow's INFUSE 9107 and INFUSE 9507, were used as compatibilizers at 4, 6, and 8 wt%. Two different recycled PP/PE blends were used: a 50/50 by weight PP/HDPE white blend (0 W), and a black blend (0B) comprising 85/15 PP/LLDPE by weight. The mechanical properties, thermal properties, and morphology of these injection‐moldable blends indicate that compatibilization took place. Elongation at break and tensile impact strength increased with compatibilizer content, especially with INFUSE 9107. For instance, the impact strength of 0 W increased almost three‐fold with 8 wt% OBC, while that of 0B was doubled with 6 wt% OBC. The tensile strain at break increased up to six‐fold with 8 wt% OBC, reaching 360% and 180% for the white and black blends, respectively. Elastic Moduli decrease to some extent, but remain within the range of applicability of PP‐based compounds. The melt flow index (MFI) values, above 20 g/10 min for 0 W and 7–8 g/10 min for 0B, allow for injection molding of these blends. Moreover, a two‐phased morphology became less apparent, the improved compatibility being driven by the lower interfacial surface energy of the blend and more efficient stress transfer between the phases. INFUSE 9107 achieved better impact strength and elongation results, mainly in the white blends, and this is explained by the better compatibility, its localization at the interface, and the lower crystallinity of the compatibilized blend.

Simple enzymatic depolymerization process based on rapid ball milling pretreatment for high-crystalline polyethylene terephthalate fibers

The high crystallinity (30 %–50 %) of discarded polyester textile waste limits the industrialization of its clean enzymatic depolymerization. In this study, a simple process based on ball milling pretreatment was developed to achieve effective enzymatic hydrolysis of high-crystalline polyester fiber. Ball milling was selected for its short, mild, and chemical-free process, which achieved a remarkable 23.8-fold (60.9 %) increase in terephthalic acid (TPA) yield from waste polyethylene terephthalate (PET) degradation, along with high TPA purity in the released soluble compounds. Just 30 min of ball milling at room temperature induced polyester amorphization, resulting in polyester with 12 % lower crystallinity compared with untreated polyester (51 %), while simultaneously increasing the surface roughness of polyester, thereby enhancing the efficiency of enzymatic hydrolysis. The simple process for effective enzymatic-depolymerization of waste polyester fiber developed in this study has potential industrial applications

Effect of solvent in the solvothermal synthesis of nickel(II)-terephthalate complex

This research aims to replace the use of dimethylformamide (DMF) with a greener solvent in the solvothermal synthesis of nickel(II)-terephthalate complex. Effect of solvent on the crystallinity degree, thermal stability, and band gap energy of the synthesized complex are also studied. The synthesis was carried out using solvothermal method at 150 0C for 10 hours with a Ni(II) : terephthalate acid mol ratio of 1:1 in several H2O:DMF solvent compositions (1:0; 1:1; and 0:1). The precipitated products underwent characterization using ATR-IR, P-XRD, SEM, TGA, Surface Area Analyzer, and UV-DRS. Findings revealed the successful formation of the Ni(II)-terephthalate complex using three different solvent compositions (H2O/DMF = 1:0, 1:1, and 0:1). This suggests that the complex can be synthesized using more environmentally friendly solvents, potentially reducing or substituting the use of DMF solvent. However, the solvent affects the characteristics of the synthesized complex, in which green block microcrystalline solid was obtained when using water as the solvent, meanwhile green aggregates with lower crystallinity degree was precipitated out when using DMF or H2O-DMF. The Ni(II)-terephthalate complexes obtained from the H2O and H2O-DMF solvents are different to that of from the DMF solvent, but they both has identical powder diffraction pattern with previously reported compound of [Ni3(OH)2(C8H4O4)2(H2O)4].2H2O. Furthermore, the use of water as the solvent increase the crystallinity degree and thermal stability of the complex but the band gap energy of the synthesized Ni(II)-terephthalate complex compared to that of obtained from the DMF solvents.

Encapsulation Engineering of Sulfur into Magnesium Oxide for High Energy Density Li-S Batteries.

This study addresses the persistent challenge of polysulfide dissolution in lithium-sulfur (Li-S) batteries by introducing magnesium oxide (MgO) nanoparticles as a novel additive. MgO was integrated with sulfur using a scalable process involving solid-state melt diffusion treatment followed by planetary ball milling. XRD measurements confirmed that sulfur (S8) retains its orthorhombic crystalline structure (space group Fddd) following the MgO incorporation, with minimal peak shifts indicating slight lattice distortion, while the increased peak intensity suggests enhanced crystallinity due to MgO acting as a nucleation site. Additionally, Raman spectroscopy demonstrated sulfur's characteristic vibrational modes consistent with group theory (point group D2h) and highlighted multiwalled carbon nanotube (MWCNT's) D, G, and 2D bands, with a low ID/IG ratio (0.47), which indicated low defects and high crystallinity in the prepared cathode. The S-MgO composite cathode exhibited superior electrochemical behavior, with an initial discharge capacity (950 mA h g-1 at 0.1 C), significantly improved compared to pristine sulfur's. The presence of MgO effectively mitigated the polysulfide shuttle effect by trapping polysulfides, leading to enhanced stability over 400 cycles and the consistent coulombic efficiency of over 99.5%. After 400 cycles, EDS and SEM analyses confirmed the structural integrity of the electrode, with only minor fractures and slight sulfur content loss. Electrochemical impedance spectroscopy further confirmed the enhanced performance.

Microwave-associated ZnCl2 pretreatment followed by enzymatic hydrolysis for high-efficiency production of nanocellulose from Eucalyptus dissolving pulp

Herein, we developed a novel microwave-associated ZnCl2 pretreatment followed by enzymatic hydrolysis for high-efficiency and environmentally friendly production of nanocellulose. With a short pretreatment time (60 s), nanocellulose was yielded with a high overall yield of 87.99 % from Eucalyptus Dissolving Pulp (EDP). Characterization analysis revealed that microwave-associated ZnCl2 pretreatment can efficiently swollen the structure of EDP, and after enzymatic hydrolysis, the nanocellulose in spherical shape was formed with abundant functional groups, low crystalline index, and poor thermal stability. By Energy Dispersive X-Ray Spectroscopy (EDS) and inductively coupled plasma mass spectrometry (ICP-MS) analysis, approximately 20 wt% of zinc distributed on the surface and in the interior of cellulose, that may lead to the low Zeta potential of the nanocellulose and the formation of nanospheres. Furthermore, through optimization of the pretreatment process, it was feasible to increase the solid concentration of EDP to 3 wt% while concurrently reducing the ZnCl2 concentration to 0.1 mol (ZnCl2·9H2O). Under this condition, ultrafine cellulose nanocrystals (CNC) and cellulose nanofiber (CNF)/CNC blend were produced with an outstanding yield of 93.3 %. Moreover, the recyclability of ZnCl2 post-pretreatment was demonstrated, as ZnCl2 could be efficiently reused for subsequent pretreatment cycles. Notably, even after five cycles of recycling, the nanocellulose yield remained consistently above 90 %. Overall, this study highlights the viability and sustainability of microwave-assisted ZnCl2 pretreatment for efficient nanocellulose production, offering a sustainable and cost-effective route for industrial-scale applications.

Recrystallizing Sputtered NiOx for Improved Hole Extraction in Perovskite/Silicon Tandem Solar Cells

AbstractSputtering nickel oxide (NiOx) is a production‐line‐compatible route for depositing hole transport layers (HTL) in perovskite/silicon tandem solar cells. However, this technique often results in films with low crystallinity and structural flaws, which can impair electronic conductivity. Additionally, the complex surface chemistry and inadequate Ni3+/Ni2+ ratio impede the effective binding of self‐assembled monolayers (SAMs), affecting hole extraction at the perovskite/HTL interface. Herein, these issues are addressed using a recrystallization strategy by treating sputtered NiOx thin films with sodium periodate (NaIO4), an industrially available oxidant. This treatment improved crystallinity and increased the Ni3+/Ni2+ ratio, resulting in a higher content of nickel oxyhydroxide. These enhancements strengthened the SAM's anchoring capability on NiOx and improved the hole extraction at the perovskite/HTL interface. Moreover, the NaIO4 treatment facilitated Na+ diffusion within the perovskite layer and minimized phase separation, thus improving device stability. As a result, single‐junction perovskite solar cells with a 1.68 eV bandgap achieve a power conversion efficiency (PCE) of 23.22% for an area of 0.12 cm2. Perovskite/silicon tandem cells with an area of 1 cm2 reached a PCE of 30.48%. Encapsulated tandem devices retained 95% of their initial PCE after 300 h of maximum power point tracking under 1‐sun illumination at 25 °C.

Epitaxial Orientation-Controlled High Crystallinity and Ferroelectric Properties in Hf0.5Zr0.5O2 Films.

Hafnium-based binary oxides are essential for fabricating nanoscale high-density ferroelectric memory devices. However, effective strategies to control and improve their thin-film single crystallinity and metastable ferroelectricity remain elusive, hindering potential applications. Here, using NdGaO3 (NGO) substrates with four crystalline orientations, we report a systematic study of the structural characterizations and ferroelectric properties of epitaxial Hf0.5Zr0.5O2 (HZO) films, demonstrating orientation-controlled high crystallinity and enhanced ferroelectric properties. HZO films grown on NGO(001) and NGO(110) substrates exhibit relatively low crystallinity and a significant presence of the monoclinic phase. In contrast, HZO films grown on NGO(100) and NGO(010) possess high single crystallinity and a dominant ferroelectric phase. These differences are attributed to the surface symmetry of the NGO substrate, which favors the formation of 4- or 2-fold domain configurations. Moreover, the optimized HZO films exhibit a large polarization (2Pr) of ∼50 μC/cm2, enhanced fatigue behavior up to 1011 cycles, improved retention of 2Pr ∼ 40 μC/cm2 after 10 years, and characteristic polarization switching speeds in the submicrosecond range. Our results highlight the importance of modulating the single crystallinity and ferroelectric phase fraction of HfO2-based films to enhance ferroelectric properties, further revealing the potential of epitaxial symmetry engineering.

Surface weak ferromagnet coupling induced giant room-temperature spontaneous exchange bias in antiferromagnet Fe3BO6 polycrystals.

The spontaneous exchange bias effect (SEB) has wide application prospects in information storage technologies. In this study, nanoscale raw materials were used to fabricate antiferromagnetic Fe3BO6 polycrystals. The obtained Fe3BO6 exhibited a large SEB effect, where the value of the spontaneous exchange bias field at room temperature was as large as ∼4234 Oe. The room-temperature training effect, temperature-dependence, and maximum field-dependence of the HSEB were investigated. We propose that this giant SEB originates from the exchange-coupling interactions between the weak ferromagnetic surface state and the bulk antiferromagnetic state. The theoretical analysis results were further verified by comparing the magnetic properties of the Fe3BO6 with relatively low crystallinity. The results of this investigation will help find promising candidate materials for devices based on the SEB effect.

Electrospun Pt-TiO2 nanofibers Doped with HPA for Catalytic Hydrodeoxygenation

Electrospinning is utilized to fabricate catalytic nanofiber scaffold for biocrude upgrading in hydrodeoxygenation (HDO) following computational studies suggesting the need for nano-catalysts for efficient HDO conversion and selectivity. Here, Pt-TiO2 nanofibers are fabricated through electrospinning, followed by wet impregnation with a heteropoly acid (HPA), tungstosilicic acid. Intensive heat treatments were incorporated during and after processes to obtain a HPA doped Pt-TiO2 nano-catalyst. Catalytic HDO was performed in a batch reactor with phenol as the raw biocrude dissolved in hexadecane. The HPA doped Pt-TiO2 catalyst demonstrated promising HDO performance of 37.2% conversion and a 78.9% selectivity to oxygen free benzene and the remainder 21.1% as diphenyl ester as a result of esterification by acidic components of the catalyst. Additionally, BET surface area characterization show a low surface area 16.9 m2 g−1 significantly lower than existing commercial catalysts and a mesoporous nature suitable for selectivity. The presence of HPA on the anatase nanofiber compensated for low platinum nanoparticles crystallinity on the nanofibers. This work might create needed alternatives for preparing HDO catalysts for efficient aromatics production.

Improved thermal, mechanical, and dielectric properties of thermotropic liquid crystalline poly(ester amide)s containing lactam-derived segmental units

We prepared two different series of thermotropic liquid crystalline poly(ester amide)s (TPEAs) via bulk polycondensation reactions of 4-hydroxybenzoic acid (HBA, 75.0 mol %) and 6-hydroxy-2-naphthoic acid (HNA, 25.0–17.5 mol %) with ε-caprolactam (CL, 0.0–7.5 mol %) or γ-butyrolactam (BL, 0.0–7.5 mol %). Our investigation aimed to explore the impact of lactam-derived aliphatic amide units’ length and content on the liquid crystalline feature, microstructure, thermal transition, thermal stability, mechanical/relaxational/rheological behavior, and dielectric characteristics of TPEAs. The molecular structure and fibrillar formation of TPEAs containing aliphatic amide units were confirmed through FT-IR and SEM analysis. With increasing CL or BL-derived units from 1.0 mol % to 5.0 mol %, we observed an increase in crystallinity, glass transition temperature, melting temperature, complex melt viscosity, and storage modulus of TPEAs, attributed to the enhanced intermolecular hydrogen bonding interactions. However, at 7.5 mol % CL or BL-derived unit content, these properties decreased due to increased chain irregularity as well as lowered crystallinity. Notably, the dielectric constants (3.31–3.04 at 2 MHz) of TPEAs decreased with the increase of lactam-derived aliphatic amide units owing to the restricted chain mobility by intermolecular hydrogen bonding interactions. We believe that the TPEAs synthesized in this study hold significant potential for applications in technical plastics, superfibers, and printed circuit board materials.

PLA based biodegradable bionanocomposite filaments reinforced with nanocellulose: development and analysis of properties

The 3D printing technique has recently become more prevalent among researchers for the fabrication of nanocomposites. The low crystallinity of polylactic acid (PLA) leads to the poor mechanical and thermal properties of its 3D-printed products, which restrict their applications in many fields. To overcome the limitations of PLA, the present work aims to develop PLA-based bionanocomposite filaments with varying percentages (1, 3, and 5 wt%) of crystalline nanocellulose (CNC) through a single screw extruder. The filaments will be further utilized for the development of bionanocomposite samples to evaluate their properties. The effect of CNC reinforcement on the chemical structure of the filaments was analyzed by FTIR analysis. XRD analysis revealed that the crystallinity of the filaments was significantly improved due to the nucleating effect of CNC. The maximum crystallinity was observed in the filament containing 1 wt% CNC, which was 26% higher than the pure PLA filament. The thermal and mechanical performance of the filaments was also considerably improved after CNC reinforcement, which was confirmed by DSC-TGA and tensile test analysis. The maximum tensile strength and tensile modulus were observed to be 48.9 MPa and 1700 MPa, respectively, in the filament reinforced with 1 wt% CNC, which was 35.5% and 21.89%, respectively, higher than those of the pure PLA filament. Rheological analysis showed that the complex viscosity, storage modulus, and loss modulus of the filaments were significantly affected by the reinforcement of CNC.