On-Demand Tunable Electrical Conductance Anisotropy in a MOF-Polymer Composite.

Property optimization through orientation control of metal-organic framework (MOF) crystals that exhibit anisotropic crystal structures continues to garner tremendous interest. Herein, an electric field is utilized to post-synthetically control the orientation of conductive layered Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) crystals dispersed in an electronically insulating poly(ethylene glycol) diacrylate (PEGDA) oligomer matrix. Optical and electrical measurements are performed to investigate the impact of the electric field on the alignment of Cu3(HHTP)2 crystals and the formation of aggregated microstructures, which leads to an ≈5000-fold increase in the conductivity of the composite. Notably, the composite thin-films containing aligned Cu3(HHTP)2 crystals exhibit significant conductivity of ≈10-3 S cm-1 despite the low concentration (≈1 wt.%) of conductive Cu3(HHTP)2. The use of an electric field to align Cu3(HHTP)2 crystals can rapidly generate various desired patterns that exhibit on-demand tunable collective charge transport anisotropy. The findings provide valuable insights toward the manipulation and utilization of conductive MOFs with anisotropic crystal structures for various applications such as adhesive electrical interconnects and microelectronics.

Photoactuators Based on Plastically Flexible α-Cyanostilbene Molecular Crystals Driven by the Solid-State [2+2] Cycloaddition Reaction.

Organic photomechanical molecular crystals are promising candidates for photoactuators, which have potential applications as smart materials in various fields. However, it is still challenging to fabricate photomechanical molecular crystals with flexibility because most of the molecular crystals are brittle and the mechanism of flexible crystals remains controversial. Here, a plastically flexible α-cyanostilbene crystal has been synthesized that can undergo solid-state [2+2] cycloaddition reaction under violet or UV irradiation and exhibits excellent photomechanical bending properties. A hook-shaped crystal can lift 0.7 mg object upward by 1.5 cm, which proves its potential for application as photoactuators. When complex with the agarose polymer, the molecules will be in the form of macroscopic crystals, which can drive the composite films to exhibit excellent photomechanical bending performance. Upon irradiation with UV light, the composite film can quickly lift 18.0 mg object upward by 0.3 cm. The results of this work may facilitate the application of macroscale crystals as photoactuators.

Bioresource Polymer Composite for Energy Generation and Storage: Developments and Trends.

The ever-growing demand of human society for clean and reliable energy sources spurred a substantial academic interest in exploring the potential of biological resources for developing energy generation and storage systems. As a result, alternative energy sources are needed in populous developing countries to compensate for energy deficits in an environmentally sustainable manner. This review aims to evaluate and summarize the recent progress in bio-based polymer composites (PCs) for energy generation and storage. The articulated review provides an overview of energy storage systems, e. g., supercapacitors and batteries, and discusses the future possibilities of various solar cells (SCs), using both past research progress and possible future developments as a basis for discussion. These studies examine systematic and sequential advances in different generations of SCs. Developing novel PCs that are efficient, stable, and cost-effective is of utmost importance. In addition, the current state of high-performance equipment for each of the technologies is evaluated in detail. We also discuss the prospects, future trends, and opportunities regarding using bioresources for energy generation and storage, as well as the development of low-cost and efficient PCs for SCs.

Development of Amorphous Solid Dispersion Sustained-Release Formulations with Polymer Composite Matrix-Regulated Stable Release Plateaus.

PURPOSE: This study was designed to develop ibuprofen (IBU) sustained-release amorphous solid dispersion (ASD) using polymer composites matrix with drug release plateaus for stable release and to further reveal intrinsic links between polymer' matrix ratios and drug release behaviors. METHODS: Hydrophilic polymers and hydrophobic polymers were combined to form different composite matrices in developing IBU ASD formulations by hot melt extrusion technique. The intrinsic links between the mixed polymer matrix ratio and drug dissolution behaviors was deeply clarified from the dissolution curves of hydrophilic polymers and swelling curves of composite matrices, and intermolecular forces among the components in ASDs. RESULTS: IBU + ammonio methacrylate copolymer type B (RSPO) + poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP VA64) physical mixtures presented unstable release behaviors with large error bars due to inhomogeneities at the micrometer level. However, IBU-RSPO-PVP VA64 ASDs showed a "dissolution plateau phenomenon", i.e., release behaviors of IBU in ASDs were unaffected by polymer ratios when PVP VA64 content was 35% ~ 50%, which could reduce risks of variations in release behaviors due to fluctuations in prescriptions/processes. The release of IBU in ASDs was simultaneously regulated by the PVP VA64-mediated "dissolution" and RSPO-PVP VA64 assembly-mediated "swelling". Radial distribution function suggested that similar intermolecular forces between RSPO and PVP VA64 were key mechanisms for the "dissolution plateau phenomenon" in ASDs at 35% ~ 50% of PVP VA64. CONCLUSIONS: This study provided ideas for developing ASD sustained-release formulations with stable release plateau modulated by polymer combinations, taking full advantages of simple process/prescription, ease of scale-up and favorable release behavior of ASD formulations.

Cotinuous precision separation of gold using a metal-organic framework/polymer composite.

Critical metals of environmental and economic relevance can be found within complex mixtures, such as mine tailings, electronic waste and wastewater, at trace amounts. Specifically, gold is a critical metal that carries desired redox active properties in various applications, including modern electronics, medicine and chemical catalysis. Here we report the structuring of sub-micron Fe-BTC/PpPDA crystallites into larger 250µm or 500µm granules for continuous packed bed experiments for the precision separation of gold. The Structured Fe-BTC/PpPDA is highly crystalline and porous with a BET surface area of 750 m2g-1. Further, the hybrid nanocomposite material maintains its selectivity for gold ions over common inorganic interferents. The structuring approach reported prevents excessive pressure drop and ensures stability over time and operation in a packed bed column. Further, we demonstrate that the Structured Fe-BTC/PpPDA can concentrate at least 42 wt% of gold under a dynamic continuous flow operation. These findings highlight the potential of Structured Fe-BTC/PpPDA for practical applications in industry, particularly in the selective capture of gold from complex mixtures.

Synergetic Improvement of Flexoelectric Coefficient in Liquid Crystal Embedded Flexible PVDF Polymer Composite for Energy Harvesting Applications.

Flexoelectricity is the universal electric polarization of dielectrics upon exertion of a non-uniform strain gradient. With the advancement of nano-technology and miniaturization of electronic devices, flexoelectricity holds the promise to address the power requirements for such device operation. The direct flexoelectric effect in liquid crystal (LC) embedded poly(vinylidene fluoride) (PVDF) polymer films is examined for the first time by the application of external strain on the films. Physical characterizations such as Differential Scanning Calorimetry (DSC), dielectric spectroscopy, X-ray diffraction, and field emission scanning electron microscopy (FESEM) are carried out to study the composite films' intrinsic and extrinsic properties like dielectric, crystallinity, and morphologies. The value of the flexoelectric coefficient (µ12) increases with the concentration of LC incorporation. At 3 wt%, µ12 attains a maximum value of 68 nC m-1, which is more than a threefold increase compared to that of the pure PVDF film. The role of Maxwell-Wagner-Sillars (MWS) polarization in determining flexoelectric polarization in polymer composites is also discussed. Moreover, the influence of the microstructure and domain size formation in determining the flexoelectric response are discussed in detail to infer the behavior of the flexoelectric coefficients of the films. Potential device applications based on this phenomenon have been proposed for future research in sensing and actuation.

Recent Advances in Bioactive Carbon Nanotubes Based on Polymer Composites for Biosensor Applications.

Recent breakthroughs in the field of carbon nanotubes (CNTs) have opened up unprecedented opportunities for the development of specialized bioactive CNT-polymers for a variety of biosensor applications. The incorporation of bioactive materials, including DNA, aptamers and antibodies, into CNTs to produce composites of bioactive CNTs has attracted considerable attention. In addition, polymers are essential for the development of biosensors as they provide biocompatible conditions and are the ideal matrix for the immobilization of proteins. The numerous applications of bioactive compounds combined with the excellent chemical and physical properties of CNTs have led to the development of bioactive CNT-polymer composites. This article provides a comprehensive overview of CNT-polymer composites and new approaches to encapsulate bioactive compounds and polymers in CNTs. Finally, biosensor applications of bioactive CNT-polymer for the detection of glucose, H2O2 and cholesterol were investigated. The surface of CNT-polymer facilitates the immobilization of bioactive molecules such as DNA, enzymes or antibodies, which in turn enables the construction of state-of-the-art, future-oriented biosensors.

Machine learning strategy to improve impact strength for PP/cellulose composites via selection of biomass fillers.

Lignocellulosic materials have inherent complexities and natural nanoarchitectures, such as various chemical constituents in wood cell walls, structural factors such as fillers, surface properties, and variations in production. Recently, the development of lignocellulosic filler-reinforced polymer composites has attracted increasing attention due to their potential in various industries, which are recognized for environmental sustainability and impressive mechanical properties. The growing demand for these composites comes with increased complexity regarding their specifications. Conventional trial-and-error methods to achieve desired properties are time-intensive and costly, posing challenges to efficient production. Addressing these issues, our research employs a data-driven approach to streamline the development of lignocellulosic composites. In this study, we developed a machine learning (ML)-assisted prediction model for the impact energy of the lignocellulosic filler-reinforced polypropylene (PP) composites. Firstly, we focused on the influence of natural supramolecular structures in biomass fillers, where the Fourier transform infrared spectra and the specific surface area are used, on the mechanical properties of the PP composites. Subsequently, the effectiveness of the ML model was verified by selecting and preparing promising composites. This model demonstrated sufficient accuracy for predicting the impact energy of the PP composites. In essence, this approach streamlines selecting wood species, saving valuable time.

This paper introduces a data-driven method to efficiently design lignocellulosic polymer composites with high-impact energy, optimizing components and surface areas using infrared spectroscopic data.

Low-Hydrophilic HKUST-1/Polymer Extrudates for the PSA Separation of CO2/CH4.

HKUST-1 is an MOF adsorbent industrially produced in powder form and thus requires a post-shaping process for use as an adsorbent in fixed-bed separation processes. HKUST-1 is also sensitive to moisture, which degrades its crystalline structure. In this work, HKUST-1, in the form of crystalline powder, was extruded into pellets using a hydrophobic polymeric binder to improve its moisture stability. Thermoplastic polyurethane (TPU) was used for that purpose. The subsequent HKUST-1/TPU extrudate was then compared to HKUST-1/PLA extrudates synthesized with more hydrophilic polymer: polylactic acid (PLA), as the binder. The characterization of the composites was determined via XRD, TGA, SEM-EDS, and an N2 adsorption isotherm analysis. Meanwhile, the gas-separation performances of HKUST-1/TPU were investigated and compared with HKUST-1/PLA from measurements of CO2 and CH4 isotherms at three different temperatures, up to 10 bars. Lastly, the moisture stability of the composite materials was investigated via an aging analysis during storage under humid conditions. It is shown that HKUST-1's crystalline structure was preserved in the HKUST-1/TPU extrudates. The composites also exhibited good thermal stability under 523 K, whilst their textural properties were not significantly modified compared with the pristine HKUST-1. Furthermore, both extrudates exhibited larger CO2 and CH4 adsorption capacities in comparison to the pristine HKUST-1. After three months of storage under atmospheric humid conditions, CO2 adsorption capacities were reduced to only 10% for HKUST-1/TPU, whereas reductions of about 25% and 54% were observed for HKUST-1/PLA and the pristine HKUST-1, respectively. This study demonstrates the interest in shaping MOF powders by extrusion using a hydrophobic thermoplastic binder to operate adsorbents with enhanced moisture stability in gas-separation columns.

Effect of different preparation designs and material types on fracture resistance of minimally invasive posterior indirect adhesive restorations.

PURPOSE: To evaluate the impact of various preparation designs and the material type on fracture resistance of minimally invasive posterior indirect adhesive restorations after aging using a digital standardization method. MATERIALS AND METHODS: One-hundred sixty human maxillary premolars free from caries were assigned into 16 groups (n = 10): bevel design on enamel substrate with mesial box only (VEM), butt joint design on enamel substrate with mesial box only (BEM), bevel design on enamel substrate with mesial and distal box (VED), butt joint design on enamel substrate with mesial and distal box (BED), bevel design on dentin substrate with mesial box only (VDM), butt joint design on dentin substrate with mesial box only (BDM), bevel design on dentin substrate with mesial and distal box (VDD), and butt joint design on dentin substrate with mesial and distal box (BDD). Each group was restored with pressable lithium disilicate (LS2) or disperse-filled polymer composite (DPC) materials. Adhesive resin cement was used to bond the restorations. The specimens were aged for 10,000 thermal cycles (5°C and 55°C), then 240,000 chewing cycles. Each specimen was subjected to compressive axial load until failure. A two-way analysis of variance (ANOVA) test followed by a post hoc Tukey test was used to analyze the data (α = 0.05). RESULTS: The two-way ANOVA test revealed a significant difference among designs (p < 0.001) and materials (p < 0.001) with no interaction effect (p = 0.07) between the variables. The Post hoc Tukey test revealed that the VEM group exhibited the highest mean fracture resistance value, while the BDM group had the lowest. The LS2 groups showed the highest mean fracture resistance values. The DPC groups showed a restorable fracture pattern compared to the LS2 groups. CONCLUSIONS: Bevel and butt joint designs with mesial or distal boxes are recommended for conservative posterior indirect adhesive restorations in premolar areas. Enamel substrate improved load distribution and fracture resistance. DPCs have restorable failure patterns, while pressed LS2 may harm underlying structures.

Highly Elastically Deformable Coiled CNT/Polymer Fibers for Wearable Strain Sensors and Stretchable Supercapacitors.

Stretchable yarn/fiber electronics with conductive features are optimal components for different wearable devices. This paper presents the construction of coil structure-based carbon nanotube (CNT)/polymer fibers with adjustable piezoresistivity. The composite unit fiber is prepared by wrapping a conductive carbon CNT sheath onto an elastic spandex core. Owing to the helical coil structure, the resultant CNT/polymer composite fibers are highly stretchable (up to approximately 300%) without a noticeable electrical breakdown. More specifically, based on the difference in the coil index (which is the ratio of the coil diameter to the diameter of the fiber within the coil) according to the polymeric core fiber (spandex or nylon), the composite fiber can be used for two different applications (i.e., as strain sensors or supercapacitors), which are presented in this paper. The coiled CNT/spandex composite fiber sensor responds sensitively to tensile strain. The coiled CNT/nylon composite fiber can be employed as an elastic supercapacitor with excellent capacitance retention at 300% strain.

Molecular Dynamics Modeling for the Determination of Elastic Moduli of Polymer-Single-Walled Carbon Nanotube Composites.

The use of carbon nanotubes to improve the mechanical properties of polymers is one of the promising directions in materials science. The addition of single-walled carbon nanotubes (SWCNTs) to a polymer results in significant improvements in its mechanical, electrical, optical, and structural properties. However, the addition of SWCNTs does not always improve the polymer properties. Also, when a certain content of SWCNTs is exceeded, the mechanical properties of the nanocomposite become worse. This article reports the results of computer simulations for predicting the mechanical properties of polymer/single-walled carbon nanotube nanocomposites. The efficiency of reinforcing polymer composites is considered depending on the concentration of carbon nanotubes in the polymer matrix, their size, and structure. The elastic moduli of the nanocomposites are predicted using computer simulations for unit cell tension (0.1%). General trends in the mechanical properties of composites with polypropylene (PP), poly(ethyl methacrylate) (PEMA), polystyrene (PS) matrices, and SWCNTs are shown.

Analysis of Aluminum Oxides Submicron Particle Agglomeration in Polymethyl Methacrylate Composites.

Agglomeration of distributed particles is the main problem in polymer composites reinforced with such particles. It leads to a decrease in mechanical performance and its poor reproducibility. Thus, development of methods to address the agglomeration of particles is relevant. Evaluation of the size and concentration of agglomerates is required to select a method to address agglomeration. The paper analyzes aluminum oxide particles agglomeration in particles-reinforced polymethyl methacrylate (PMMA) composites. Quantitative parameters of polystyrene-coated aluminum oxide particles agglomerates are obtained for the first time in this article. Unlike uncoated aluminum oxide particles, when coated aluminum oxide particles are used, agglomerates concentration in polymer composites decreases approx. 10 times. It demonstrates that modification of submicron particles by a polymer coating decreases the number of agglomerates in the polymer composite. The use of transmittance and opacity values to estimate particles agglomerates is reasonable in this article. It is shown that the difference in optical performance of specimens reinforced with coated and the original particles is related to the number and average size of agglomerates in the specimens. For example, when the concentration exceeds 0.2%, transmittance values for the specimens reinforced with coated particles are greater than the ones for the specimens reinforced with the original particles.

Effects of Different Surface Treatments of Woven Glass Fibers on Mechanical Properties of an Acrylic Denture Base Material.

Silanized glass fibers are popular reinforcements of acrylic denture base materials. To increase the number of surface hydroxyl groups and to improve interfacial adhesion between the matrix and reinforcements, acid or base treatments of glass fibers are commonly performed before the silanization. However, limited data are available on the effect of these treatments on the mechanical properties of acrylic matrix composite materials used for denture base applications. In this work, before the silanization of a woven glass fiber fabric (GF) with 3-(trimethoxysilyl) propyl methacrylate, activation pretreatments using HCl and NH4OH aqueous solutions have been performed. To characterize the glass surface, FTIR spectroscopy was used. Specimens of cured acrylic denture base resin and composites were divided into five groups: (1) cured acrylic denture base resin-control group; (2) composite with non-silanized GF; (3) composite with silanized GF; (4) composite with NH4OH activated and silanized GF; (5) composite with HCl activated and silanized GF. The flexural and impact properties of specimens were evaluated by means of three-point-bending tests and Charpy impact testing, respectively. The residual reactivity of the samples was analyzed using differential scanning calorimetry. The results of mechanical testing showed that acid and base pretreatments of the glass fabric had a positive effect on the flexural modulus of prepared composites but a negative effect on their impact strength. Possible interfacial adhesion mechanisms and the diffusion control of isothermal cure reactions due to vitrification have been discussed.

Thermal and Morphological Analysis of Linear Low-Density Polyethylene Composites Containing d-limonene/ß-cyclodextrin for Active Food Packaging.

Composites made of linear low-density polyethylene (LLDPE) and ß-cyclodextrin/d-limonene inclusion complex (CD-lim) were prepared by melt extrusion to develop a novel food packaging material. Scanning electron microscopy evidenced a fairly good dispersion of the filler within the polymeric matrix. Infrared spectroscopy coupled with thermogravimetric analysis confirmed the presence of CD-lim in the composites, proving that the applied technology of including the essential oil within ß-CD cages allows for preventing a sizable loss of d-limonene despite a high temperature and shear applied upon extrusion processing. Moreover, the influence of the filler on the thermal properties of PE was assessed. It was found that the cyclodextrin-based inclusion complex significantly fastens the crystallization path of the polyethylene matrix with an improved crystallization rate of the PE/CD-lim composites compared to the neat polymer.

Plastic orbital foreign body: the rise of plastic and its unintended consequences.

Intraorbital foreign bodies (IOrFBs) are a significant cause of ocular morbidity. Although plastic IOrFBs are rare, the increasing use of plastic and polymer composites in motor vehicles will increase their prevalence. Although challenging to identify, plastic IOrFBs have unique radiographic characteristics. The authors describe a case of an 18-year-old man with a history of a motor vehicle accident and a left upper eyelid laceration. In retrospect, imaging suggested a plastic IOrFB, which was initially overlooked. A follow-up examination demonstrated persistent left upper lid ptosis with an underlying mass. Further work-up revealed a retained IOrFB, which was removed via anterior orbitotomy. Scanning electron microscopy of the material was consistent with a plastic polymer. This case demonstrates the importance of maintaining a high suspicion for IOrFBs in the correct clinical context, the need for increased awareness of plastic and polymer composite IOrFBs, and the use of diagnostic imaging for identification.

Polarization improvement of perovskite nanowire composite films by mechanical stretching method.

Perovskite nanowires (NWs) have attracted considerable interest because of their excellent polarization properties. In this work, we first synthesized colloidal lead halide CsPbBr3NWs with suitable lengths and excellent polarization performance by the method of the thermal injection. By embedding the NWs in polyvinyl alcohol (PVA) to prepare practical a polymer composite and combining it with the mechanical stretching method, we achieved films with higher polarizing properties. The optimized stretched composite film achieved a polarization degree of 0.4992, which is superior to that of the unstretched one. The stretched PVA molecules are arranged in a straight line, which absorbs the polarized light parallel to the alignment direction, and only allows the polarized light in the vertical direction to pass through. Therefore, the arrangement of the spin-coated NWs combined with the arrangement direction of the PVA molecules led to an improvement in the polarization performance of the composite film. The NWs-PVA-stretched composite films will show important application value in the manufacture of next-generation polarization-sensitive optoelectronic devices and other fields.

Variations of tunnelling resistance between CNTs with strain in composites: non-monotonicty and influencing factors.

The electro-mechanical response of conductive carbon-nanotube(CNT)-polymer composites is vital when they are used as smart-sensing materials. Clarifying the variation trend of resistance with strain is the key to design and regulate the piezoresistive property of such material. Here, we present some finite element simulations to predict the electro-mechanical response using a geometrical model comprising two hollow cylindrical CNTs and a cuboid matrix. The electrical contact between CNTs is represented by some elements which account for quantum tunnelling effects and capture the sensitivity of conductivity to separation. Different from classical simulations using solid model or one-dimensional beam model, in which the tunnelling resistance between two CNTs changes monotonously with strain, the results in this work show that the trend is non-monotonic in some cases, i.e. it increases at first and then decreases with the uniaxial compressive strain when the elastic modulus of the matrix is high. In addition, factors affecting the different variation trends are discussed in details, which include geometric model, elastic modulus and Poisson's ratio of the matrix, and orientation angle.

Elastomeric Core/Conductive Sheath Fibers for Tensile and Torsional Strain Sensors.

Motion sensing, aimed at detecting and monitoring mechanical deformation, has received significant attention in various industrial and research fields. In particular, fiber-structured mechanical strain sensors with carbon-based materials have emerged as promising alternatives for wearable applications owing to their wearability and adaptability to the human body. Various materials, structures, sensing mechanisms, and fabrication methods have been used to fabricate high-performance fiber strain sensors. Nevertheless, developing multi-modal strain sensors that can monitor multiple deformations remains to be accomplished. This study established core/sheath fiber multi-modal strain sensors using polymer and carbon nanotubes (CNTs). Specifically, a flexible and conductive CNT sheet was wrapped onto the elastomeric core fiber at a certain angle. This wrapping angle allowed the CNTs to mechanically deform under tensile and torsional deformations without fatal structural damage. The CNTs could sense both tensile and torsional strains through reversible structural changes during deformations. The fiber strain sensor exhibited an increase of 124.9% and 9.6% in the resistance during tensile and torsional deformations of 100% and 1250 rad/m, respectively.

CNT/Graphite/SBS Conductive Fibers for Strain Sensing in Wearable Telerehabilitation Devices.

Rapid growth of personal electronics with concurrent research into telerehabilitation solutions discovers opportunities to redefine the future of orthopedic rehabilitation. After joint injury or operation, convalescence includes free active range of movement exercises, such as joints bending and straightening under medical supervision. Flexion detection through wearable textile sensors provides numerous potential benefits such as: (1) reduced cost; (2) continuous monitoring; (3) remote telerehabilitation; (4) gamification; and (5) detection of risk-inducing activities in daily routine. To address this issue, novel piezoresistive multi-walled carbon nanotubes/graphite/styrene-butadiene-styrene copolymer (CNT/Gr/SBS) fiber was developed. The extrusion process allowed adjustable diameter fiber production, while being a scalable, industrially adapted method of manufacturing textile electronics. Composite fibers were highly stretchable, withstanding strains up to 285%, and exhibited exceptional piezoresistive parameters with a gauge factor of 91.64 for 0-100% strain range and 2955 for the full scope. Considering the composite's flexibility and sensitivity during a series of cyclic loading, it was concluded that developed Gr/CNT/SBS fibers were suitable for application in wearable piezoresistive sensors for telerehabilitation application.