In-Depth Understanding of the Effect of the Distribution of Substituents on the Morphology and Physical Properties of Ethylcellulose: Molecular Dynamics Simulations Insights.

Ethylcellulose (EC) is a crucial cellulose derivative with widespread applications, particularly in the pharmaceutical industry, where precise property adjustments through chemical modification are imperative. The degree of substitution (DS) and the localization of substituents along the cellulose chains are pivotal factors in this process. However, the impact of the substituent location within the repeating unit of EC remains unexplored. To address this gap, we conducted molecular dynamics simulations on amorphous EC, comparing randomly and uniformly substituted ethyl groups in the repeating units. This comprehensive study of pairwise interactions revealed significant differences in intramolecular and intermolecular hydrogen-bonding capabilities, depending on whether the hydroxyl groups were substituted at C2, C3, or C6. While our simulations demonstrated that substituent localization in the repeating unit influenced the density, number of hydrogen bonds, and conformations, the DS emerged as the dominant determinant. This insight led us to propose and validate a hypothesis: a straightforward linear function using the properties of uniform models and molar fractions can predict the properties of randomly substituted EC with a given DS. This innovative approach is anticipated to contribute to the selection of cellulose derivatives with desirable properties for the pharmaceutical industry and new applications in other fields.

Molecular Dynamics Simulations of Cellulose and Dialcohol Cellulose under Dry and Moist Conditions.

The development of wood-based thermoplastic polymers that can replace synthetic plastics is of high environmental importance, and previous studies have indicated that cellulose-rich fiber containing dialcohol cellulose (ring-opened cellulose) is a very promising candidate material. In this study, molecular dynamics simulations, complemented with experiments, were used to investigate how and why the degree of ring opening influences the properties of dialcohol cellulose, and how temperature and presence of water affect the material properties. Mechanical tensile properties, diffusion/mobility-related properties, densities, glass-transition temperatures, potential energies, hydrogen bonds, and free volumes were simulated for amorphous cellulosic materials with 0-100% ring opening, at ambient and high (150 °C) temperatures, with and without water. The simulations showed that the impact of ring openings, with respect to providing molecular mobility, was higher at high temperatures. This was also observed experimentally. Hence, the ring opening had the strongest beneficial effect on "processability" (reduced stiffness and strength) above the glass-transition temperature and in wet conditions. It also had the effect of lowering the glass-transition temperature. The results here showed that molecular dynamics is a valuable tool in the development of wood-based materials with optimal thermoplastic properties.

Sustainable Wheat Protein Biofoams: Dry Upscalable Extrusion at Low Temperature.

Glycerol-plasticized wheat gluten was explored for producing soft high-density biofoams using dry upscalable extrusion (avoiding purposely added water). The largest pore size was obtained when using the food grade ammonium bicarbonate (ABC) as blowing agent, also resulting in the highest saline liquid uptake. Foams were, however, also obtained without adding a blowing agent, possibly due to a rapid moisture uptake by the dried protein powder when fed to the extruder. ABC's low decomposition temperature enabled extrusion of the material at a temperature as low as 70 °C, well below the protein aggregation temperature. Sodium bicarbonate (SBC), the most common food-grade blowing agent, did not yield the same high foam qualities. SBC's alkalinity, and the need to use a higher processing temperature (120 °C), resulted in high protein cross-linking and aggregation. The results show the potential of an energy-efficient and industrially upscalable low-temperature foam extrusion process for competitive production of sustainable biofoams using inexpensive and readily available protein obtained from industrial biomass (wheat gluten).

Microplastics Originating from Polymer Blends: An Emerging Threat?

No one can have missed the growing global environmental problems with plastics ending up as microplastics in food, water, and soil, and the associated effects on nature, wildlife, and humans. A hitherto not specifically investigated source of microplastics is polymer blends. A 1 g polymer blend can contain millions to billions of micrometer-sized species of the dispersed phase and therefore aging-induced fragmentation of the polymer blends can lead to the release of an enormous amount of microplastics. Especially if the stability of the dispersed material is higher than that of the surrounding matrix, the risk of microplastic migration is notable, for instance, if the matrix material is biodegradable and the dispersed material is not. The release can also be much faster if the matrix polymer is biodegradable. The purpose of writing this feature article is to arise public and academic attention to the large microplastic risk from polymer blends during their development, production, use, and waste handling.

Novel definition of the synergistic effect between carbon nanotubes and carbon black for electrical conductivity.

Anisotropic ternary composites comprising poly(methy-methacrylate) (PMMA), carbon black (CB), and carbon nanotubes (CNTs) were extruded using a capillary rheometer and the electrical conductivities of the composites were measured and presented in a detailed contour plot covering a large range of filler fractions (up to 30 vol% CNTs, 20 vol% CB). A recent generic conductivity model for ternary composites was successfully validated using the conductivity measurements. When analyzing the conductivity measurements using four traditional definitions of 'synergy' between two conductive fillers, no clear synergetic effect was observed between CB and CNT. Also, when all the conductivity data for ternary CNT/CB composites from the existing literature was carefully gathered and analyzed, the number of confirmed occurrences of strong and convincing CNT/CB synergies was surprisingly low. Finally, a novel definition of synergy based on the physical aspect, in particular, its maximum, the 'synergasm', was defined in order to obtain a more precise instrument for revealing regions of potential synergy.

Three-Dimensional Nanometer Features of Direct Current Electrical Trees in Low-Density Polyethylene.

Electrical trees are one reason for the breakdown of insulating materials in electrical power systems. An understanding of the growth of electrical trees plays a crucial role in the development of reliable high voltage direct current (HVDC) power grid systems with transmission voltages up to 1 MV. A section that contained an electrical tree in low-density polyethylene (LDPE) has been visualized in three dimensions (3D) with a resolution of 92 nm by X-ray ptychographic tomography. The 3D imaging revealed prechannel-formations with a lower density with the width of a couple of hundred nanometers formed around the main branch of the electrical tree. The prechannel structures were partially connected with the main tree via paths through material with a lower density, proving that the tree had grown in a step-by-step manner via the prestep structures formed in front of the main channels. All the prechannel structures had a size well below the limit of the Paschen law and were thus not formed by partial discharges. Instead, it is suggested that the prechannel structures were formed by electro-mechanical stress and impact ionization, where the former was confirmed by simulations to be a potential explanation with electro-mechanical stress tensors being almost of the same order of magnitude as the short-term modulus of low-density polyethylene.

Reduced and Surface-Modified Graphene Oxide with Nonlinear Resistivity.

Field-grading materials (FGMs) are used to reduce the probability for electrical breakdowns in critical regions of electrical components and are therefore of great importance. Usually, FGMs are heavily filled (40 vol.%) with semi-conducting or conducting particles. Here, polymer-grafted reduced graphene oxide (rGO) is used as a filler to accomplish percolated networks at very low filling ratios (<2 vol.%) in a semi-crystalline polymer matrix: poly(ethylene-co-butyl acrylate) (EBA). Various simulation models are used to predict the percolation threshold and the flake-to-flake distances, to complement the experimental results. A substantial increase in thermal stability of rGO is observed after surface modification, either by silanization or subsequent polymerizations. The non-linear DC resistivity of neat and silanized rGO and its trapping of charge-carriers in semi-crystalline EBA are demonstrated for the first time. It is shown that the polymer-grafted rGO improve the dispersibility in the EBA-matrix and that the graft length controls the inter-flake distances (i.e. charge-carrier hopping distances). By the appropriate selection of graft lengths, both highly resistive materials at 10 kV mm-1 and FGMs with a large and distinct drop in resistivity (six decades) are obtained, followed by saturation. The nonlinear drop in resistivity is attributed to narrow inter-flake distance distributions of grafted rGO.

A Review of Polyolefin-Insulation Materials in High Voltage Transmission; From Electronic Structures to Final Products.

This review focuses on the use of polyolefins in high-voltage direct-current (HVDC) cables and capacitors. A short description of the latest evolution and current use of HVDC cables and capacitors is first provided, followed by the basics of electric insulation and capacitor functions. Methods to determine dielectric properties are described, including charge transport, space charges, resistivity, dielectric loss, and breakdown strength. The semicrystalline structure of polyethylene and isotactic polypropylene is described, and the way it relates to the dielectric properties is discussed. A significant part of the review is devoted to describing the state of art of the modeling and prediction of electric or dielectric properties of polyolefins with consideration of both atomistic and continuum approaches. Furthermore, the effects of the purity of the materials and the presence of nanoparticles are presented, and the review ends with the sustainability aspects of these materials. In summary, the effective use of modeling in combination with experimental work is described as an important route toward understanding and designing the next generations of materials for electrical insulation in high-voltage transmission.

Coarse-Grained Model for Prediction of Hole Mobility in Polyethylene.

Electrical conductivity measurements of polyethylene indicate that the semicrystalline structure and morphology influence the conductivity. To include this effect in atomistic charge transport simulations, models that explicitly or implicitly take morphology into account are required. In the literature, charge transport simulations of amorphous polyethylene have been successfully performed using short oligomers to represent the polymer. However, a more realistic representation of the polymer structure is desired, requiring the development of fast and efficient charge transport algorithms that can handle large molecular systems through coarse-graining. Here, such a model for charge transport simulations in polyethylene is presented. Quantum chemistry calculations were used to define six segmentation rules on how to divide a polymer chain into shorter segments representing localized molecular orbitals. Applying the rules to amorphous systems yields distributions of segments with mode and median segment lengths relatively close to the persistence length of polyethylene. In an initial test, the segments of an amorphous polyethylene were used as hopping sites in kinetic Monte Carlo (KMC) simulations, which yielded simulated hole mobilities that were within the experimental range. The activation energy of the simulated system was lower compared to the experimental values reported in the literature. A conclusion may be that the experimental result can only be explained by a model containing chemical defects that generate deep traps.

Electric Resistance of Elastic Strain Sensors-Fundamental Mechanisms and Experimental Validation.

Elastic strain sensor nanocomposites are emerging materials of high scientific and commercial interest. This study analyzes the major factors influencing the electrical behavior of elastic strain sensor nanocomposites. The sensor mechanisms were described for nanocomposites with conductive nanofillers, either dispersed inside the polymer matrix or coated onto the polymer surface. The purely geometrical contributions to the change in resistance were also assessed. The theoretical predictions indicated that maximum Gauge values are achieved for mixture composites with filler fractions slightly above the electrical percolation threshold, especially for nanocomposites with a very rapid conductivity increase around the threshold. PDMS/CB and PDMS/CNT mixture nanocomposites with 0-5.5 vol.% fillers were therefore manufactured and analyzed with resistivity measurements. In agreement with the predictions, the PDMS/CB with 2.0 vol.% CB gave very high Gauge values of around 20,000. The findings in this study will thus facilitate the development of highly optimized conductive polymer composites for strain sensor applications.

Large-scale synthesis of 2D-silica (SiOx) nanosheets using graphene oxide (GO) as a template material.

Graphene oxide (GO) was used in this study as a template to successfully synthesize silicon oxide (SiOx) based 2D-nanomaterials, adapting the same morphological features as the GO sheets. By performing a controlled condensation reaction using low concentrations of GO (<0.5 wt%), the study shows how to obtain 2D-nanoflakes, consisting of GO-flakes coated with a silica precursor that were ca. 500 nm in lateral diameter and ca. 1.5 nm in thickness. XPS revealed that the silanes had linked covalently with the GO sheets at the expense of the oxygen groups present on the GO surface. The GO template was shown to be fully removable through thermal treatment without affecting the nanoflake morphology of the pure SiOx-material, providing a methodology for large-scale preparation of SiOx-based 2D nanosheets with nearly identical dimensions as the GO template. The formation of SiOx sheets using a GO template was investigated for two different silane precursors, (3-aminopropyl) triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS), showing that both precursors were capable of accurately templating the graphene oxide template. Molecular modeling revealed that the choice of silane affected the number of layers coated on the GO sheets. Furthermore, rheological measurements showed that the relative viscosity was significantly affected by the specific surface area of the synthesized particles. The protocol used showed the ability to synthesize these types of nanoparticles using a common aqueous alcohol solvent, and yield larger amounts (∼1 g) of SiOx-sheets than what has been previously reported.

Highly insulating thermoplastic nanocomposites based on a polyolefin ternary blend for high-voltage direct current power cables.

Octyl-silane-coated Al2O3 nanoparticles are found to be a promising conductivity-reducing additive for thermoplastic ternary blends comprising low-density polyethylene (LDPE), isotactic polypropylene and a styrenic copolymer. The ternary blend nanocomposites were prepared by compounding the blend components together with an LDPE-based masterbatch that contained the nanoparticles. The nanoparticles did not affect the superior stiffness of the ternary blends, compared to neat LDPE, between the melting temperatures of the two polyolefins. As a result, ternary blend nanocomposites comprising 38 wt% polypropylene displayed a storage modulus of more than 10 MPa up to at least 150 °C, independent of the chosen processing conditions. Moreover, the ternary blend nanocomposites featured a low direct-current electrical conductivity of about 3 × 10-15 S m-1 at 70 °C and an electric field of 30 kV mm-1, which could only be achieved through the presence of both polypropylene and Al2O3 nanoparticles. This synergistic conductivity-reducing effect may facilitate the design of more resistive thermoplastic insulation materials for high-voltage direct current (HVDC) power cables.

Validation of a 3D CT method for measurement of linear wear of acetabular cups.

BACKGROUND: We evaluated the accuracy and repeatability of a 3D method for polyethylene acetabular cup wear measurements using computed tomography (CT). We propose that the method be used for clinical in vivo assessment of wear in acetabular cups. MATERIAL AND METHODS: Ultra-high molecular weight polyethylene cups with a titanium mesh molded on the outside were subjected to wear using a hip simulator. Before and after wear, they were (1) imaged with a CT scanner using a phantom model device, (2) measured using a coordinate measurement machine (CMM), and (3) weighed. CMM was used as the reference method for measurement of femoral head penetration into the cup and for comparison with CT, and gravimetric measurements were used as a reference for both CT and CMM. Femoral head penetration and wear vector angle were studied. The head diameters were also measured with both CMM and CT. The repeatability of the method proposed was evaluated with two repeated measurements using different positions of the phantom in the CT scanner. RESULTS: The accuracy of the 3D CT method for evaluation of linear wear was 0.51 mm and the repeatability was 0.39 mm. Repeatability for wear vector angle was 17°. INTERPRETATION: This study of metal-meshed hip-simulated acetabular cups shows that CT has the capacity for reliable measurement of linear wear of acetabular cups at a clinically relevant level of accuracy.

Electrical conductivity of anisotropic PMMA composite filaments with aligned carbon fibers - predicting the influence of measurement direction.

In order to study the electrical conductivity of anisotropic PMMA/carbon fiber (CF) composites, cylindrical PMMA/CF filaments were extruded through a capillary rheometer, resulting in an induced CF orientation along the extrusion direction. The aspect ratios of the CFs in the filaments were accurately regulated using a two-step melt mixing process. By measuring the vertical and horizontal resistances of filaments where the outermost layer was successively peeled off, the anisotropic conductivities could be calculated. This was done using a novel analytical model where each cylindrical composite filament was defined as a structure consisting of three concentric cylinders with potentially different conductivities and CF orientations. The electrical conductivity increased with the degree of fiber orientation along the voltage direction and the effects of anisotropy and measurement direction were incorporated into the (isotropic) McLachlan equation. The required distance for electrical contact between the CFs was calculated to be 16 nm. Finite element (FEM) simulations were successfully utilized to confirm the data.

Lamellae-controlled electrical properties of polyethylene - morphology, oxidation and effects of antioxidant on the DC conductivity.

Destruction of the spherulite structure in low-density polyethylene (LDPE) is shown to result in a more insulating material at low temperatures, while the reverse effect is observed at high temperatures. On average, the change in morphology reduced the conductivity by a factor of 4, but this morphology-related decrease in conductivity was relatively small compared with the conductivity drop of more than 2 decades that was observed after slight oxidation of the LDPE (at 25 °C and 30 kV mm-1). The conductivity of LDPE was measured at different temperatures (25-60 °C) and at different electrical field strengths (3.3-30 kV mm-1) for multiple samples with a total crystalline content of 51 wt%. The transformation from a 5 µm coherent structure of spherulites in the LDPE to an evenly dispersed random lamellar phase (with retained crystallinity) was achieved by extrusion melt processing. The addition of 50 ppm commercial phenolic antioxidant to the LDPE matrix (e.g. for the long-term use of polyethylene in high voltage direct current (HVDC) cables) gave a conductivity ca. 3 times higher than that of the same material without antioxidants at 60 °C (the operating temperature for the cables). For larger amounts of antioxidant up to 1000 ppm, the DC conductivity remained stable at ca. 1 × 10-14 S m-1. Finite element modeling (FEM) simulations were carried out to model the phenomena observed, and the results suggested that the higher conductivity of the spherulite-containing LDPE stems from the displacement and increased presence of polymeric irregularities (formed during crystallization) in the border regions of the spherulite structures.

Biocompatible, Flexible Strain Sensor Fabricated with Polydopamine-Coated Nanocomposites of Nitrile Rubber and Carbon Black.

A flexible, biocompatible, nitrile butadiene rubber (NBR)-based strain sensor with high stretchability, good sensitivity, and excellent repeatability is presented for the first time. Carbon black (CB) particles were embedded into an NBR matrix via a dissolving-coating technique, and the obtained NBR/CB composite was coated with polydopamine (PDA) to preserve the CB layer. The mechanical properties of the NBR films were found to be significantly improved with the addition of CB and PDA, and the produced composite films were noncytotoxic and highly biocompatible. Strain-sensing tests showed that the uncoated CB/NBR films possess a high sensing range (strain of ∼550%) and good sensitivity (gauge factor of 52.2), whereas the PDA/NBR/CB films show a somewhat reduced sensing range (strain of ∼180%) but significantly improved sensitivity (gauge factor of 346). The hysteresis curves obtained from cyclic strain-sensing tests demonstrate the prominent robustness of the sensor material. Three novel equations were developed to accurately describe the uniaxial and cyclic strain-sensing behavior observed for the investigated strain sensors. Gloves and knee/elbow covers were produced from the films, revealing that the signals generated by different finger, elbow, and knee movements are easily distinguishable, thus confirming that the PDA/NBR/CB composite films can be used in a wide range of wearable strain sensor applications.

Starch/Alkane Diol Materials: Unexpected Ultraporous Surfaces, Near-Isoporous Cores, and Films Moving on Water.

The aim of this study was to find alternative starch plasticizers to glycerol that yielded a less tacky material in high-moisture conditions without leading to starch crystallization. A range of glycerol films containing different potential plasticizers (linear alkane diols) were therefore produced, and it was shown that 1,3-propanediol, in combination with glycerol, was a possible solution to the problem. Several additional interesting features of the starch films were however also revealed. The larger diols, instead of showing plasticizing features, yielded a variety of unexpected structures and film properties. Films with 1,6-hexanediol and 1,7-heptanediol showed an ultraporous film surface and near-isoporous core. The most striking feature was that starch films with these two diols moved/rotated over the surface when placed on water, with no other stimulus than the interaction with water. Films with 1,8-octanediol and 1,10-decanediol did not show these features, but there was clear evidence of a structure with phase-separated crystallized diol in a starch matrix, as observed in high-resolution scanning electron microscopy (SEM) images.

Understanding and modelling the diffusion process of low molecular weight substances in polyethylene pipes.

Peroxides are widely used as crosslinkers in polyethylene (PE) drinking water pipes. Cross-linked polyethylene (PEX) has better mechanical properties than PE, but peroxide decomposition by-products can migrate from PEX water pipes into the drinking water unless sufficient preventive actions are undertaken. This work systematically examines the migration of tert-Butyl methyl ether (MTBE), a dominating crosslinking by-product from PEX water pipes, into tap water by utilizing both experimental techniques and finite element (FEM) diffusion modeling. The effects of pipe geometry, tap water temperature (23-80 °C), boundary conditions (air or water interface) and degasing (at 180 °C) were considered. The MTBE diffusivity increased strongly with increasing temperature and it was concluded that a desired water quality can be achieved with proper degasing of the PEX pipes. As the FEM simulations were in excellent agreement with the experimental results, the model can accurately predict the MTBE concentration as a function of time, water temperature and PEX pipe geometry, and enable the pipe manufacturers to aid in ensuring desirable drinking water quality.

Characterization of Reduced and Surface-Modified Graphene Oxide in Poly(Ethylene-co-Butyl Acrylate) Composites for Electrical Applications.

Promising electrical field grading materials (FGMs) for high-voltage direct-current (HVDC) applications have been designed by dispersing reduced graphene oxide (rGO) grafted with relatively short chains of poly (n-butyl methacrylate) (PBMA) in a poly(ethylene-co-butyl acrylate) (EBA) matrix. All rGO-PBMA composites with a filler fraction above 3 vol.% exhibited a distinct non-linear resistivity with increasing electric field; and it was confirmed that the resistivity could be tailored by changing the PBMA graft length or the rGO filler fraction. A combined image analysis- and Monte-Carlo simulation strategy revealed that the addition of PBMA grafts improved the enthalpic solubility of rGO in EBA; resulting in improved particle dispersion and more controlled flake-to-flake distances. The addition of rGO and rGO-PBMAs increased the modulus of the materials up to 200% and the strain did not vary significantly as compared to that of the reference matrix for the rGO-PBMA-2 vol.% composites; indicating that the interphase between the rGO and EBA was subsequently improved. The new composites have comparable electrical properties as today's commercial FGMs; but are lighter and less brittle due to a lower filler fraction of semi-conductive particles (3 vol.% instead of 30-40 vol.%).

Critical considerations on load-to-failure test for monolithic zirconia molar crowns.

Application of monolithic zirconia crowns (MZCs) with reduced thickness to the molar region has been proposed, but potential complications have yet to be fully evaluated in laboratory tests. The present study aimed to develop a clinically relevant load-to-failure test in combination with fatigue treatments involving thermal and mechanical cycling (TC and MC) to evaluate the fracture resistance of molar MZCs. MZCs with a minimal thickness of 0.5 mm were bonded to dies made of resin-based composite (RBC), epoxy resin (EP), or polyoxymethylene-copolymer (POM-C). The samples were either untreated (UT) or subjected to TC (5-55 °C for 1â€¯× 105 cycles) and MC (300 N for 2.4â€¯× 106 cycles). The stress generated by TC and MC was simulated by finite element modeling. The load-to-failure test was performed using an inverse V-shaped two-plane indenter and was followed by fractographic analysis. The median values of fracture load for MZC/RBC and MZC/EP in the TC group were significantly lower than those in the UT group. MC also decreased the median value of fracture load for MZC/RBC significantly, but not that for MZC/EP and MZC/POM-C. Fractography revealed that the fracture started in the cervical area in all groups, which is similar to clinically failed crowns. The simulation confirmed stress concentration at the cervical area in both TC and MC groups. The present study suggests that the load-to-failure test using a two-plane indenter could induce clinically relevant fracture of MZCs, the vulnerability of the MZCs depends largely on the die material employed, and MZCs are more likely to be damaged by thermal fatigue than mechanical fatigue.