Amorphous Regions Research Articles

Innovative Mn3−xO4−y@NCA design: Leveraging Mn/O vacancies and amorphous architecture for enhanced sodium-ion storage

Manganese-based oxide electrode materials suffer from severe Jahn-Teller (J-T) distortion, leading to severe cycle instability in sodium ion storage. However, it is difficult to adjust the electron at d orbitals exactly to a low spin state to eliminate orbital degeneracy and suppress J-T distortion fundamentally. This article constructed concentration-controllable Mn/O coupled vacancy and amorphous network in Mn3O4 and coated it with nitrogen-doped carbon aerogel (Mn3−xO4−y@NCA). The existence of Mn/O vacancies has been confirmed by scanning transmission electron microscopy (STEM) and positron annihilation lifetime spectroscopy (PALS). Atomic absorption spectroscopy (AAS) and X-ray photoelectron spectroscopy (XPS) determine the most optimal ratio of Mn/O vacancies for sodium ion storage is 1:2. Density functional theory (DFT) calculations prove that Mn/O coupled vacancies with the ratio of 1:2 could exactly induce a low spin states and a d4 electron configuration of Mn, suppressing the J-T distortion successfully. The abundant amorphous regions can shorten the transport distance of sodium ions, increase the electrochemically active sites and improve the pseudocapacitance response. From the synergetic effect of Mn/O coupled vacancies and amorphous regions, Mn3−xO4−y@NCA exhibits an energy density of 37.5 W h kg−1 and an ultra-high power density of 563 W kg−1 in an asymmetric supercapacitor. In sodium-ion batteries, it demonstrates high reversible capacity and exceptional cycling stability. This research presents a new method to improve the Na+ storage performance in manganese-based oxide, which is expected to be generalized to other structural distortion.

Atomistic Simulations of the Shock and Spall Behavior of the Refractory High-Entropy Alloy HfNbTaTiZr

AbstractUsing molecular dynamics simulation, we study the effect of a shock wave on the refractory high-entropy alloy HfNbTaTiZr. A single-crystalline sample, shocked along the [001] direction, is considered. The initial compression leads to only weak dislocation activity and a bcc $$\rightarrow$$ → hcp transformation in some regions of the sample. After the shock wave is reflected from the free back surface of the sample, hcp transforms back to bcc, and twins are formed in the bcc phase. The sample spalls under the high tensile pressures developing after wave reflection. In this stage, we observe dislocation activity from the twin boundaries and inside the nanograins generated by twinning. Under the large tensile stresses, some fcc phase appears together with disordered amorphous regions where voids nucleate and lead to spall. The fracture surfaces follow the twin boundaries set up in the compression phase. The spall strength is similar to the one found in simulations of other bcc metals at similar strain rates. Similar simulations for the equiatomic HfNbTaZr HEA show the same qualitative behavior, with twins and reduced dislocation activity, but without phase transformations.

Effect of Acetylation on the Morphology and Thermal Properties of Maize Stalk Cellulose Nanocrystals: A Comparative Study of Green-Extracted CNC vs. Acid Hydrolysed Followed by Acetylation

This study highlights the advantages of employing acetylation to enhance the morphology and thermal properties of cellulose nanocrystals (CNCs) derived from maize stalks. Utilizing a green synthesis approach for CNC extraction, this research presents a novel comparison between green extracted CNCs, and their acid hydrolysed, followed by their acetylated counterparts (ACCNCs). This comparison reveals significant improvements in the properties of acetylated CNCs over those produced through conventional acid hydrolysis. The study employs advanced characterization techniques, including Fourier Transform Infrared (FTIR) spectroscopy, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Thermogravimetric Analysis (TGA), to analyze untreated maize stalk extracted cellulose, green extracted CNCs, and acetylated CNCs. FTIR spectroscopy identifies changes in functional groups, underscoring the efficacy of the extraction and modification processes. XRD analysis demonstrates a beneficial transformation from cellulose I to cellulose II allomorphs post-acetylation, with increased crystallinity index values indicating effective removal of amorphous regions. SEM imaging reveals the preservation of rod-like structures in CNCs, while acetylated CNCs exhibit advantageous morphological changes, such as reduced nanocrystal length and increased branching. TGA results show superior thermal stability in green extracted CNCs and favorable thermal degradation behavior in acetylated CNCs. Overall, this study underscores the potential of acetylation to develop sustainable nanomaterials with tailored properties, offering significant advancements for various applications. Emphasizing the advantages of the prepared ACCNCs and the green synthesis method over traditional acid hydrolysis extraction, this research paves the way for innovative applications in diverse fields.

Biodegradation study of poly(hydroxybutyrate-co-hydroxyvalerate)/halloysite/oregano essential oil compositions in simulated soil conditions

The aim of this work was to evaluate the influence of halloysite clay nanoparticles – unmodified (Hal) and organically modified (mHal) – and oregano essential oil (OEO), used as an antimicrobial agent in active packaging, on the biodegradation behavior of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) films. Five samples were prepared by melt mixing using 3 wt% clay, and 8 wt% and 10.4 wt% OEO. PHBV compositions containing OEO presented the highest rate of biodegradation, achieving 46% of mass loss after aging for 12 weeks in simulated soil. The addition of clay nanoparticles reduced the polymer's biodegradation to 32%. The compositions containing OEO showed a rough and layered surface with visible cracks, indicating degradation occurring through layer-by-layer erosion from the surface. This degradation was confirmed by the chemical changes on the surface of all samples, with a slight decrease in molar masses. The composition containing 8 wt% OEO presented an increase in the crystallization degree as a result of the preferential consumption of amorphous phase, whereas for the compositions containing clay nanoparticles, both crystalline and amorphous regions were degraded at similar rates. Therefore, the combination of additives allows the biodegradation process of PHBV to be controlled for use in the production of active packaging.

The key role of unique crystalline property in the hydrolytic degradation process of microcrystalline cellulose-reinforced stereo-complexed poly(lactic acid) composites

Stereo-complexed poly(lactic acid) (SC-PLA) has unique stereo-complexed crystallites (SC) and homogeneous crystallites (HC), but the effect of this special crystalline property on the hydrolytic degradation of SC-PLA has not been researched. In this study, the hygrothermal aging behaviour of injection-molded SC-PLA and SC-PLA/microcrystalline cellulose (MCC) composites at different temperatures (25 °C and 60 °C) was investigated from micro- and macroscopic perspectives. The results demonstrated that the hydrolysis of SC-PLA was sequentially dominated by the amorphous region, the homogeneous crystalline region, the stereo-complexed crystalline region (three stages). The hydrolytic degradation of SC-PLA only completed the first stage after 4 weeks aging at 25 °C, while it was in the third stage after 4 weeks aging at 60 °C. On this basis, the accelerating effect of 10 wt% MCC on the hydrolysis process of SC-PLA at different stages was investigated. It was found that MCC shortened the hydrolysis time in the stereo-complexed crystalline region by reducing the rearrangement of amorphous structure to form SC and causing cracks and interfacial deterioration by water absorption-swelling-degradation. In addition, the thermal properties and impact strength of SC-PLA and SC-PLA/MCC composites decreased dramatically due to rapid hydrolytic degradation at 60 °C. Overall, the results of this study can provide theoretical basis for the application of SC-PLA and SC-PLA/MCC composites in hygrothermal environment.

Green preparation of cellulose nanocrystals and nanofibers by ball milling assisted citric acid hydrolysis

In order to solve the drawbacks of carboxylated cellulose nanocrystals (CNCs) prepared by critic acid (CA) hydrolysis method, such as low yield and low esterification degree, herein, ball milling assisted CA hydrolysis method was applied to obtain carboxylated CNCs and cellulose nanofibers (CNFs) with fine and uniform size, high yield and carboxyl content, good crystallinity, and good thermal stability. It was discovered that the diameter of CNCs and CNFs were decreased and the size uniformity was improved. The yield of CNCs was obviously improved to 39.8 % due to the promoted esterification reaction, which was 3.3 times of that without ball milling. Moreover, the carboxyl group content of CNCs and CNFs were improved to a maximum of 0.52 and 0.48 mmol/g, respectively. As ball milling progressing, more amorphous regions were destroyed and cellulose bundles were dissociated, resulting in CNCs and CNFs with high crystallinity. The thermal decomposition temperature of CNCs and CNFs were ranged from 317 to 331℃, which was higher than that had reported. This work provided an effective route for carboxylated CNCs with good yield, esterification degree and other performance, which was beneficial for the subsequent applications in the field of biomaterials.

Enhanced EMI shielding effectiveness of green Eucommia ulmoides gum composites through heterogeneous and crystalline structures

In order to mitigate the increasing severity of electromagnetic interference (EMI), it is imperative to develop advanced rubber composites. Despite recent advancements in structural design and filler hybridization for enhancing their EMI shielding performance, challenges persist in terms of suboptimal mechanical properties and intricate processing techniques. To overcome these limitations, bio-based Eucommia ulmoides gum (EUG) composites with segregated network structures were fabricated by simple mechanical blending, capitalizing on the characteristics of highly cross-linked rubbers with restricted molecular chains. Highly cross-linked EUG (HCE) effectively segregated the conductive fillers into the EUG phase, while the crystallization of EUG promoted the dispersion of fillers within the amorphous region of the EUG. Therefore, a highly efficient 3D conductive network was formed due to the segregated structure and crystallization, enabling the EUG/HCE/CNT composite to achieve an exceptional shielding effectiveness (SE) value of 83.0 dB with a high absorption loss ranging from 8.2 GHz to 12.4 GHz.

High wear resistance of metallocene polyethylene with long-chain branch for artificial joints

Ultra-low-wear polyethylene (ULWPE) is a promising material for artificial joint implants, owing to its good biocompatibility and wear resistance. However, its molecular weight is almost an order of magnitude lower than that of Ultrahigh molecular weight polyethylene (UHMWPE). The mechanism between wear resistance and the structure of ULWPE is still unknown. This study analyzed their attributes from microstructure to macroscopic performance and revealed the wear resistance mechanisms of ULWPE by conducting an in-depth investigation of four types of polyethylene, including ULWPE, UHMWPE, and high-density polyethylene. Impact tests showed that ULWPE, with a molecular weight of 282 kg/mol, exhibited an impact energy of 110 kJ/m2, surpassing the 97 kJ/m2 recorded for UHMWPE (molecular weight over 5000 kg/mol). Furthermore, tribology tests indicated that the wear rate of the most anti-wear ULWPE was 4.479 ± 0.040 mm³/Mc, which was significantly lower than the 5.601 ± 0.456 mm³/Mc for UHMWPE. The excellent mechanical properties and wear resistance of ULWPE were derived from its unique structure. Dynamic rheological assessments and thermal classification techniques confirmed that ULWPE had long-branched chains. The long-branched chains markedly increased the proportion of the high entanglement and the tie molecules in the amorphous regions, endowing it with superior toughness. At the same time, the high crystallinity of ULWPE gives it sufficient hardness and strength. The combination of high crystallinity and high entanglement endowed ULWPE with a good balance between strength and toughness, leading to its exceptional mechanical properties and wear resistance. This study provided robust data for ULWPE's clinical use and theoretical insights for designing durable, implantable polymers.

In-situ TEM investigation of dislocation healing and recrystallization in nanoscratched silicon at elevated temperatures up to 800 °C

Nanoscratching introduces detrimental surface and subsurface defects like amorphous regions, dislocations, and stacking faults in monocrystalline silicon, hindering its application in microelectronics and high-performance optics. This study leverages in-situ transmission electron microscopy to unveil the thermal evolution of these defects in atomic scale. A key finding is the amorphous phase recrystallization starting at ∼500 °C. Epitaxial growth from the crystalline-amorphous boundary, guided by adjacent crystal planes, restores the original diamond structure phase. By 700–800 °C, almost complete recrystallization occurs, maintaining similar interplanar spacing despite residual crystal distortions and dislocations. Notably, heating above 600 °C results in the gradual vanishing of stacking faults, suggesting a dynamic thermal evolution of the crystal defects induced by surface nanoscratching. This work demonstrates thermal annealing as a promising strategy to mitigate nanoscratch-induced defects, paving the way for defect-free-surface of silicon components in ultra-precision machining processes. It offers valuable insights into the interplay between nanoscratching, temperature, and defect evolution, laying the groundwork for surface and subsurface defects elimination in silicon under thermal fields.

The influence of sub-surface damage microstructure on ultra-thin die flexural strength

In the semiconductor industry, where miniaturization is a key driver, mechanical properties of ultra-thin dies are increasingly important research topics. Sub-surface damage (SSD) is a common issue in wafer thinning processes, but there is a lack of research on the relationship between SSD microstructure and ultra-thin die strength. In this study, the influence of SSD microstructure on flexural strength was investigated through three-point bending tests of ultra-thin dies prepared by distinct wafer-thinning methods, coupled with SSD microstructure characterization. Flexural strength was highest for dies dry polished with N pad, intermediate for dies dry polished with M pad, and lowest for dies with fine grinding. We researched SSD microstructure by high-resolution transmitted electron microscope (HRTEM), revealing that it comprises amorphous regions, micro-cracks, and high-density distortion areas. The SSD of the fine grinding samples was thick and intermittent, with observable micro-cracks. Comparatively, the SSD structure from M pad polishing was uniform but thicker, whereas SSD from N pad polishing was thinner but exhibited greater variability. SSD thickness not only influences the average value but also dictates the distribution of flexural strength. This research enhances the understanding of SSD microstructure's impact on ultra-thin die flexural strength, providing valuable insights for optimizing wafer thinning processes to enhance die reliability.

Enhanced Marine Biodegradation of Polycaprolactone through Incorporation of Mucus Bubble Powder from Violet Sea Snail as Protein Fillers.

Microplastics' spreading in the ocean is currently causing significant damage to organisms and ecosystems around the world. To address this oceanic issue, there is a current focus on marine degradable plastics. Polycaprolactone (PCL) is a marine degradable plastic that is attracting attention. To further improve the biodegradability of PCL, we selected a completely new protein that has not been used before as a functional filler to incorporate it into PCL, aiming to develop an environmentally friendly biocomposite material. This novel protein is derived from the mucus bubbles of the violet sea snail (VSS, Janthina globosa), which is a strong bio-derived material that is 100% degradable in the sea environment by microorganisms. Two types of PCL/bubble composites, PCL/b1 and PCL/b5, were prepared with mass ratios of PCL to bubble powder of 99:1 and 95:5, respectively. We investigated the thermal properties, mechanical properties, biodegradability, surface structure, and crystal structure of the developed PCL/bubble composites. The maximum biochemical oxygen demand (BOD) degradation for PCL/b5 reached 96%, 1.74 times that of pure PCL (≈55%), clearly indicating that the addition of protein fillers significantly enhanced the biodegradability of PCL. The surface morphology observation results through scanning electron microscopy (SEM) definitely confirmed the occurrence of degradation, and it was found that PCL/b5 underwent more significant degradation compared to pure PCL. The water contact angle measurement results exhibited that all sheets were hydrophobic (water contact angle > 90°) before the BOD test and showed the changes in surface structure after the BOD test due to the newly generated indentations on the surface, which led to an increase in surface toughness and, consequently, an increase in surface hydrophobility. A crystal structure analysis by wide-angle X-ray scattering (WAXS) discovered that the amorphous regions were decomposed first during the BOD test, and more amorphous regions were decomposed in PCL/b5 than in PCL, owing to the addition of the bubble protein fillers from the VSS. The differential scanning calorimeter (DSC) and thermal gravimetric analysis (TGA) results suggested that the addition of mucus bubble protein fillers had only a slight impact on the thermal properties of PCL. In terms of mechanical properties, compared to pure PCL, the mucus-bubble-filler-added composites PCL/b1 and PCL/b5 exhibited slightly decreased values. Although the biodegradability of PCL was significantly improved by adding the protein fillers from mucus bubbles of the VSS, enhancing the mechanical properties at the same time poses the next challenging issue.

Electronic transport in amorphous Ge2Sb2Te5 phase-change memory line cells and its response to photoexcitation

We electrically characterized melt-quenched amorphized Ge2Sb2Te5 (GST) phase-change memory cells of 20 nm thickness, ∼66–124 nm width, and ∼100–600 nm length with and without photoexcitation in the 80–275 K temperature range. The cells show distinctly different current–voltage characteristics in the low-field (≲19 MV/m), with a clear response to optical excitation by red light, and high-field (≳19 MV/m) regimes, with a very weak response to optical excitation. The reduction in carrier activation energy with photoexcitation in the low-field regime increases from ∼10 meV at 80 K to ∼50 meV at 150 K (highest sensitivity) and decreases again to 5 meV at 275 K. The heterojunctions at the amorphous–crystalline GST interfaces at the two sides of the amorphous region lead to formation of a potential well for holes and a potential barrier for electrons with activation energies in the order of 0.7 eV at room temperature. The alignment of the steady state energy bands suggests the formation of tunnel junctions at the interfaces for electrons and an overall electronic conduction by electrons. When photoexcited, the photo-generated holes are expected to be stored in the amorphous region, leading to positive charging of the amorphous region, reducing the barrier for electrons at the junctions and hence the device resistance in the low-field regime. Holes accumulated in the amorphous region are drained under a high electric field. Hence, the potential barrier cannot be modulated by photogenerated holes, and the photo-response is significantly reduced. These results support the electronic origin of resistance drift in amorphous GST.

Biodegradation of PHB/PBAT films and isolation of novel PBAT biodegraders from soil microbiomes

Polyhydroxyalkanoates (PHAs) are important candidates for replacing petroleum-based plastics. This transition is urgent for the development of a biobased economy and to protect human health and natural ecosystems. PHAs are biobased and biodegradable polyesters that when blended with other polymers, such as poly(butylene adipate-co-terephthalate) (PBAT), acquire remarkable improvements in their properties, which allow them to comply with the requirements of packaging applications. However, the biodegradation of such blends should be tested to evaluate the impact of those polymers in the environment. For instance, PBAT is a compostable aliphatic-aromatic copolyester, and its biodegradation in natural environments, such as soil, is poorly studied. In this work, we evaluated the biodegradation of a bilayer film composed of PHB and PBAT, by a soil microbiome.The bilayer film reached 47 ± 1 % mineralization in 180 days and PHB was no longer detected after this period. The increased crystallinity of the PBAT residue was a clear sign of biodegradation, indicating that the amorphous regions were preferentially biodegraded. Seven microorganisms were isolated, from which 4 were closely related to microorganisms already known as PHB degraders, but the other 3 species, closely related to Streptomyces coelicoflavus, Clonostachys rosea and Aspergillus insuetus, were found for the first time as PHB degraders. Most remarkably, two fungi closely related to Purpureocillium lilacinum and Aspergillus pseudodeflectus (99.83 % and 100 % identity by ITS sequencing) were isolated and identified as PBAT degraders. This is very interesting due to the rarity of isolating PBAT-degrading microorganisms.These results show that the bilayer film can be biodegraded in soil, at mesophilic temperatures, showing its potential to replace synthetic plastics in food packaging.

Comparative analysis of millet bran nanocelluloses with various morphologies: Revealing differences in the formation mechanism and structure characteristics

To investigate the differences of nanocelluloses with various morphologies, ammonium persulphate (APS) oxidation, H3PO4 dissolution and regeneration, and ball milling combined with 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) as a medium were applied to isolate cellulose nanocrystals (MCNCs), cellulose nanospheres (MCNSs) and cellulose fibrils (MCNFs) from millet bran. The structure, properties, and formation mechanism of three nanocelluloses were comparatively investigated by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, atomic force microscope, scanning electronic microscope, and emulsifying ability evaluation. MCNCs had needle-like structures due to the removal of amorphous regions, MCNFs appeared fibrous structures due to swelling and mechanical force, and MCNSs displayed spherical structures through self-assembly. MCNCs and MCNFs were confirmed to exhibit cellulose I structures with crystallinities of 61.24 % and 50.09 %, respectively. MCNSs showed the highest crystallinity of 68.41 % with a cellulose II structure. MCNFs and MCNSs exhibited higher initial decomposition temperatures, while MCNCs showed the highest residual mass. MCNFs suspension showed the highest apparent viscosity, while MCNSs suspension demonstrated superior dispersion. MCNSs-emulsion displayed the smallest droplet size, and MCNFs-emulsion exhibited the highest viscosity. This study reveals the formation mechanisms and relationship between morphologies and properties of three millet bran nanocelluloses, providing a theoretical basis for their application.

Degradation Behaviors of Polylactic Acid, Polyglycolic Acid, and Their Copolymer Films in Simulated Marine Environments.

Poly(lactic acid) (PLA) and poly(glycolic acid) (PGA) are extensively studied biodegradable polymers. However, the degradation behavior of their copolymer, poly(lactic-co-glycolic acid) (PLGA), in marine environments has not yet been confirmed. In this study, the changes in macroscopic and microscopic morphology, thermal properties, aggregation, and chemical structure of PLA, PGA, PLGA-85, and PLGA-75 (with 85% and 75% LA content) in simulated marine environments were investigated. Results revealed that degradation occurred through hydrolysis of ester bonds, and the degradation rate of PGA was faster than that of PLA. The amorphous region degraded preferentially over the crystalline region, leading to cleavage-induced crystallization and decreased thermal stability of PLA, PLGA-85, and PLGA-75. The crystal structures of PLGAs were similar to those of PLA, and the higher GA content, the faster was the degradation rate. This study provides a deeper understanding of the seawater degradation behaviors of PLA, PGA, and their copolymers, and provides guidance for the preparation of materials with controllable degradation performance.

Cell Wall Modification Based on Combination Reagents to Improve Dimensional Stability of Wood with High Efficiency.

Although γ-methacryloxypropyltrimethoxysilane (MPS) was proved to be an effective reagent for improving the dimensional stability of wood, a bottleneck in ASE value (around 50%) existed. The reason was that MPS with low polarity opened few hydrogen bonds in the amorphous region of cellulose, while these hydrogen bonds could be reopened by water. Therefore, citric acid (CA) is chosen to cooperate with MPS to further enhance the dimensional stability of wood. In this paper, MPS and CA were used to modify wood individually (MW and CW) or with different combinations, that is, one-step modification (M/CW) and two-step modification with MPS first (M-CW) or CA first (C-MW). CA and MPS concentrations were optimized at 5 wt%. The ASE value for M/CW was only 25.74% at a weight percent gain (WPG) of 6.43%, which was only 0.6 times to MW or 0.7 times to CW. For M-CW, the ASE value gradually decreased with the soaking cycles, from 65.64% at a WPG of 9.05% to 51.20%. The C-MW had the best dimensional stability, with the ASE value 75.35% at a WPG of 11.50%. Although it decreased during the first soaking cycle, it stabilized at 62.20% at last. SEM and EDS images showed that the polymer mainly distributed in cell walls and few in cell lumen in C-MW. Thus, the enhanced dimensional stability of C-MW could be explained by CA opening the hydrogen bonds in the amorphous region of cellulose first, which provided more binding sites for MPS.

Improving resistant starch content of cassava starch by pulsed electric field-assisted esterification

This study aims to investigate the effect of pulsed electric field (PEF) assisted OSA esterification treatment on the multi-scale structure and digestive properties of cassava starch and structure-digestion relationships. The degree of substitution (DS) of starch dually modified at 1.5–4.5 kV/cm was 37.6–55.3 % higher than that of starch modified by the conventional method. Compared with native starch, the resistant starch (RS) content of esterified starch treated with 3 kV/cm significantly increased by 17.13 %, whereas that of starch produced by the conventional method increased by only 5.91 %. Furthermore, assisted esterification at low electric fields (1.5–3 kV/cm) promotes ester carbonyl grafting on the surface of starch granules, increases steric hindrance and promotes the rearrangement of the amorphous regions of starch, which increases the density of the double-helical structure. These structural changes slow down starch digestion and increase the RS content. Therefore, this study presents a potential method for increasing the RS content of starch products using PEF to achieve the desired digestibility.

Impact of an Infrared Pulsed Laser on the Optical Properties of Polycarbonate/Polyethylene Oxide/Chromium Oxide Nanocomposite Films

Nanocomposite films (NC) of amorphous polycarbonate (PC), semicrystalline polyethylene oxide (PEO), and chromium oxide (Cr2O3) nanoparticles (NP) were synthesized. We believe that this study is novel in the area of the effect of laser radiation on such NC. The synthesized Cr2O3 had a nanonature of average particle size 29 nm, as indicated from the Rietveld refinement of the XRD scans. Samples of the PC-PEO/Cr2O3 NC films were irradiated with infrared energy fluences ranging from 5 to 95 Joule/cm2 (J/cm2) using an infrared pulsed laser. We used UV-vis spectroscopy and the International Commission on Illumination (CIE) color changes technique to investigate the resulting effects of the laser irradiation on the optical bandgap energy and color properties of the prepared films. As the laser fluence increased up to 95 J/cm2, the maximum fluence used, both the direct and indirect bandgaps decreased. The Urbach energy showed an opposite tendency; it increased from 0.32 to 0.56 eV. This can be attributed to the dominance of chain crosslinks that destroyed the ordered structure and thus increased the amorphous regions. Also, the optical dielectric loss (ε″) aided in detecting the nature of the microelectronic transitions. It was found that the PC/PEO/Cr2O3 NC films had direct allowed transitions. Additionally, the effect of laser irradiation on the absorbance, refractive index, real and imaginary dielectric parameters, and optical conductivity of the blend composite samples were studied. Moreover, the optical color changes between the pristine and the irradiated films were evaluated. The pristine blend film was uncolored. It showed significant color changes when irradiated with the laser at increasing fluences up to 95 J/cm2. The change in the optical properties of PC/PEO/Cr2O3 NC film suggested its usage as a promising candidate for future optoelectronics manufacturing.

Indicator Films Containing Dendrobium Orchid Flower Extract and TiO2 Nanoparticles for Monitoring Fish Fillet Spoilage

This work aimed to study a novel pH indicator film prepared from carboxymethyl cellulose (CMC)/tapioca starch (TS) incorporating Dendrobium orchid flowers and TiO2 nanoparticles for monitoring fish fillet freshness. The films were prepared based on carboxymethyl cellulose (CMC) and tapioca starch (TS) blend (CMC/TS) incorporated with TiO2 nanoparticles and Dendrobium orchid flower (DOF) extract. The result showed that the DOF extract contained peonidin-3,5-O-diglucoside and exhibited distinguishable color changes in different pH buffers. Likewise, the CMC/TS+TiO2+DOF film’s color changed corresponding to the extract. The X-ray diffraction analysis revealed the expansion of the film’s amorphous region, due to the intermolecular interactions. Analyzing scanning electron microscope images showed the effects of TiO2 and DOF extract on the surface morphology of films. The incorporation of TiO2 and DOF extract into the film formulation improved various film properties, such as redness, opacity, tensile strength, and water solubility. For the sensitivity testing, the color of the CMC/TS+TiO2+DOF film responded to ammonia vapor more than acetic acid vapor, suitable for monitoring seafood spoilage behavior. In addition, the application of film for monitoring the freshness of fish fillets was conducted. The CMC/TS+TiO2+DOF film color changed from purple to bluish-purple corresponding to the spoilage of samples. Indicating its potential as an indicator for monitoring fish fillets' freshness.

Biodegradation behavior of poly (glycolic acid) (PGA) and poly (butylene adipate-co-terephthalate) (PBAT) blend films in simulation marine environment

Polyglycolic acid (PGA) and poly (butylene adipate-co-terephthalate) (PBAT), as widely applied biodegradable polymers, the degradation behavior of their blends in marine environments has not been proven. This study investigated the changes of macroscopic and microscopic morphology, thermal properties, crystalline and chemical structure, degradation rate of PGA/PBAT blends with different ratios in the simulation marine environment containing sediments and marine organisms. The results showed that degradation primarily occurred due to ester bond breakage, and PGA exhibited a faster degradation rate than PBAT films. The amorphous region degraded more rapidly than the crystalline region, and the thermal stability of the materials decreased. The degradation of PGA and PBAT blends followed their respective single degradation laws and the compatibility of blend samples decreased after degradation. The degradation rate of the samples was obtained by measuring the biochemical oxygen demand, which indicated that a higher PGA content could result in a faster degradation rate for PGA/PBAT films. This study provides an efficient method for constructing materials with controlled biodegradability.