Interactions Between an Ionic Liquid and Silica,Silica and Silica,and Rubber and Silica and Their Effects on the Properties of Styrene-Butadiene Rubber Composites

An investigation of the effect of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMI), on the properties of silica reinforced styrene-butadiene rubber (SBR), aimed to correlate the interactions between the ionic liquid and silica, silica and silica, and silica and rubber with the macro-properties and microstructure of SBR and SBR/silica vulcanizates is described. The interaction between the ionic liquid and silica was characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), the interaction between silica and silica was characterized by a rubber processing analyzer (RPA), and the interaction between rubber and silica was characterized by the bound rubber content. The FTIR analysis revealed that BMI can react with the hydroxyl groups on the surface of silica, improving the compatibility between the rubber and silica. The RPA and bound rubber testing indicated that the interactions between silica and silica particles were weakened and the interaction between silica and rubber increased with the incorporation of BMI into the SBR rubber. The bound rubber content showed a maximum with a BMI content of 3 phr. At the same time, the dispersion of silica in SBR was improved with the incorporation of BMI. With the increase of BMI content, the curing rate was greatly improved and the crosslink density increased. BMI also increased the tensile strength and abrasion resistance of the SBR vulcanizates. Most important, the BMI significantly improved the dynamic properties of the rubber composites, especially the wet-skid resistance and rolling resistance. However, excessive BMI (beyond 3 phr) acted as a plasticizer and was detrimental to the mechanical properties, resulting in a decrease of tensile strength and abrasion resistance.     

Reduced filler flocculation in the silica-filled styrene–butadiene–glycidyl methacrylate terpolymer

This study presents a method to improve the dispersion of silica in rubber compounds using a styrene-butadiene-glycidyl methacrylate terpolymer (GMA-SBR) synthesized by cold emulsion polymerization. It has been demonstrated that silica particles in conventional rubbers tend to agglomerate during storage, as well as at the onset of vulcanization, because of their polarity. GMA-SBR can improve the compatibility with silica by the formation of covalent bonds between the epoxy groups of GMA-SBR and silanol groups on the silica surface. SBR 1721 and GMA-SBR silica-filled compounds were prepared without curatives by a kneader and a two-roll mill. After compounding, the reaction of the epoxy group, filler flocculation, and morphology of the compounds were analyzed using infrared spectroscopy, a rubber process analyzer, and transmission electron microscopy, respectively. In addition, the content of bound rubber in the compounds was determined by extracting the unbound rubber material with toluene. The GMA-SBR silica-filled compounds had a higher bound rubber content and exhibited significantly different filler flocculation and silica dispersion behaviors compared with the SBR 1721 silica-filled compounds.     

Characterization of Filler-rubber Interaction,Filler Network Structure,and Their Effects on Viscoelasticity for Styrene-butadiene Rubber Filled with Different Fillers

For styrene-butadiene rubber (SBR) compounds filled with the same volume fraction of carbon black (CB), precipitated silica and carbon–silica dual phase filler (CSDPF), filler-rubber interactions were investigated thru bound rubber content (BRC) of the compounds and solid-state ¹H low-field nuclear magnetic resonance (NMR) spectroscopy. The results indicated that the BRC of the compound was highly related to the amount of surface area for interaction between filler and rubber, while the solid-state ¹H low-field NMR spectroscopy was an effective method to evaluate the intensity of filler-rubber interaction. The silica-filled compound showed the highest BRC, whereas the CB-filled compound had the strongest filler-rubber interfacial interaction, verified by NMR transverse relaxation. The strain sweep measurements of the compounds were conducted thru a rubber process analyzer; the results showed that the CSDPF-filled compound presented the lowest Payne effect, which is mainly related to the weakened filler network structure in polymer matrix. The temperature sweep measurement, tested by dynamic mechanical thermal analysis, indicated that the glass transition temperature did not change when SBR was filled with different fillers, whereas the storage modulus in rubbery state and the tanδ peak height were greatly affected by the filler network structure of composites.     

Ultrasonic shear wave properties of soft tissues and tissuelike materials

Determinations of shear wave speeds of sound and attenuation coefficients are reported for soft tissues, a silicone rubber reference material, and a gel used in manufacturing ultrasonically tissue-mimicking materials. Fresh bovine tissues were investigated, including calfskin, liver, cardiac muscle, and striated muscle. Because of the very large shear wave attenuation coefficients, reasonably accurate determinations of shear wave properties are difficult to make. The quantity measured directly was the complex reflection coefficient for shear waves at a planar interface between the sample and fused silica. Measurements were made at frequencies spanning the range 2-14 MHz. The shear wave attenuation coefficients increase with frequency and are of the order of 10(4) times the longitudinal wave attenuation coefficients. The shear wave speeds of sound also increase with frequency but are only a few percent of the longitudinal wave speeds of sound. The results are accurate enough to allow frequency dependencies to be proposed.     

Measurement of the B0-->phiK*0 decay amplitudes

With a sample of about 227x10(6) BB pairs recorded with the BABAR detector we perform a full angular analysis of the decay B0-->phiK(*0)(892). We make novel measurements of five parameters sensitive to CP violation. We also measure the branching fraction to be (9.2+/-0.9+/-0.5)x10(-6) and determine the fractions of longitudinal and parity-odd transverse contributions as f(L)=0.52+/-0.05+/-0.02 and f( perpendicular)=0.22+/-0.05+/-0.02. The phases of the parity-even and parity-odd transverse amplitudes relative to the longitudinal amplitude are found to be phi( parallel)=2.34(+0.23)(-0.20)+/-0.05 rad and phi( perpendicular)=2.47+/-0.25+/-0.05 rad. We also observe the decay B0-->phiK(*0)(1430).     

Precise measurements of bulk-wave ultrasonic velocity dispersion and attenuation in solid materials in the VHF range

A general method was established for precisely measuring velocity dispersion and attenuation in solid specimens with acoustic losses in the very high frequency (VHF) range, using the complex-mode measurement method and the diffraction correction method. Experimental procedures were presented for implementing such a method and demonstrated this measurement method in the frequency range of 50-230 MHz, using borosilicate glass (C-7740) as a dispersive specimen and synthetic silica glass (C-7980) as a nondispersive standard specimen. C-7980 exhibited no velocity dispersion; velocity was constant at 5929.14 +/- 0.03 m/s. C-7740 exhibited velocity dispersion, from 5542.27 m/s at 50 MHz to 5544.47 m/s at 230 MHz with an increase of about 2 m/s in the measured frequency range. When frequency dependence of attenuation was expressed as alpha = alpha(0)f(beta), the results were as follows: alpha0 = 1.07 x 10(-16) s2/m and beta = 2 for C-7980 and alpha0 = 5.16 x 10(-9) s(1.25)/m and beta = 1.25 for C-7740.     

New piezoelectric polymer for air-borne and water-borne sound transducers

Acoustic transducers made of a charged cellular polymer called EMFi have been designed and investigated with respect to air-borne and water-borne sound. The longitudinal transducer constant is around 90 pC/N, strongly exceeding the values of other piezoelectric polymers. This is mainly attributed to the very low Young's modulus of about 2 MPa. The acoustic impedance is only 2.6 x 10(4) kg/(m2 s) and results in good matching to air but strong loading under water. Due to this strong loading, a pronounced reduction of resonance frequency from 300 kHz in air down to 17 kHz under water is observed. The experiments indicate that fluid loading is not only mass-like but also compliant, reducing the transducer's sensitivity below the resonance frequency of about -63 dB re 1 V/Pa (0.7 mV/Pa) in air to -71 dB re 1 V/Pa under water. This compliance is attributed to the medium's compressibility. Piezoelectricity of EMFi films is limited to temperatures below 70 degrees C; above, irreversible discharge of trapped charges takes place. Furthermore, a second type of EMFi, called "OS" was investigated, having a piezoelectric constant of 15 pC/N and a Young's modulus of 6 MPa. In quasi-static sensor measurements, the piezoelectric constant increases with the applied load. This nonlinearity explains the higher values reported in other publications on the same materials.     

Valence changes and structural distortions in "charge ordered" manganites quantified by atomic-scale scanning transmission electron microscopy

We investigate the microscopic nature of the "charge ordering" modulation in mixed-valent manganites in real space using scanning transmission electron microscopy. The modulation in Bi0.5Sr0.4Ca0.1MnO3 has a uniform periodicity appearing as stripes in high angle annular dark field images. Geometric phase analysis shows the modulation to be a displacement wave with transverse amplitude (0.008+/-0.001)a and longitudinal amplitude (0.003+/-0.001)a. Series of energy loss spectra taken across the stripes show no periodic changes and place an upper bound of +/-0.04 on any valence changes of the Mn ions.     

Molecular interaction and other thermodynamic properties in ternary liquid mixtures

Molecular interaction, adiabatic compressibility, intermolecular free length, molar volume, available volume and free volume have been computed by measuring ultrasonic velocity and density at 23°C in three ternary liquid mixtures with p-xylene as common component. The systems are I p-xylene-acetone-carbon tetrachloride, II p-xylene-acetone-cyclohexane and III p-xylene-benzene-cyclohexane. Molecular interaction is maximum when the mole fraction of acetone is 0.5 in I and 0.6 in II. It remains almost constant in III indicating no interaction in this case. The excess properties have also been given and the interactions explained.     

Insights into the Reinforcement of Butyl Rubber by Carbon Black and Silica with the Aid of Their Dynamic Properties

Carbon black (N234) and silica (Vulksail N) with a silane coupling agent Si-69 were chosen as reinforcing fillers in butyl rubber (IIR). The rheological behavior of the IIR compounds and the dynamic mechanical properties of IIR vulcanizates were investigated with a rubber processing analyzer and dynamic mechanical analysis (DMA) to examine the filler dispersion in the rubber matrix and the interaction between filler and matrix. The data indicated that the N234 filled IIR compounds had more filler networks than those filled with silica. Filler networks first appeared at 30 phr N234 and 45 phr silica with silane coupling agent Si-69. The interaction between N234 and IIR was far stronger than that between silica and IIR. However, the silica Vulksail N filled IIR had better wet-grip and lower rolling resistance compared to the carbon black-filled IIR should IIR be chosen as a substitute of styrene-butadiene rubber (SBR) in tire tread. The reinforcing factor, R, R (related to the difference in tan d peak height at T_g for the filled and nonfilled rubbers), also demonstrated that the N234-IIR interaction was stronger than for the silica. IIR with 30 phr N234 exhibited the largest tensile strength, 20.1 MPa, for those vulcanizates examined. The tensile and tear strengths of N234 filled IIR were higher than those of IIR with similar amounts of silica. Thus, it was concluded that N234 is a more active reinforcing filler in IIR than silica (Vulksail N) even with a silane coupling agent (Si-69).     

Phase diagram involving the mesomorphic behavior of binary mixture of sodium oleate and orthophosphoric acid

The present investigation deals with the binary mixture of two non-mesogenic compounds, viz. sodium oleate (Naol) and orthophosphoric acid (H₃PO₄) which exhibits very interesting liquid crystalline smectic phases at large range of concentrations and temperature. The mixtures with concentrations ranging from 10% to 90% Naol in H₃PO₄ exhibit SmA, SmC, SmE and SmB phases, sequentially when the specimen is cooled from its isotropic phase. Physical properties, such as ultrasonic velocity, adiabatic compressibility and molar compressibility, show anomalous behavior at the isotropic to mesosphase transition.     

Very high Q measurements on a fused silica monolithic pendulum for use in enhanced gravity wave detectors

We present for the first time the results of very high Q factor measurements for a 2.8 kg fused silica mass suspended by two fused quartz fibers attached by a novel technique for joining fused silica or quartz. The Q for the pendulum mode at 0.93 Hz was (2.3+/-0. 2)x10(7), the highest value demonstrated to date for a mass of this size. By employing such a new suspension system the sensitivity of the gravitational wave detectors currently under construction can be increased up to 1 order of magnitude.     

Ultrasonic studies on polystyrene/styrene butadiene rubber polymer blends filled with glass fiber and talc

The compatibility of solid blends: PS/SBR, PS/SBR filled with glass fiber and PS/SBR filled with talc were studied using ultrasonic pulse echo technique. Measurements were carried out at room temperature (298 K) and a frequency of 3 MHz. The ultrasonic velocity for the compressional wave and that for shear wave have been measured to obtain the elastic moduli data by knowing of density. The variation of ultrasonic wave velocities and elastic moduli with weight percent of the blend was found to be linear in PS/SBR blend, indicating some degree of compatibility but the drawback of elastic moduli indicate incompatibility of the system blend, while it deviates from linearity in blends of PS/SBR filled with glass fiber and talc but the increase in elastic moduli indicates that there is an increase in degree of compatibility between PS and SBR due to adding of glass fiber or talc. The ultrasonic absorptions for longitudinal wave in the temperature range from 298 to 423 K in the studied system were measured using ultrasonic pulse echo technique. Typical results showing the temperature dependence of the ultrasonic absorption at frequencies of 1, 2, 3 and 5 MHz are illustrated for all samples of the different compositions. The study of compositional and temperature dependence of the ultrasonic absorption in the present studied blends reveals the same behavior of the compatibility degree of the blends. Density data of the blends confirmed the ultrasonic results. Also the correlation between hardness and elastic moduli for the present blend systems has been studied.     

Study of stress-strain characteristics of SBR and blended NR/SBR rubber

The effect of temperature and carbon black (CB) on the mechanical characteristics of styrene-butadine rubber (SBR) and natural rubber (NR) was studied at various temperatures. The relation obtained between true stress and true strain for both types of rubber showed three regions at room temperature and two regions at high temperature. The optimum CB concentration was found to be 95 phr for the unblended samples as it increases the stiffness of the SBR rubber materials at a maximum value. It was also found that the addition of NR to SBR increases the elasticity in the plastic region. The activation energy at the fracture of SBR samples decreased from about 2.7×10^–20 to 1.8×10^–20 J while for the blended samples NR/SBR it increased from 8×10^–20 to 10.1×10^–20 J with increasing CB concentration.     

Silicas modified with silane pro-adhesive compounds - active fillers of rubbers

In order to improve filler-polymer interaction, a modification of the silica surface character was indispensable, from a hydrophilic to a partially or fully hydrophobic one. The changes were effected in the course of precipitation by modification of silica surface with silane coupling agents. The modified silicas obtained were tested in SBR rubber and appropriate strengthening parameters of the filled SBR vulcanizates were established.     

Bose-Einstein condensation of metastable helium

We have observed a Bose-Einstein condensate in a dilute gas of 4He in the (3)2S(1) metastable state. We find a critical temperature of (4.7+/-0.5) microK and a typical number of atoms at the threshold of 8 x 10(6). The maximum number of atoms in our condensate is about 5 x 10(5). An approximate value for the scattering length a = (16+/-8) nm is measured. The mean elastic collision rate at threshold is then estimated to be about 2 x 10(4) s(-1), indicating that we are deeply in the hydrodynamic regime. The typical decay time of the condensate is 2 s, which places an upper bound on the rate constants for two-body and three-body inelastic collisions.     

Collision-induced vibrational energy transfer: K2[1(1) sigmau+ (nu'=2)]+He, H2-->K2[1(1) sigmau+(nu'=1,3)]+He, H2

Collisional energy transfer processes K2[1(1) sigmau+ (nu'=2)]+He, H2-->K2[1(1) sigmau+(nu'=1,3)]+He, H2 were studied by laser induced fluorescence under gas cell conditions. During the experiments, the cell temperature was kept constant at 420K. The buffer gas pressure was varied over the range from 40 to 250 Pa, Kz molecules were irradiated with pulses of radiation from an OPO laser, populating K2[1(1) sigmau+ (nu'=2)] by photon absorption. The resulting fluorescence included the direct component emitted in the decay of the optically excited state and the sensitized components arising from collisionally populated states. The decay signal of time-resolved fluorescence from 1(1) sigmau+ (nu'=2)]-->1(1) sigmag+(nu"=0) transition was monitored. In the early period after excitation, only very little population in states v'= 1 or 3 had yet accumulated, the rate of collisional activation to the state nu'=2 was negligible. The decay curve of the nu' = 2-->nu" = 0 was treated as a single exponential function. From the measurement of the time-resolved fluorescence, the semilog plot was shown. The slope yielded the effective lifetime of the nu' = 2--> nu' = 0 transition. Based on the Stern-Volmer equation, the radiative lifetime (36 +/- 7) ns was obtained. The total cross sections for deactivation of 1(1) sigmau1 (nu'=2) state by means of collisions with He and H2 are (3.0 +/- 0.5) x 10(-16) cm2 and (6.4 +/- 1.2) x 10(-15) cm2, respectively. The radiative lifetimes of 1(1) sigmau+(nu' = 1,3) states can also be determined through time-resolved fluorescence in pure K vapor. The time-integrated intensities of 1(1)sigmau+(nu' = 1,2,3)-->1(1) sigmag+(nu"=0) transition at different He or Hz pressure were measured. The ratio of fluorescence intensities versus 1/P(He, H2) can be fitted by a straight line. The slopes yield the cross sections sigma(nu'=2-->nu'=1) = (1.4 +/- 0.5) x 10(-16) cm2 and (3.2 +/- 1.0) x 10(-15) cm2; sigma(nu'=2-->nu'=3)= (1.2 +/- 0.4) x 10(-16) cm2 and (2.6 +/- 0.9) x 10(-15) cm2 for He and H2, respectively. Cross sections for the effective quenching of the nu' = 1,2,3 states were also determined. To our knowledge, the cross-sections for these processes are reported for first time.     

Styrene Butadiene Rubber/Silicone Rubber Blends Filled With Dough Moulding Compound

Blends of styrene butadiene rubber (SBR)/methyl-vinyl silicone rubber (MVQ) filled with dough molding compound (DMC) were prepared and the effects of various amounts of the SBR, as a compatibilizer of MVQ and DMC, on the mechanical properties and the oxygen index of the DMC filled SBR/MVQ blends were investigated. Dynamic mechanical analysis (DMA) and infrared spectrum analysis (IR) of the DMC/SBR/MVQ blends were also investigated. The results showed that the mechanical properties of the DMC filled MVQ blends were improved when SBR was used as a compatibilizer; the best mass ratio was 60 phr (parts per hundred total rubber) DMC, 25 phr SBR and 75 phr MVQ. The volume electric resistivities of the DMC filled SBR/MVQ blends with various DMC mass ratios were all above 5.8?×?10¹² Ω?m; i.e., the electrical insulating property of the blends was excellent. Compared with the blends without DMC and the blends without SBR, the energy storage modulus and the peak area of the loss factor tan δ of the DMC reinforced SBR/MVQ blends were largest; the addition of DMC and SBR improved the thermal properties of the blends.     

Multireference quantum Monte Carlo study of the O4 molecule

Fixed-node diffusion quantum Monte Carlo (FN-DMC) calculations are performed to obtain the most accurate dissociation barrier and heat of formation with respect to dissociation into molecular oxygen for the chemically bound tetraoxygen molecule. Multireference trial wave functions were used and built from truncated CASSCF(16,12) through a weight-consistent scheme allowing to control the fixed-node error. Results are compared with the previous ab initio benchmark Complete Active Space SCF Averaged Coupled Pair Functional/aug-cc-pVQZ (CASSCF-ACPF/AVQZ) results. The FN-DMC barriers to dissociation and heat of formation obtained are 11.6+/-1.6 kcal/mol and 98.5+/-1.9 kcal/mol, respectively. These thermochemical energies should be taken as the theoretical references when discussing the relevance of tetraoxygen in a variety of experiments and atmospheric chemical processes.     

Phase transition studies in polymesomorphic compounds (ii): Ultrasonic velocity studies in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline

The variation of ultrasonic velocity in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline with temperature in the isotropic, nematic, S_A S_B and S_G phases is measured. All the phase transitions are of first order. The adiabatic compressibility β _ad , molar sound veclocity or Rao number R_n , and molar compressibility or Wada constant A are computed. Molar sound velocity and molar compressibility of HBBA are compared with the values of other compounds. They are found to be in good agreement with theory.