Effect of the sol fraction and hydrostatic deformation on the viscoelastic behavior of prestrained highly filled elastomers

This study focuses on the relations between the microstructure and the viscoelastic behavior of an industrial solid propellant belonging to the class of highly filled elastomers. Precisely, the study aims at determining the impact on the viscoelastic behavior of the presence of the sol fraction inside the polymer network. The sol fraction is the part of the binder that a good solvent can extract. The solid propellant is swollen to various extents by solutions of plasticizer and polymer molecules. This swelling leads to a hydrostatic deformation of the polymer network, corresponding to an extension or contraction loading for each specimen. Prestrained dynamic mechanical analysis tests, superimposing a small oscillating strain on a prestrain, characterize the viscoelastic behavior. The degree of swelling of the network and the effective filler fraction drive the viscoelastic response. In addition, the mechanical behavior does not depend on the chemical nature of the introduced sol fraction. Moreover, a nonlinear behavior, i.e., an increase in both storage and loss moduli with increasing prestrain, is initiated at low prestrain. This nonlinearity depends on the contraction or extension of the network and could result from particles aligning with prestrain, which is expected in such highly filled materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A comparison of white rice husk ash and silica as fillers in ethylene–propylene–diene terpolymer vulcanizates

White rice husk ash (WRHA) and silica filled ethylene–propylene–diene terpolymer (EPDM) vulcanizates were prepared using a laboratory size two‐roll mill. Curing characteristics and physical properties of vulcanizates were studied with respect to the filler loading and filler type. Filler loading was varied from 0–50 parts per hundred resin (phr) at 10 phr intervals. Curing was carried out using a semi‐efficient vulcanization system in a Monsanto rheometer. Enhancement of the curing rate was observed with increasing WRHA loading, whereas the opposite trend was observed for silica‐filled vulcanizates. It was also indicated by the maximum torque and Mooney viscosity results that WRHA offers processing advantages over silica. Compared to the silica‐filled vulcanizates, the effect of filler loading on the physical properties of WRHA‐filled vulcanizates was not significant. According to these observations, WRHA could be used as a diluent filler for EPDM rubber, while silica can be used as a reinforcing filler. © 2001 Society of Chemical Industry     

Effect of filler–filler interaction on rheological behaviour of natural rubber compounds filled with both carbon black and silica

Rubber compounds are reinforced with fillers such as carbon black and silica. In general, filled rubber compounds show smooth rheological behaviour in measurement of Mooney viscosity or Mooney scorch time. Variation in rheological behaviour was studied in terms of the filler composition using natural rubber compounds filled with both carbon black and silica (carbon black/silica = 60/20,40/40, and 20/60 phr). The compound filled with carbon black/silica of 60/20 phr showed normal rheological behaviour. However, the compounds filled with carbon black/silica of 40/40 and 20/60 phr showed abnormal rheological behaviour, in which the viscosity increased suddenly and then decreased at a certain point during the measurement. The abnormal behaviour was explained by the strong filler–filler interaction of silica. Moreover, the abnormal rheological behaviour was displayed more clearly as the storage time of compounds is increased. © 2003 Society of Chemical Industry     

Influence of the silica content on rheological behaviour and cure characteristics of silica‐filled styrene–butadiene rubber compounds

Rheological behaviour and cure characteristics of silica‐filled styrene–butadiene rubber (SBR) compounds and SBR compounds filled with both silica and carbon black with different silica contents were investigated. Rheocurves of the time versus the torque of the compounds showed specific trends with the silica content. For the compounds with low silica content (less than 50 phr), the torque decreased immediately after the steep increase at the initial point of the rheocurve and then increased very slowly. For the compounds with high silica content (more than 50 phr), the rheographs showed two minimum torque points; the torque decreased immediately after the steep increase at the start point of the rheocurve and then increased sharply before reaching the second minimum point. This can be explained by the strong filler–filler interaction of silica. The minimum torque of the compound increased slightly with an increase of the silica content up to 50 phr silica content and then increased appreciably. For the silica‐filled compounds, cure times of the t₀₂, t₄₀, and t₉₀ became shorter with an increase of the filler content. For the compounds filled with both silica and carbon black (total filler content of 80 phr), the cure times became longer with an increase of the silica content ratio. © 2001 Society of Chemical Industry     

Effect of loading chemically and mechanically pre-treated fumed silica as filler on an etch & rinse model dental adhesive

Fumed silica is one of the most commonly used fillers for dental resin adhesives. However, fumed silica produced by flame hydrolysis of chlorosilanes are typically agglomerated aggregates instead of isolated primary particles. The fumed silica aggregates may affect the dispersion of fillers in the resin matrix, thus affect the bonding performance of the dental adhesives. In this study, fumed silica fillers chemically treated with methacrylsilane were loaded into an etch & rinse model dental adhesive. Filler 1 was only chemically pre-treated, while Filler 2 was combined chemically and mechanically pre-treated to break the agglomerated aggregates. The experiment result indicated that Filler 1 has faster rheology control effect than Filler 2 on the handling property of the filled resin adhesive showing as the rapid increased viscosity, which may due to the fast inorganic phase growing in the Filler 1 filled resin matrix. As for the mechanical properties, neither Filler 1 nor Filler 2 has an positive effect on the micro-tensile bond strength in short term and long term, despite of the fact that lower weight percent of Filler 2 loading is favourable to the penetration of the experimental adhesive into dentin substrate. In conclusion, mechanically pre-treatment to break the agglomerated fumed silica is helpful to increase the limit of filler loading percent while maintaining appropriate handling property, but the chemically and mechanically pre-treatment cannot provide positive effect on bonding performance within the range of this study.     

The effect of cationic surfactant and some organic/inorganic additives on the morphology of mesostructured silica templated by pluronics

Tri-block copolymers (poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide), represented as EO_xPO_yEO_x), pluronics (F127 = EO₁₀₆PO₇₀EO₁₀₆, P65 = EO₂₀PO₃₀EO₂₀, P85 = EO₂₇PO₃₉EO₂₇, P103 = EO₁₇PO₅₅EO₁₇, and P123 = EO₂₀PO₇₀EO₂₀) and cationic surfactants (cethyltrimethylammonium bromide (CTAB)), two surfactant systems, form complex micelles that self-assemble into mesostructured particles with distinct morphology depending on the pluronic type, the concentration of the cationic surfactant and the organic–inorganic ingredients in a siliceous reaction media under acidic conditions. The CTAB–P65 and CTAB–P85 systems form spheres, CTAB–P103 and CTAB–P123 systems form wormlike particles, and CTAB–F127 system form single crystals of mesostructured silica particles under very similar conditions. However addition of various salts (such as KCl and NaNO₃) into a CTAB–P103 or CTAB–P123 solution system and cyclohexane and KCl into a CTAB–P85 solution system produces the mesostructured silica spheres and wormlike particles, respectively. By controlling the hydrophilic–hydrophobic character of the pluronics, core–corona interface, by means of additives, such as small organic molecules or salts, one could obtain the desired morphology that is dictated by the shape of the micelles of the pluronic–cationic surfactant complex. The effects of the additives and the formation mechanism of those morphologies have been discussed using spectroscopy (FT-IR and Raman), diffraction (XRD) and microscopy (POM and SEM) data.     

Development of Fe‐, Sb‐, Bi‐ and Al‐impregnated silica catalysts using rice husk silica as a support for Friedel–Crafts benzylation of arenes

The milling by‐product of rice, rice husk, constitutes a major waste of the agricultural industry. It is mainly used as a fuel additive for various purposes, leaving behind residual ash which is rich in silica (Biogenic silica). In the present project, rice husk silica was impregnated with Fe³⁺, Sb³⁺, Bi³⁺ and Al³⁺ from both their aqueous and organic solutions. The resultant catalysts were activated at 120 °C and 550 °C and used for the Friedel–Crafts benzylation of benzene using benzyl chloride. Copyright © 2003 Society of Chemical Industry     

Computing the distance between a nonlinear model and its linear approximation: an approach

In this paper we consider the following problem: viewing both a nonlinear system model and its linearization as mappings from input-to-state, we define the error between the state of the original nonlinear system and that of the linearization and find the region of the state space where this error is norm-bounded, in the integral-square (or -norm) sense. Using the Hamilton–Jacobi inequality we define the distance between these two systems as the upper bound of this error.     

Exploring the simultaneous effect of nano‐silica reinforcement and electron‐beam irradiation on a model LDPE/EVA‐based TPE system

BACKGROUND: The technical properties of polyolefinic thermoplastic elastomer (TPE) systems can be modified significantly using fillers like nano‐silica. Controlled irradiation can potentially be an effective way of tailoring the technical properties of such nano‐silica‐filled TPE systems. RESULTS: The effect of controlled electron‐beam irradiation on the properties of a pristine silica nanoparticle‐filled model low‐density polyethylene/ethylene–(vinyl acetate) (LDPE/EVA) TPE system is explored in this paper. The morphology of such a filled system was investigated using scanning electron microscopy (SEM) and field‐emission SEM. The dispersion of silica particles was analysed using transmission electron microscopy which clearly indicates that at low loading a fine dispersion of silica occurs in the polymer matrix. Swelling studies and Fourier transform infrared analyses indicate the occurrence of a favourable EVA–silica interaction. On the whole, it is observed that electron‐beam irradiation induces a high degree of reinforcement in all the silica‐filled samples through interfacial crosslinking as well as controlled crosslinking in the two polymer phases. In a few samples the processing characteristics are remarkably preserved following concurrent nano‐silica reinforcement and irradiation, while the technical properties of TPE systems, including set, solvent swelling and mechanical properties, are improved. However, the improvement in properties is a strong function of sequence of addition of filler in the LDPE/EVA blends. CONCLUSION: The green technique studied can be potentially extended for the improvement of the technical properties of conventional TPE systems. Copyright © 2009 Society of Chemical Industry     

Target Hopping as a Useful Tool for the Identification of Novel EphA2 Protein–Protein Antagonists

Lithocholic acid (LCA), a physiological ligand for the nuclear receptor FXR and the G‐protein‐coupled receptor TGR5, has been recently described as an antagonist of the EphA2 receptor, a key member of the ephrin signalling system involved in tumour growth. Given the ability of LCA to recognize FXR, TGR5, and EphA2 receptors, we hypothesized that the structural requirements for a small molecule to bind each of these receptors might be similar. We therefore selected a set of commercially available FXR or TGR5 ligands and tested them for their ability to inhibit EphA2 by targeting the EphA2‐ephrin‐A1 interface. Among the selected compounds, the stilbene carboxylic acid GW4064 was identified as an effective antagonist of EphA2, being able to block EphA2 activation in prostate carcinoma cells, in the micromolar range. This finding proposes the “target hopping” approach as a new effective strategy to discover new protein–protein interaction inhibitors.     

Methyl,Ethyl, Propyl,Butyl: Futile But Not for Water,as the Correlation of Structure and Thermodynamic Signature Shows in a Congeneric Series of Thermolysin Inhibitors

Water is ubiquitously present in any biological system and has therefore to be regarded as an additional binding partner in the protein–ligand binding process. Upon complex formation, a new solvent‐exposed surface is generated and water molecules from the first solvation layer will arrange around this newly formed surface. So far, the influence of such water arrangements on the ligand binding properties is unknown. In this study, the binding modes of nine congeneric phosphonamidate‐type inhibitors with systematically varied, size‐increasing hydrophobic P₂′ substituents (from methyl to phenylethyl) addressing the hydrophobic, solvent‐exposed S₂′ pocket of thermolysin were analyzed by high‐resolution crystal structures and correlated with their thermodynamic binding profiles as measured by isothermal titration calorimetry. Overall, ΔΔG spreads over 7.0 kJ mol^?1, ΔΔH varies by 15.8 kJ mol^?1, and ?TΔΔS by 12.1 kJ mol^?1. Throughout the series, these changes correlate remarkably well with the geometric differences of water molecules arranged adjacent to the P₂′ substituents. Ligands with medium‐sized P₂′ substituents exhibit highest affinities, presumably because of their optimal solvation patterns around these complexes. The addition, removal, or rearrangement of even a single methyl group can result in a strong modulation of the adjacent water network pattern shifting from enthalpy to entropy‐driven binding. In conclusion, the quality of a water network assembled around a protein–ligand complex influences the enthalpy/entropy signature and can even modulate affinity to a surprising extent.     

Selective repartition of in situ generated silica produced during the evolution of an epoxide network from a homogeneous precursors mixture and effects on properties

Phase separation of organic networks derived from mixtures of reactive monomers and/or oligomers can take place through the formation of IPNs or precipitation of particles. The latter systems are widely used as a means of increasing the fracture toughness of thermosetting resins, and particularly for products obtained from mixtures of epoxy resins and functionalized aliphatic oligomers. In the present work several mixtures comprised of difunctional epoxy resins, silane functionalized perfluoroether oligomers, prehydrolyzed tetraethoxysilane, and an aromatic amine hardener were examined in a variety of compositions and preparative procedures. The aims were to control the kinetics of phase separation and the repartition of the different components in the two phases, so that the silica domains could be preferentially located within the precipitated soft particles. It was found that the silane functionalization of the perfluoroether oligomer provided an effective mechanism for the localization of the siloxane networks within the precipitated particles. However, phase separation by the precipitation of particles would only take place for systems in which the perfluoroether oligomer could be reacted with an excess of epoxy resin prior to adding the alkoxysilane solution and the hardener. Moreover, it was difficult to achieve the total localization of the siloxane component into the perfluoroether network. The siloxane species remaining dissolved in the resin gave rise to severe embrittlement of the products through reactions with the epoxy chains. Using mixtures of suitably functionalized perfluoroether oligomers it was possible to produce the conditions by which the localization of the silica domains into the precipitated particles could be maximized. This has resulted also in the formation of graded interphase regions and to a global improvement in mechanical properties, manifested as a concomitant increase in modulus, strength, and toughness. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1279–1290, 2004     

One‐step formation of polyurea gel as a multifunctional approach for biological and environmental applications

This work presents a facile one‐pot fabrication of polyurea (PU) organogels based on polyetheramine (PEO, Jeffamine ED‐2003) and a crosslinker hexamethylene diisocyanate trimer (HDI) which were subsequently used as a drug carrier to incorporate a curcumin hydrophobic molecule in aqueous conditions and for removal of an anionic pollutant in water. PU can be obtained in different shapes with easy control of film thickness with high transparency, flexibility and homogeneous dispersion of curcumin in the matrix. Due to the hydrophilic nature of PEO a high swelling degree was demonstrated by the PU gel. The phase separated domains and the temperature's influence on the system's structural order/disorder were examined by small‐angle X‐ray scattering, showing a more PU ordered system (interface between hard and soft segments) after decreasing the temperature to ?90 °C. The presence of curcumin in the structure of PU was confirmed by Fourier transform infrared, photoluminescence and release studies. A highly efficient removal of Congo red dye from aqueous solution using PU as adsorbent was observed. Moreover, the effect of unloaded and curcumin‐loaded PU gels was evaluated on Schistosoma mansoni adult worms. Detailed in vitro cell viability experiments showed the biocompatibility of loaded and unloaded PU gels. The easy processability of the multifunctional PU shows that it has promising applications as transdermal and soft tissue implantable delivery devices for a large number of poorly water‐soluble drugs and as an efficient adsorbent for removal of organic dyes; it can also be used in the future in dermatological treatments against malignant melanoma. © 2020 Society of Chemical Industry     

Kaolin modified with sodium salt of rubber seed oil as a reinforcing filler for blends of natural rubber,polybutadiene rubber and acrylonitrile–butadiene rubber

Blends of natural rubber (NR) and synthetic rubbers are widely used in the rubber industry to meet specific performance requirements. Further, the emerging field of organomodified clay/rubber nanocomposites could provide a host of novel materials having a unique combination of properties to meet various stringent service conditions. Previous studies have shown that at very low dosages, china clay (kaolin) modified with sodium salt of rubber seed oil (SRSO) improved the cure characteristics and physico‐mechanical properties of NR. Results of the present study show improved cure characteristics and physico‐mechanical properties for blends of NR with butadiene rubber and nitrile rubber containing 4 phr of SRSO‐modified kaolin as indicated by reduction in optimum cure time along with higher tensile strength, tensile modulus and elongation at break for their vulcanizates as compared to those containing unmodified kaolin. The SRSO‐modified kaolin/rubber nanocomposites showed improved flex resistance, reduced heat build‐up, tan delta and loss modulus and higher chemical crosslink density index, indicating a reinforcing effect of the SRSO‐modified kaolin, enabling the nanocomposites to have potential industrial applications. © 2015 Society of Chemical Industry     

Characterization of the Stereochemical Structures of 2H‐Thiazolo[3,2‐a]pyrimidine Compounds and Their Binding Affinities for Anti‐apoptotic Bcl‐2 Family Proteins

In a previous study we reported a class of compounds with a 2H‐thiazolo[3,2‐a]pyrimidine core structure as general inhibitors of anti‐apoptotic Bcl‐2 family proteins. However, the absolute stereochemical configuration of one carbon atom on the core structure remained unsolved, and its potential impact on the binding affinities of compounds in this class was unknown. In this study, we obtained pure R and S enantiomers of four selected compounds by HPLC separation and chiral synthesis. The absolute configurations of these enantiomers were determined by comparing their circular dichroism spectra to that of an appropriate reference compound. In addition, a crystal structure of one selected compound revealed the exocyclic double bond in these compounds to be in the Z configuration. The binding affinities of all four pairs of enantiomers to Bcl‐x_L, Bcl‐2, and Mcl‐1 proteins were measured in a fluorescence‐polarization‐based binding assay, yielding inhibition constants (K_i values) ranging from 0.24 to 2.20 μM . Interestingly, our results indicate that most R and S enantiomers exhibit similar binding affinities for the three tested proteins. A binding mode for this compound class was derived by molecular docking and molecular dynamics simulations to provide a reasonable interpretation of this observation.     

Kinetic and thermodynamic investigations of non-isothermal decomposition process of a commercial silver nitrate in an argon atmosphere used as the precursors for ultrasonic spray pyrolysis (USP): The mechanistic approach

The non-isothermal decomposition process of commercial silver nitrate used as the precursor for the USP procedure was investigated by simultaneous TGA–DTA measurements at different heating rates, in an argon atmosphere. Detailed kinetic and thermodynamic analyses, with special emphasis on the formation of a complete mechanistic scheme of the process were performed. It was found that the process under study can be described by the acceleratory power law kinetic model (P2), in the range of the extent of conversion (α) values (0.15 ≤ α ≤ 0.85), where the value of the apparent activation energy (E_a) can be considered as the constant (141.3 kJ mol⁻¹). The kinetic prediction analysis was shown that only the power law kinetic model (f(α) = 2α^1/2) gives the value of E_a which is consistent with the value obtained from the isothermal conditions. The critical temperature (T_c) of decomposition process was determined. The resulting value of T_c was in fairly good agreement with the starting temperature of thermal decomposition of silver oxide (Ag₂O). The thermodynamic functions of decomposition process are calculated by the activated complex theory and showed that the silver–oxygen bond secession can be interpreted as a “slow” stage of the decomposition process.