In recent years, the demand direction for electronic equipment has expanded into embedded and miniaturized devices. The heat radiation problem has become one of the most significant factors for hindering the development of electronic devices. Since heat radiation material is one of the important components in electronic devices, the demand for enhancing thermal conductivity is also increasingly urgent. Research on thermal conductive polymer composites has become a major direction for developing functional composites. This work reviewed the recent progress in the fabrication of thermal conductive polymer composites. Five different structures are presented, including the using of single fillers, hybrid fillers, double threshold percolation structure, segregated structure and other complex multiphase structures. Specifically, the preparation of high-performance thermal conductive polymer composites was introduced through the combination of various thermal conductive fillers. Finally, the development direction of high thermal conductive polymer composites was briefly explored.

Isothiourea is an important class of sulfur-containing molecules showing unique catalytic and biological activities. As such, polyisothiourea is envisioned to be an interesting type of polymer that potentially exhibits a number of interesting properties. However, there is no access to synthesizing well-defined polyisothiourea, and currently isothiourea-containing polymers are mainly prepared by immobilizing onto other polymer’s side chain. Herein, we report the first facile synthesis of polyisothioureas via alternating copolymerization of aziridines and isothiocayanates. Mediated by the catalytic system of phosphazene superbases/alcohol, a broad scope of aziridines and isothiocayanates could be transformed into polyisothioureas with adjustable substitutions (11 examples). The structures of obtained polyisothioureas were fully characterized with ¹H-NMR, ¹³C-NMR, and ¹H-¹³C HMBC NMR. Moreover, the polyisothioureas show tunable thermal properties depending on substitutions on the isothiourea linkages. The novel structure of these polyisothioureas will enable a powerful platform for the discovery of next-generation functional plastics.

Critical-sized bone defects, commonly encountered in clinical orthopedic surgery, present a significant challenge. One of the promising solutions is to prepare synthetic bone substitute materials with precise structural control, mechanical compatibility, and enhanced osteogenic induction performance, nevertheless the successful preparation of such materials remains difficult. In this study, a two-step technique, integrating an extrusion-based printing process with biomimetic mineralization induced by alkaline phosphatase (ALP), was developed. Initially, a pre-cured hydrogel of regenerated silk fibroin (RSF) with a small quantity of hydroxypropyl cellulose (HPC) and ALP was prepared through heating the mixed aqueous solution. This pre-cured hydrogel demonstrated thixotropic property and could be directly extruded into predetermined structures through a 3D-printer. Subsequently, the 3D-printed RSF-based materials with ALP underwent biomimetic in situ mineralization in calcium glycerophosphate (Ca-GP) mineralizing solution, utilizing the polymer chains of RSF as templates and ALP as a trigger for cleaving phosphate bonds of Ca-GP. The resulting 3D-printed RSF-mineral composites including hydrogel and sponge possessed adjustable compression modulus of megapascal grade and variable hydroxyapatite content, which could be controlled by manipulating the duration of the mineralization process. Moreover, these 3D-printed RSF-mineral composites demonstrated non-cytotoxicity towards rat bone marrow mesenchymal stem cells. Therefore, they may hold great potential for applications involving the replacement of tissues characterized by osteoinductivity and intricate structures.

Incorporation of siloxane-functionalized units into polymers backbone has proven to be an efficient strategy to improve photovoltaic performance. In this work, a low-cost siloxane-containing unit was developed to construct a series of terpolymers, and the effects of siloxane on the polymer performance were systematically studied. Different contents of thiophene containing siloxane-functionalized side chain were introduced into PM6 to obtain a series of polymers (PM6, PM6-SiO-10, PM6-SiO-20 and PM6-SiO-30). The siloxane-functionalized side chains in polymers have only a slight effect on the absorption behavior and frontier molecular orbitals. However, when the siloxane content increased, the terpolymers’ aggregation property decreased and the temperature-dependency increased, leading to improved donor-acceptor compatibility. The power conversion efficiency (PCE) based on PM6:Y6, PM6-SiO-20:Y6 and PM6-SiO-30:Y6 devices was 15.64%, 16.03% and 15.82%, respectively. In comparison, the active layer based on PM6-SiO-10:Y6 exhibits the most appropriate phase separation morphology, resulting in effective exciton dissociation, more balanced hole-electron transport and less recombination. Consequently, the highest PCE of 16.69% with an outstanding short-circuit current density of 26.96 mA·cm⁻² was obtained, which are one of the highest values for siloxane-functionalized polymer-based devices. This work demonstrates that finely controlling the content of siloxane-functionalized thiophene is beneficial for obtaining high-performance terpolymer donors and provides a novel and low-cost method to improve photovoltaic performance.

Polymer dielectrics with a high energy density and an available energy storage capacity have been playing an important role in advanced electronics and power systems. Nevertheless, the use of polymer dielectrics in harsh environments is limited by their low energy density at high temperatures. Herein, zirconium dioxide (ZrO₂) nanoparticles were decorated with amino group utilizing 4,4-methylenebis (phenyl isocyanate) (AMEO) and successfully incorporated into polyetherimide (PEI) matrix. The dielectric properties, breakdown strength, and energy storage performances of PEI/ZrO₂-AMEO nanocomposites were investigated from 25 °C to 150 °C. It is found that the combination of moderate bandgap ZrO₂ with modest dielectric constant and polar groups at interface with deep trap can offer an available strategy to simultaneously increase the dielectric constant and breakdown strength of polymer dielectrics. As a result, the composites containing ZrO₂-AMEO exhibit excellent energy storage performance at elevated temperatures. Specially, the PEI-based composites with 3 vol% ZrO₂-AMEO display a maximum discharged energy density (U_d) of 3.1 J/cm³ at 150 °C, presenting 90% higher than that of neat PEI. This study may help to better develop the polymer-based dielectric composite applied at elevated temperatures.

Green method for preparation of ion-conducting membranes (ICM) based on bacterial cellulose nanofibers (CNF) modified by a copolymer of sodium acrylate and 2-acrylamido-2-methylpropanesulfonic acid was elaborated. FTIR and NMR data confirmed grafting of polyacrylate onto cellulose surface. Formation of porous structure of the ICM was controlled by SEM and AFM. The maximal ionic conductivity of the membranes reaches 1.5 and 3.1 mS·cm⁻¹ (60 °C and 98% relative humidity) when they are saturated with water or H₂SO₄ (1 mol·L⁻¹) electrolyte, respectively. Prepared ICM was tested as a separator in a symmetrical supercapacitor with electrodes based on polyaniline hydrogel. The assembled cell demonstrate ability to operate at high current density up to 100 A·g⁻¹ maintaining specific capacitance 165 F·g⁻¹. Maximal specific capacitance of 289 F·g⁻¹ was achieved at current density 1 A·g⁻¹. Retaining of 90% of initial capacitance after 10000 of charge-discharge cycles proves high electrochemical stability of prepared ICM.

Ethylene-propylene block copolymer (EbP) is a vital component in impact polypropylene copolymer (IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanical properties are not well understood. In this work, four IPCs were investigated by atomic force microscopy-infrared (AFM-IR) to assess the phase compositions in situ, based on which in conjunction with the chain microstructure information obtained ex situ the distributions of the copolymer components were derived for each alloy. For the IPCs whose EbP comprises long P and long E segments, the EbP fraction was found to phase separate from the rubber and the PP matrix to form the cores of the disperse particles with the E-P segmented copolymer (EsP). In contrast, in the IPC with EbP composed of long P and short E segments, the EbP fraction formed an outer shell for the rubber particles with the cores comprising the EsP alone, and this IPC, containing a lower E comonomer content than its counterpart, exhibited both better impact resistance and higher flexural modulus. These results clarify how the chain structure of EbP governs the phase morphology in IPC, which in turn impacts the properties of the composite material.

Silicone rubber (SR) composites are most widely used as thermal interface materials (TIMs) for electronics heat dissipation. Thermal impedance as the main bottleneck limiting the performance of TIMs is usually neglected. Herein, the thermal impedance of SR composites loaded with different levels of hexagonal boron nitride (h-BN) as TIMs was elaborated for the first time by the ASTM D 5470 standard test and finite element analysis. It was found that elastic modulus and surface roughness of SR composites increased with the increase of h-BN content, indicating that the conformity was reduced. When the assembly pressure was 0.69 MPa, there existed an optimal h-BN content at which the contact resistance was minimum (0.39 K·cm²·W⁻¹). Although the decreased bond line thickness (BLT) by increasing the assembly pressure was beneficial to reduce the thermal impedance, the proper assembly pressure should be selected to prevent the warpage of the contact surfaces and the increase in contact resistance, according to the compression properties of the SR composites. This study provides valuable insights into fabrication of high-performance TIMs for modern electronic device applications.

To better characterize the properties of surface-initiated polymers, simultaneous bulk- and surface-initiated polymerizations are usually carried out by assuming that the properties of the surface-initiated polymers resemble those of the bulk-initiated polymers. Through a Monte Carlo simulation using a heterogeneous stochastic reaction model, it was discovered that the bulk-initiated polymers exhibit a higher molecular weight and a lower dispersity than the corresponding surface-initiated polymers, which indicates that the equivalent assumption is invalid. Furthermore, the molecular weight distributions of the two types of polymers are also different, suggesting different polymerization mechanisms. The results can be simply explained by the heterogeneous distributions of reactants in the system. This study is helpful to better understand surface-initiated polymerization.

The perfluorosulfonic acid (PFSA) membrane doped with two-dimensional conductive filler Ti₃C₂T_x is a fuel cell proton exchange membrane with high application potential. Experimental studies showed that the proton conductivity of Nafion/Ti₃C₂T_x composite membrane is improved significantly compared with that in pure Nafion. However, the microscopic mechanism of doping on the enhancement of membrane performance is remain unclear now. In this work, molecular dynamics simulation was used to investigate the microscopic morphology and proton transport behaviors of Nafion/Ti₃C₂T_x composite membrane at the molecular level. The results shown that there were significant differences about the diffusion kinetics of water molecules and hydroxium ions in Nafion/Ti₃C₂T_x at low and high hydration levels in the nanoscale region. With the increase of water content, Ti₃C₂T_x in membrane was gradually surrounded by ambient water molecules to form a hydration layer, and forming a relatively continuous proton transport channel between Nafion polymer and Ti₃C₂T_x monomer. The continuous proton transport channel could increase the number of binding sites of proton and thus achieving high proton conductivity and high mobility of water molecules at higher hydration level. The current work can provide a theoretical guidance for designing new type of Nafion composite membranes.

We study the effect of chain rigidity on tailoring the nanoparticle locations for neutral and selective particles embedded in the lamellar morphology formed by semiflexible diblock copolymer chains using self-consistent field calculations. The nanoparticles are modeled through a cavity function, and the semiflexible chains are represented by the continuous Kratsky-Porod chain model. In general situation, the nanoparticles prefer to stay at the interface in order to reduce the interface areas and thus the system free energy. However, the particle distribution at the domain center is subtle, and the underlying physics is intrinsically different depending on the polymer flexibility. In the case of flexible chains, the entropy just contributes a constant shift to the free energy when the nanoparticles move around the domain center indicating that the local metastable state if appears at the domain center is wholly attributed to the local minimum in the enthalpy. If the polymers are rigid, the variation of the particle distribution at the domain center has a close relation with the polymer rigidity and nanoparticle size. In the case of strongly rigid polymers with small nanoparticles, a nearly uniform particle distribution at the domain center is observed, while in other cases, a local enhancement of particle distribution there is found. In contrast to the case of flexible chains, further analysis reveals the crucial role of entropy in controlling the shape of particle distributions at the phase domain. Specifically, the local metastable state appears in the domain center is determined by the large entropy there which arises from the weak coupling of bond orientations that allows the polymer chains to be relatively relaxed. When the particle becomes selective, its distribution in the phase domain exhibits a shift almost uniformly rather than changes its profile, and the underlying physics still holds. In all, our study establishes a strong coupling between the chain rigidity and effect of entropy.

The polymer with nanoparticles tethered at each end is a unique model for unraveling the effect of chain ends on the polymer dynamics. We investigated the rheological behavior of this kind of polymer by using nonequilibrium molecular dynamics simulation. The effect of polymer lengths and nanoparticle radii on the complex moduli and viscosity was examined. The dependence of complex moduli on the frequency becomes less pronounced as the polymer is short or the nanoparticle is large. The shear thinning behavior was revealed for these systems, and the scaling exponent of complex viscosity with respect to the frequency was found to change from −1/2 to −3/4 as the polymer shortens or the nanoparticle enlarges. The rheological behavior was further explained by analyzing the mean square distance of nanoparticles. The simulation results were compared with the existing experimental finding, showing an agreement. The work provides information for understanding the chain end effect on polymer rheology.

To understand the dynamic process of polymer detachment, it is necessary to determine the mean detachment time of a single breakable link, which is modeled as a spring. Normally, this time can be viewed as the escape of a Brownian particle from the potential well of the spring. However, as the free dangling length of the polymer chain increases, the conformational entropy of the chain is affected by geometric confinement. It means that the wall exerts a repulsive force on the chain, resulting in accelerated link detachment from a macroscopic perspective. In this work, we investigate the effect of entropy on the detachment rate in the case where the substrate is spherical. We demonstrate that spherical confinement accelerates chain detachment both inside and outside the sphere. An analytical expression for the mean detachment time of breakable links is given, which includes an additional pre-factor that is related to the partition function. Additionally, we analyze the expressions for entropic forces inside the sphere, outside the sphere, and on a flat wall, comparing their magnitudes to explain the difference in mean detachment time.