Electron beam crosslinked gels—Preparation,characterization and their effect on the mechanical,dynamic mechanical and rheological properties of rubbers

Electron beam (EB) crosslinked natural rubber (NR) gels were prepared by curing NR latex with EB irradiation over a range of doses from 2.5 to 20 kGy using butyl acrylate as sensitizer. The NR gels were systematically characterized by solvent swelling, dynamic light scattering, mechanical and dynamic mechanical properties. These gels were introduced in virgin NR and styrene butadiene rubber (SBR) matrices at 2, 4, 8 and 16 phr concentration. Addition of the gels improved the mechanical and dynamic mechanical properties of NR and SBR considerably. For example, 16 phr of 20 kGy EB-irradiated gel-filled NR showed a tensile strength of 3.53 MPa compared to 1.85 MPa of virgin NR. Introduction of gels in NR shifted the glass transition temperature to a higher temperature. A similar effect was observed in the case of NR gel-filled SBR systems. Morphology of the gel-filled systems was studied with atomic force microscopy. The NR gels also improved the processability of the virgin rubbers greatly. Both the shear viscosity and the die swell values of EB-irradiated gel-filled NR and SBR were lower than their virgin counterparts as investigated by capillary rheometer.     

Bacterial cellulose films with controlled microstructure–mechanical property relationships

Bacterial cellulose (BC) films with different porosities have been developed in order to obtain improved mechanical properties. After 13 days of incubation of Gluconobacter xylinum bacteria in static culture, BC pellicles have been set. BC films have been compression molded after water dispersion of BC pellicles and filtration by applying different pressures (10, 50, and 100 MPa) to obtain films with different porosities. Tensile behavior has been analyzed in order to discuss the microstructure–property relationships. Compression pressure has been found as an important parameter to control the final mechanical properties of BC films where slightly enhanced tensile strength and deformation at break are obtained increasing mold compression pressure, while modulus also increases following a nearly linear dependence upon film porosity. This behavior is related to the higher densification by increasing mold compression pressure that reduces the interfibrillar space, thus increasing the possibility of interfibrillar bonding zones. Network theories have been applied to relate film elastic properties with individual nanofiber properties.     

Stability of mechanical properties of molecular layer–deposited alucone

We report on the effect of aging on the mechanical properties of molecular layer–deposited (MLD) thin films. We studied the mechanical failure of the films during uniaxial tensile testing and observed a sixfold difference in the crack-onset strain (COS) and related flexibility within the first two days after the samples were exposed to ambient air. The MLD films made using trimethylaluminum and ethylene glycol are notorious for exhibiting structural changes after the fabrication; we show that these changes are detrimental for mechanical robustness of the films. This information aids to plan the handling or the protection of these films to achieve better performance with these materials. The interfacial shear strains and COSs of the shortly air-exposed 300-nm-thick films were observed to be roughly 0.3% and 1.8%, respectively. These values are the highest reported so far for hybrid organic–inorganic MLD thin films and would extrapolate to about 14% COS for 5-nm-thick film, indicating potential applications as interfacial adhesion layer for films on polymer substrates and as a protective coating in battery applications.     

Tl(I)‐the strongest structure‐breaking metal ion in water? A quantum mechanical/molecular mechanical simulation study

Structural and dynamical properties of the Tl(I) ion in dilute aqueous solution have been investigated by ab initio quantum mechanics in combination with molecular mechanics. The first shell plus a part of the second shell were treated by quantum mechanics at Hartree-Fock level, the rest of the system was described by an ab initio constructed potential. The radial distribution functions indicate two different bond lengths (2.79 and 3.16 A) in the first hydration shell, in good agreement with large-angle X-ray scattering and extended X-ray absorption fine structure spectroscopy results. The average first shell coordination number was found as 5.9, and several other structural parameters such as coordination number distributions, angular distribution functions, and tilt- and theta-angle distributions were evaluated. The ion-ligand vibration spectrum and reorientational times were obtained via velocity auto correlation functions. The Tl-O stretching force constant is very weak with 5.0 N m(-1). During the simulation, numerous water exchange processes took place between first and second hydration shell and between second shell and bulk. The mean ligand residence times for the first and second shell were determined as 1.3 and 1.5 ps, respectively, indicating Tl(I) to be a typical "structure-breaker". The calculated hydration energy of -84 +/- 16 kcal mol(-1) agrees well with the experimental value of -81 kcal mol(-1). All data obtained for structure and dynamics of hydrated Tl(I) characterize this ion as a very special case among all monovalent metal ions, being the most potent "structure-breaker", but at the same time forming a distinct second hydration shell and thus having a far-reaching influence on the solvent structure.     

Numerical modelling of sample–furnace thermal lag in dynamic mechanical analyser

Due to dynamic nature of processes taking place during the experiment (chemical reaction and physical processes, heat flow, gas flow, etc.) the results obtained by thermal methods may considerably depend on the conditions used during the experiment. Therefore, whenever the results of thermal analysis are reported, the experimental conditions used should be stated. In this paper we have studied the heat transfer from the furnace to the sample and through the sample during dynamic mechanical analysis measurements. Numerical modelling of the heat transfer was done using an own computer program based on the heat conduction equation, solved numerically applying the finite difference methods. The calculated values of the thermal lag between the furnace and the sample were compared with the values experimentally determined on samples of a composite polymeric energetic material (double-base rocket propellant). Also, the temperature distribution within the sample as a function of the heating rate was analysed using the same numerical model. It was found out that using this model and temperature dependent heat transfer coefficient, experimentally obtained values of the thermal lag between the furnace and the sample can be satisfactory described. It was also shown that even at slow heating rates, such is, e.g. 2 °C min⁻¹, the thermal lag between the furnace and the sample can reach several degrees, while the thermal gradient within 3-mm thick rectangular sample can reach 0.4 °C.     

Inclusion complexes of ortho-anisidine and β-cyclodextrin: A quantum mechanical calculation

The structural aspects for the complexation of ortho-anisidine (O-AN)/β-cyclodextrin were explored by using PM6, density function theory B3LYP/6-31G*, M05-2X/6-31G*, B3PW91/6-31G*, MPW1PW91/6-31G*, HF/6-31G* methods and several combinations of ONIOM2 hybrid calculations. Calculations were performed upon the inclusion complexation of β-cyclodextrin (β-CD) with neutral (O-AN1) and cationic (O-AN2) species of ortho-anisidine. The obtained results with PM6 method clearly indicate that the formed complexes are energetically favored, the complex of O-AN2/β-CD in B orientation is significantly more favorable than the others energetically. The structures show the presence of several intermolecular hydrogen bond interactions that were studied on the basis of natural bonding orbital (NBO) analysis, employed to quantify the donor–acceptor interactions between ortho-anisidine and β-CD.     

Quantum mechanical reaction dynamics in collisions of chlorine atom with hydrogen molecule

We report the accurate determinations of quantum mechanical state-to-state probabilities tor reactions Cl H2 - HCl H and H' HCl - H'Cl H by the generalized Newton variational principle, on the most accurate available potential energy surface. We compare the results for three versions of realistic potential energy surfaces, and to those from hyperspherical close-coupling calculations.     

Modification of mechanical and thermal property of chitosan–starch blend films

Chitosan–starch blend films (thickness 0.2 mm) of different composition were prepared by casting and their mechanical properties were studied. To improve the properties of chitosan–starch films, glycerol and mustard oil of different composition were used. Chitosan–starch films, incorporated with glycerol and mustard oil, were further modified with monomer 2-hydroxyethyl methacrylate (HEMA) using gamma radiation. The modified films showed improvement in both tensile strength and elongation at break than the pure chitosan–starch films. Water uptake of the films reduced significantly than the pure chitosan–starch film. Thermo gravimetric analysis (TGA) and dynamic mechanical analysis (DMA) showed that the modified films experience less thermal degradation than the pure films. Scanning electron microscopy (SEM) and FTIR were used to investigate the morphology and molecular interaction of the blend film, respectively.     

Structural and mechanical characterizations of microporous silica–boron membranes for gas separation

This paper presents structural and mechanical characterizations of microporous silica membranes for gas separation. The membrane separative layer is made of microporous silica–B₂O₃ produced via a sol–gel process. This layer of about 200 nm of thickness is deposited on the internal surface of a tubular asymmetric γ-alumina/α-alumina support. FTIR and Raman analyses indicate the presence of the boron in the silica net and the above methods in conjunction with ¹¹B MAS NMR analyses of the samples indicate that boron is located mainly in the tetrahedral framework position. Such membranes present interesting gas separation properties at temperatures up to 500 °C and transmembrane pressures lower than 8 bar. He permeance values close to 10⁻¹⁰ kmol m⁻² s⁻¹ Pa⁻¹ are obtained, associated with ideal selectivity α(He/CO₂) which can reach 55. Mechanical properties of separative silica-modified layers are measured by nanoindentation and the coefficient of thermal expansion is obtained from pure material.     

Exact quantum mechanical vibration-rotation kinetic energy operator of four-particle system in various coordinates

The vibration-rotational kinetic energy operators of four-particle system in various coordinates are derived using a new and simple angular momentum method. The operators are respectively suitable for studying the systems described by scattering coordinate, valence coordinate, Radau coordinate, Radau/Jacobi and Jacobi/valence hybrid coordinates and so on. Certain properties of these operators and their possible applications are discussed.     

Synergistic mechanical effects of calcite micro- and nanoparticles and β-nucleation in polypropylene copolymers

For improving the understanding of mechanical effects in micro- and nanocomposites based on polypropylene (PP) copolymers and precipitated or ground calcium carbonate (PCC or GCC), especially in the presence of significant portions of the β-modification, a set of compounds based on different PP grades and fillers with optional β-nucleation prepared by melt compounding was studied. A synergistic improvement of mechanical properties by a combination of calcite particles and β-nucleation was found for two of the investigated high-impact base polymers up to 20 wt.% of nanofiller. While in the past research positive toughness effects were always limited to PP homopolymers with a moderate original impact strength and to particles of less than 100 nm average diameter, the toughness of high impact ethylene–propylene impact copolymers could be increased by more than 150% even at sub-zero temperatures where the failure behaviour is determined by the disperse elastomer phase.     

Breaking bonds by mechanical stress: when do electrons decide for the other side?

Using first-principles molecular dynamics, we have simulated reactions that can be induced by mechanical stress in a polymer. We have stretched a small piece of poly(ethylene glycol) (PEG) in water at finite temperature. Both the molecule and the solvent were described quantum mechanically on an equal level. The formation of ions was observed, which corresponds to a heterolytic bond cleavage. We were able to monitor the motion of the electrons during the reactions. Our simulations show that the electron transfer and the breaking of the bond occur almost simultaneously and that both processes are initiated by the approach of a solvent molecule toward the destabilized bond.     

Sintering studies on Ni–Cu–YSZ SOFC anode cermet processed by mechanical alloying

New 40 vol%[(Cu)–Ni]–YSZ cermet materials processed by mechanical alloying (MA) of the row powders are prepared. The powder compacts are sintered in air, hydrogen and inert (argon) atmospheres at a dilatometer and tubular furnace up to 1,350 °C. Sintering by activated surface concept (SAS) can anticipate and enhance the densification in such powders. Stepwise isothermal dilatometry (SID) sintering kinetics study is performed allowing determining kinetic parameters for Ni–YSZ and Ni–Cu–YSZ pellets. Two-steps sintering processes is indicated while Cu-bearing material features the smallest activation energy for sintering. The allied MA–SAS method is a promising route to prepare SOFC fuel cell anode materials.     

Interfacially induced additional damping peaks in dynamic mechanical spectra – micromechanical transitions in multipolymeric materials

The viscoelastic properties of several hypothetical multiphase polymeric materials were investigated in relation to their phase-property dependencies and microstructures. Theoretical mechanical considerations based on the self-consistent interlayer model were performed to point out that specific geometrical arrangements into phases of a set of properties of the pure constituents can lead to interfacially induced damping peaks in dynamic mechanical spectra (DMS). Such additional contributions in DMS were referred to micromechanical transitions to distinguish them from ordinary molecular transitions.     

Statistical–mechanical models with separable many-body interactions: especially partition functions and thermodynamic consequences

We start from a classical statistical–mechanical theory for the internal energy in terms of three- and four-body correlation functions g ₃ and g ₄ for homogeneous atomic liquids like argon, with assumed central pair interactions f(r_ij){\phi(r_{ij})} . The importance of constructing the partition function (pf) as spatial integrals over g ₃, g ₄ and f{\phi} is stressed, together with some basic thermodynamic consequences of such a pf. A second classical example taken for two-body interactions is the so-called one-component plasma in two dimensions, for a particular coupling strength treated by Alastuey and Jancovici (J Phys (France) 42:1, 1981) and by Fantoni and Tellez (J Stat Phys 133:449, 2008). Again thermodynamic consequences provide a particular focus. Then quantum–mechanical assemblies are treated, again with separable many-body interactions. The example chosen is that of an N-body inhomogeneous extended system generated by a one-body potential energy V(r). The focus here is on the diagonal element of the canonical density matrix: the so-called Slater sum S(r, β), related to the pf by pf(b) = òS(r, b)d[(r)\vec]{{\rm pf}(\beta) = \int {S({\bf r}, \beta)}d\vec {r}}, β = (k _B T)⁻¹. The Slater sum S(r, β) can be related exactly, via a partial differential equation, to the one-body potential V(r), for specific choices of V which are cited. The work of Green (J Chem Phys 18:1123, 1950), is referred to for a generalization, but now perturbative, to two-body forces. Finally, to avoid perturbation series, the work concludes with some proposals to allow the treatment of extended assemblies in which regions of long-range ordered magnetism exist in the phase diagram. One of us (Z.D.Z.) has recently proposed a putative pf for a three-dimensional (3D) Ising model, based on two, as yet unproved, conjectures and has pointed out some important thermodynamic consequences of this pf. It would obviously be of considerable interest if such a pf, together with conjectures, could be rigorously proved.     

Energy release characteristics of impact-initiated energetic aluminum–magnesium mechanical alloy particles with nanometer-scale structure

Aluminum–magnesium alloys, fabricated by bi-directional rotation ball milling, were used as a kind of promising solid fuel in “reactive material” that can be ignited by impact to release a large quantity of heats. Different percentages of Mg were added to Al to yield Al_90%–Mg_10% and Al_70%–Mg_30% alloys in order to probe the effect of Mg content on the microstructure and thermal reactivity of Al–Mg alloys. Structural characterization revealed that a nanometer-scale structure was formed and oxidation of as-fabricated alloy powders was faint. Moreover, as the Mg percentage increased, the particle size of alloy decreased with increasing brittleness of Al–Mg. TGA/DSC curves of the [Al_70%–Mg_30%]–O₂ system exhibited an intense exothermic peak before melting with reaction heat of 2478 J g^?1 and its weight increase reached 90.16% of its theoretical value, which contrasted clearly with 181.2 J g^?1 and 75.35% of [Al_90%–Mg_10%]–O₂ system, respectively. In addition, other than [Al_90%–Mg_10%]–Fe₂O₃ system, the [Al_70%–Mg_30%]–Fe₂O₃ system exhibited a considerable solid–solid reaction and a low activation energy. Finally, target penetration experiments were conducted and the results confirmed that a projectile composed of [Al_70%–Mg_30%]–Fe₂O₃ displayed a more complete ignition of target than that of Al–Fe₂O₃ formulation.     

Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host–guest binding energies

We have estimated free energies for the binding of nine cyclic carboxylate guest molecules to the octa-acid host in the SAMPL4 blind-test challenge with four different approaches. First, we used standard free-energy perturbation calculations of relative binding affinities, performed at the molecular-mechanics (MM) level with TIP3P waters, the GAFF force field, and two different sets of charges for the host and the guest, obtained either with the restrained electrostatic potential or AM1-BCC methods. Both charge sets give good and nearly identical results, with a mean absolute deviation (MAD) of 4 kJ/mol and a correlation coefficient (R ²) of 0.8 compared to experimental results. Second, we tried to improve these predictions with 28,800 density-functional theory (DFT) calculations for selected snapshots and the non-Boltzmann Bennett acceptance-ratio method, but this led to much worse results, probably because of a too large difference between the MM and DFT potential-energy functions. Third, we tried to calculate absolute affinities using minimised DFT structures. This gave intermediate-quality results with MADs of 5–9 kJ/mol and R ² = 0.6–0.8, depending on how the structures were obtained. Finally, we tried to improve these results using local coupled-cluster calculations with single and double excitations, and non-iterative perturbative treatment of triple excitations (LCCSD(T0)), employing the polarisable multipole interactions with supermolecular pairs approach. Unfortunately, this only degraded the predictions, probably because of a mismatch between the solvation energies obtained at the DFT and LCCSD(T0) levels.     

Improvement of UV stability and mechanical properties of biopolyesters through the addition of β-carotene

β-carotene, the most abundant carotenoid in nature and a natural antioxidant, has been added at a concentration of 2 × 10⁻⁴ g per mL of polymer film forming solution to three biopolyester matrices, poly(lactic acid) (PLA), polycaprolactone (PCL) and polyhydroxybutyrate-co-valerate (PHBV). The dispersion and stability of the antioxidant within the films was studied using confocal Raman imaging spectroscopy, colorimetry and UV/visible spectrophotometry. The films were characterized in terms of thermal and mechanical properties in comparison with control films without β-carotene. Addition of β-carotene to the three biopolyesters studied resulted in significant increases in the deformation at break and lower Young modulus. This antioxidant is thought to act as a plasticizer in the biopolyesters, thus increasing their free volume and causing a change in their thermal properties. Moreover, when exposed to UV light the mechanical properties of the films with β-carotene were less affected displaying, in general, higher modulus and similar ultimate tensile strength while keeping the films more ductile than the pure films. Therefore, β-carotene can be potentially used as a natural additive to increase the UV stability of the biopolyesters.