Constructing Self-Healing Polydimethylsiloxane through Molecular Structure Design and Metal Ion Bonding.

Self-healing polydimethylsiloxane (PDMS) has garnered significant attention due to its potential applications across various fields. In this study, a functionalized modification of PDMS containing di-aminos was initially conducted using 2,6-pyridinedicarbonyl chloride to synthesize pyridine-PDMS (Py-PDMS). Subsequently, rare earth metal europium ions (Eu3+) were incorporated into Py-PDMS. Due to the coordination interaction between Eu3+ and organic ligands, a coordination cross-linking network was created within the Py-PDMS matrix, resulting in the fabrication of Eu3+-Py-PDMS elastomer. At a molar ratio of Eu3+ to ligands of 1:1, the tensile strength of Eu3+-Py-PDMS reached 1.4 MPa, with a fracture elongation of 824%. Due to the dynamic reversibility of coordination bonds, Eu3+-Py-PDMS with a metal-to-ligand molar ratio of 1:2 exhibited varying self-healing efficiencies at different temperatures. Notably, after 4 h of repair at 60 °C, its self-healing efficiency reached nearly 100%. Furthermore, the gas barrier properties of Eu3+-Py-PDMS with a molar ratio of 1:1 was improved compared with that of Eu3+-Py-PDMS with a molar ratio of 1:1. This study provides an effective strategy for the design and fabrication of PDMS with high mechanical strength, high gas barrier properties, and exceptional self-healing efficiency.

Fluorination Modification of Methyl Vinyl Silicone Rubber and Its Compatibilization Effect on Fluorine/Silicone Rubber Composites.

Among numerous rubbers, high-performance rubber composites can be obtained by mixing fluororubber (FKM) with excellent oil resistance and silicone rubber (SiR) with excellent low-temperature resistance. While the difference in polarity between these two kinds of rubbers leads to a reduction in the properties of the composites. To solve the compatibility problem between the two-phase interfaces in FKM/SiR composites, in this research, fluorinated silicone rubbers (MVQ-g-PFDT) of methyl vinyl silicone rubber (MVQ) grafted with 1H,1H,2H,2H-perfluorodecanethiol (PFDT) were prepared via a facile and efficient thiol-ene click reaction, which was then added into FKM/SiR composites. The results showed that the fluorine-containing side chains could effectively inhibit the low-temperature crystallization phenomenon of silicone rubber and further broaden its application ranges in low-temperature environments. The properties of FKM/SiR composites with the addition of MVQ-g-PFDT were significantly improved, with the highest tensile strength of 14.1 MPa and the lowest mass change rate of 6.71% after 48h immersion at 200 °C in IRM903 oil. Additionally, the hydroxyl groups between the fluorine-containing side chains of MVQ-g-PFDT and the surface of silica facilitate the enhancement of the uniform dispersion of fillers. Atomic force microscopy (AFM) characterization results showed a distinct enhancement of the compatibility between the two phases of FKM and SiR. This work would provide further insight into efforts to improve compatibility between rubbers with widely different polarities.

High Barrier Properties of Butyl Rubber Composites Containing Liquid Rubber and Graphene Oxide.

The high elasticity and excellent gas barrier properties of rubber composites make them irreplaceable in the field of sealing. Constructing a complicated barrier network to reduce free volume is crucial to improving gas barrier properties. In this research, liquid acrylonitrile-butadiene rubber/γ-Methacryloxypropyl trimethoxy silane (KH570) modified graphene oxide/butyl rubber composites (LNBR/KGO/IIR) were fabricated. A KGO lamellar network was constructed to resist gas diffusion in the IIR matrix. Meanwhile, LNBR macromolecules further occupied the free volume inside the IIR composites, thereby maximizing the retardation of the path of small molecule gas permeation. The modification of GO by KH570 was successfully demonstrated through FTIR and XRD. The grafting rate of KH570 was calculated to be approximately 71.4%. KGO was well dispersed in IIR due to emulsion compounding and the formation of lamellar networks. The 300% modulus, tensile strength and tear strength of KGO/IIR were improved by 43.5%, 39.1% and 14.8%, respectively, compared to those of the IIR composite. In addition, the introduction of LNBR resulted in a 44.2% improvement in the gas barrier performance of nitrogen permeability relative to the original IIR composite.

Effect of 3-dimensional Collagen Fibrous Scaffolds with Different Pore Sizes on Pulp Regeneration.

INTRODUCTION: In this study, we generated a 3-dimensional (3D) collagen fibrous scaffold for potential pulp regeneration and investigated the influence of various pore sizes of these scaffolds on proliferation, odontoblastic differentiation of human dental pulp cells (hDPCs), and subsequent tissue formation during pulp regeneration. METHODS: Electrospinning followed by freeze-drying was used to fabricate 3D fibrous collagen scaffolds. hDPCs were cultured on these scaffolds. Cell growth was detected by a Cell Counting Kit-8 assay and observed via scanning electron microscopy. Odontogenic genes and protein expression were analyzed by real-time reverse transcription polymerase chain reaction and immunofluorescence staining. The formation of mineralized nodules was tested by von Kossa staining, scanning electron microscopy, and energy-dispersive X-ray microanalysis. Subcutaneous transplantation of the seeded scaffold/tooth fragments into nude mice was performed to observe tissue formation for pulp regeneration. RESULTS: Collagen 3D fibrous scaffolds with 3 distinct mean pore sizes (approximately 20 µm, 65 µm, and 145 µm) were fabricated, which showed good biocompatibility and bioactivity. Scaffolds with larger mean pore sizes of 65 and 145 µm improved hDPC ingrowth and proliferation, with the 65-µm scaffold group presenting the highest level of odontogenic gene expression (DSPP and DMP-1), protein expression (DMP-1), mineralized area ratio, and vascular pulplike tissue formation after 6 weeks of subcutaneous implantation. CONCLUSIONS: The pore size of collagen 3D fibrous scaffolds significantly affected cell adhesion, proliferation, odontoblastic differentiation, and tissue rehabilitation. Scaffolds with a mean pore size of 65 µm presented superior results and could be an alternative for pulp regeneration.

Molecular dynamics simulation of the formation mechanism of the thermal conductive filler network of polymer nanocomposites.

In this work, the thermal transfer capabilities of spherical and laminar/spherical filled polymer nanocomposites (PNCs) were systematically investigated by using molecular dynamics (MD) simulation. The effects of various factors such as physical interfacial interaction, filler size and filler shape on the thermal conductivity were explored. The relationship between thermal conductivity and its corresponding microstructure was examined. The thermal transfer ability of the PNCs was characterized using two approaches, including thermal conductivity (TC) and the filler conductive network. Our results showed that the increase in the filling fraction and the matrix-filler physical interfacial interaction were both conducive to the formation of the thermally conductive network. The non-linear effect of the filler size on the TC results from a competition between the filler overlapped structure and the physical interfacial interaction. Besides, the introduction of spherical nanoparticles (NPs) into laminar-filled PNCs and increasing the NP-polymer physical interfacial strength could remarkably promote the formation of a hybrid overlapping filler network and also a thermal conduction pathway. Moreover, the oscillatory shear could significantly increase the thermal conductivity of laminar/spherical filled PNCs by enhancing the overlapped structure between spherical fillers. This study provides some insights on understanding the relationship between the microstructures and the thermal conductivity of laminar/spherical NP filled PNCs at the molecular level.

Constructing Chemical Interface Layers by Using Ionic Liquid in Graphene Oxide/Rubber Composites to Achieve High-Wear Resistance in Environmental-Friendly Green Tires.

The harm caused by small rubber particles generated from tire abrasion to the atmosphere is receiving a continuing concern. For developing environmental-friendly tire tread materials with high wear resistance, building the strong interface between nano-fillers and rubber matrix is the primary challenge. Herein, ionic liquid (IL, 1-allyl-3-methylimidazole chloride) was used to modify graphene oxide (GO) by π-cation interaction and hydrogen bonding between IL and GO. Furthermore, an IL-GO/natural rubber (NR) masterbatch possessing fine dispersion of GO was prepared by the emulsion compounding method, and thereafter, a further compound with solution polymerized styrene butadiene rubber (SSBR) was fabricated for the tread rubber composite. Results showed that the double bond in the IL enhanced the cross-linking reaction during the vulcanization of rubber composites occurred at high temperature, leading to an elevated interfacial interaction between the IL-modified GO and the rubber macromolecules. Compared with silicon dioxide (SiO2)-filled NR/SSBR composites, the cross-link density, 300% modulus, and tear strength of the IL-GO/SiO2/NR/SSBR composites were increased by 10.2, 42.6, and 20.2%, respectively. Importantly, the wear resistance of the IL-GO/SiO2/NR/SSBR composites was improved by 17.3%, ascribing to the strong interface between IL-GO and rubber macromolecules.

High antibacterial and barrier properties of natural rubber comprising of silver-loaded graphene oxide.

The antibacterial and barrier properties of natural rubber used as gloves are very important for the safety of medical staffs. In this research, the silver (Ag) particles were loaded on the surface of graphene oxide (GO) first modified by polydopamine (PDA). Then, the complex particles (Ag-PDA-GO) were introduced into the natural rubber (NR) latex, and the Ag-PDA-GO/NR film composites were obtained by the dipping method. Results showed that a fine dispersion of Ag-PDA-GO in NR film was obtained due to the isolation effect of Ag and PDA between GO sheets. Compared with those of pristine NR composite, when the GO content was only 0.2 phr, the tensile strength, tear strength and modulus at 100% and 300% strains of the composites increase by 66.7%, 128%, 37.7% and 30.7%, respectively, compared with the pure NR. The gas diffusion coefficient was reduced by 15.6% due to the strong interface interaction between GO and NR macromolecules. When the GO content was only 0.1 phr, the minimum inhibitory concentrations (MIC) of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were 16 and 32 µg/mL, respectively. These results are of great significance for improving the barrier and antibacterial properties of medical rubber products.

Effect of the Topology of Carbon-Based Nanofillers on the Filler Networks and Gas Barrier Properties of Rubber Composites.

The topology of nanofillers is one of the key factors affecting the gas barrier properties of rubber composites. In this research, three types of carbon-based nanofillers, including spherical carbon black (CB), fibrous carbon nanotubes (CNTs), and layered graphene (GE) were chosen to investigate the effect of the topological structures of nanofillers on the gas barrier properties of styrene-butadiene rubber (SBR) composites. Results showed that the structure and strength of the filler networks in SBR composites were closely associated with the topology of nanofillers. When filled with 35 phr CB, 8 phr CNTs, and 4 phr GE, the SBR composites had the same strength of the filler network, while the improvement in gas barrier properties were 39.2%, 12.7%, and 41.2%, respectively, compared with pure SBR composites. Among the three nanofillers, GE exhibited the most excellent enhancement with the smallest filler content, demonstrating the superiority of two-dimensional GE in improving the barrier properties of rubber composites.

Enhanced Fatigue and Durability Properties of Natural Rubber Composites Reinforced with Carbon Nanotubes and Graphene Oxide.

Fibrous carbon nanotubes (CNTs) and lamellar graphene oxide (GO) exhibit significant advantages for improving the fatigue properties of rubber composites. In this work, the synergistic effect of CNTs and GO on the modification of the microstructure and fatigue properties of natural rubber (NR) was comprehensively investigated. Results showed that CNTs and GO were interspersed, and they formed a strong filler network in the NR matrix. Compared with those of CNT/NR and GO/NR composites, the CNT-GO/NR composites showed the smallest crack precursor sizes, the lowest crack growth rates, more branching and deflections, and the longest fatigue life.

Characterization and Quantitative Analysis of Crack Precursor Size for Rubber Composites.

In the field of engineering, the annual economic loss caused by material fatigue failure reaches 4% of the total economic output. The deep understanding of rubber fatigue failure can help develop and prepare rubber composites with high durability. The crack precursor sizes within the rubber composites are vital for the material mechanical and fatigue properties. In this study, we adopted three different characterization methods to analyze crack precursor sizes and their distribution. First, based on the theoretical formula of fracture mechanics, the size of the crack precursor was deduced from 180 µm to 500 µm by the uniaxial tensile experiment combined with tear test (nicked angle tear, planar tear and trouser tear). Second, by combining the uniaxial fatigue test of dumbbell specimen with the fatigue crack growth rate test, the average size of the crack precursor was calculated as 3.3 µm based on the Thomas fatigue crack growth model. Third, the average size of the crack precursor was 3.6 µm obtained by scanning electron microscope. Through theoretical calculations and experimental tests, the size and distribution of the crack precursors of rubber composites were systematically presented. This work can provide theoretical guidance for the improvement of fatigue performance of rubber composites.

Molecular dynamics simulation of the electrical conductive network formation of polymer nanocomposites by utilizing diblock copolymer-mediated nanoparticles.

It is very important to improve the electrical conductivities of polymer nanocomposites (PNCs) as this can widen their application. In this work, by employing a coarse-grained molecular dynamics simulation, we investigated the effect of the amphiphilic diblock copolymer (BCP)-mediated nanoparticle (NP) on the conductive probability of polymer nanocomposites (PNCs) in the quiescent state and under a shear field. The conductive probability of PNCs first increases and then decreases with increasing content of BCPs while, interestingly, it exhibits an N-type dependence on the A-Block-NP interaction. Furthermore, the conductive probability shows a non-monotonic dependence on the fraction of A block (fA) in the BCPs, which reaches the maximum value at moderate fA. Under the shear field, NPs self-assemble to form the sandwich-like structures in the matrix above a critical concentration of BCPs, which leads to the anisotropic conductive probability of PNCs. In addition, the sandwich-like structures of NPs will be broken down at a high shear rate, which reduces the difference of the directional conductive probabilities. Last, the mechanism of the formation of the sandwich-like structures of NPs is discussed. In summary, this work presents a simple method to control the conductive network formation, which can help to design PNCs with high electrical conductivity, and especially anisotropy.

Impact of uniaxial tensile fatigue on the evolution of microscopic and mesoscopic structure of carbon black filled natural rubber.

This investigation addresses the evolution of the microscopic and mesoscopic structures distribution, and micro-defects of carbon black (CB) filled natural rubber (NR) under uniaxial tensile condition during the fatigue process. NR was filled with three different grades of CB in order to understand the impact of the structural degree and specific surface areas of CB and fatigue degree on the Payne effect. It was found that the Payne effect was initially suppressed and then enhanced by increasing the degree of fatigue. The decrease of the storage modulus in the low strain area was attributed to the CB network destruction and the breakdown of the matrix cross-linking network in the early fatigue stage. However, by further increasing the degree of fatigue, the spatial rearrangement of CB aggregates with the orientation of molecular chains between adjacent CB aggregates will results in mechanical reinforcement before the appearance of micro-defects. Moreover, it has been demonstrated that the structural degree of CB has a stronger impact on the mesoscopic structures than the specific surface area of CB during the tensile fatigue process.

In-chain functionalized polymer induced assembly of nanoparticles: toward materials with tailored properties.

We adopt a molecular dynamics simulation method to describe the self-assembly of nanoparticles in in-chain functionalized polymers. In such novel systems, the organization of nanoparticles is governed by the interplay of the intrinsic attractions between nanoparticles and the entropy of redistributing the functionalized polymers that are adsorbed on the nanoparticles. Our simulations also demonstrate that this approach to nanoparticle assembly enables considerable control for the creation of polymer nanocomposites with tailored properties.

Fabrication of highly oriented hexagonal boron nitride nanosheet/elastomer nanocomposites with high thermal conductivity.

A homogeneous dispersion of hexagonal boron nitride nanosheets (BNNSs) in elastomers is obtained by solution compounding methods, and a high orientation of BNNSs is achieved by strong shearing. The composites show high thermal conductivities, especially when BNNS loading exceeds 17.5 vol%, indicating that the material is promising for thermal-management applications which need high thermal conductivity, low dielectric constant, and adequate softness.

Molecular simulation study of role of polymer-particle interactions in the strain-dependent viscoelasticity of elastomers (Payne effect).

The strain-amplitude dependence of viscoelastic behavior of model crosslinked elastomers containing various concentrations of spherical nanoparticles (NPs) was studied by non-equilibrium molecular dynamics simulation. All the filler NPs were in monodispersed state and the interactions between these particles were purely repulsive. The polymer-particle interactions were attractive and their interaction energies were tuned in a broad range. Through the computational study, many important features of the behavior of particle-reinforced elastomers observed in experiments, including the Payne effect, were successfully reproduced. It was shown that the magnitude of the Payne effect was found to depend on the polymer-particle interaction and the filler loading. By examining the microstructures of the simulation systems and their evolution during oscillatory shear, four different mechanisms for the role of the polymer-particle interactions in the Payne effect were revealed that consist of the debonding of polymer chains from NP surfaces, the breakage of polymer-shell-bridged NP network, the rearrangement of the NPs in the network into different layers and the shear-induced yielding of the rigid polymer shell in-between neighboring NPs.

Computational study of nanoparticle dispersion and spatial distribution in polymer matrix under oscillatory shear flow.

In this work, nonequilibrium molecular dynamics simulations were performed to investigate the dispersion and spatial distribution of spherical nanoparticles (NPs) in polymer matrix under oscillatory shear flow. We systematically analyzed the influences of four important factors that consist of NP-polymer interfacial strength, volume fraction of NPs, shear conditions, and polymer chain length. The simulation results showed that the oscillatory shear can greatly improve the dispersion of NPs, especially for the polymer nanocomposites (PNCs) with high NP-polymer interfacial strength. Under specific shear conditions, the NPs can exhibit three different spatial distribution states with increasing the NP-polymer interfacial strength. Interestingly, at high interfacial strength, we observed that the NPs can be distributed on several layers in the polymer matrix, forming the PNCs with sandwich-like structures. Such well-ordered nanocomposites can exhibit a higher tensile strength than those with the NPs dispersed randomly. It may be expected that the information derived in present study provides a useful foundation for guiding the design and preparation of high-performance PNCs.

High performance graphene oxide based rubber composites.

In this paper, graphene oxide/styrene-butadiene rubber (GO/SBR) composites with complete exfoliation of GO sheets were prepared by aqueous-phase mixing of GO colloid with SBR latex and a small loading of butadiene-styrene-vinyl-pyridine rubber (VPR) latex, followed by their co-coagulation. During co-coagulation, VPR not only plays a key role in the prevention of aggregation of GO sheets but also acts as an interface-bridge between GO and SBR. The results demonstrated that the mechanical properties of the GO/SBR composite with 2.0 vol.% GO is comparable with those of the SBR composite reinforced with 13.1 vol.% of carbon black (CB), with a low mass density and a good gas barrier ability to boot. The present work also showed that GO-silica/SBR composite exhibited outstanding wear resistance and low-rolling resistance which make GO-silica/SBR very competitive for the green tire application, opening up enormous opportunities to prepare high performance rubber composites for future engineering applications.

Preparation and characterization of polystyrene/Ag core-shell microspheres--a bio-inspired poly(dopamine) approach.

A facile and versatile method using a biopolymer as a chelating agent for silver ions and as a reducing agent for the formation of catalytic sites is proposed to prepare polystyrene (PS)/Ag core-shell microspheres. More specifically, the core-shell microspheres were fabricated by electroless plating after the formation of poly(dopamine) (PDA) on the surface of PS microspheres through insitu spontaneous oxidative polymerization of dopamine. The PS-PDA microspheres were characterized by SEM, XPS, and TGA. The results showed that a uniform PDA layer was formed on the PS microsphere surface and the thickness of the PDA layer could be well controlled by varying the concentration of dopamine solution. The PDA layer was used as a chelating agent for silver ions, as a reducing agent for the formation of catalytic sites by reducing the silver ions into silver nanoparticles, and as an adhesion layer between the PS microspheres and silver layer. SEM and XRD results indicate that the diameter of the silver nanoparticles decreased with the increase in the thickness of the PDA layer. The silver nanoparticles could form a continuous and compact silver layer on the surface of the PS microspheres. Furthermore, the PS-PDA/Ag core-shell microspheres showed a good conductivity of 10S/cm and a low effective density of 1.8 g/cm(3), much lower than the corresponding values for block silver. Finally, hollow silver microspheres could be prepared by removing the PS core through calcination. SEM images showed that the hollow Ag microspheres remained unbroken and retained the spherical shape.

Diaqua-(2,2'-bipyridine-6,6'-dicarboxyl-ato)nickel(II).

In the title compound, [Ni(C(12)H(6)N(2)O(4))(H(2)O)(2)], the Ni(II) atom (site symmetry 2) displays a distorted cis-NiN(2)O(4) octa-hedral coordination geometry with two N atoms and two O atoms of the tetra-dentate 2,2'-bipyridine-6,6'-dicarboxyl-ate ligand in the equatorial plane and two water mol-ecules in axial positions. The complete dianionic ligand is generated by crystallographic twofold symmetry. In the crystal, a two-dimensional supra-molecular structure parallel to (001) is formed through O-H⋯O hydrogen-bond inter-actions between the coordinated water mol-ecules and the O atoms of nearby carboxyl-ate groups.