Synthesis and properties of optically active poly(amide-imide)s containing axially dissymmetric 1,1 '-binaphthyl moieties

Novel optically active aromatic poly(amide-imide)s (PAIs) containing 1,1'-binaphthyl-2,2'-diyl units in the main chain were prepared by polycondensation reactions of newly synthesized dianhydride, 2,2'-bis(3,4-dicarboxylzenzamido)-1,1'-binaphthyl dianhydride[(S)-BN-DADA and (+/-)-BNDADA], with diamines, The properties of the resulted PAIs were fully characterized by a combination of investigations on inherent viscosity, thermal properties(DSC and TGA), specific rotation, CD and UV-Vis absorbance. These PAIs showed good solubilities, thermal properties and optical stabilities. Interesting UV-Vis absorption behavior of films casted from these PAIs was observed and analyzed.

Thermal analysis of ethylene propylene copolymer-grafted-acrylic acid

The thermal properties of ethylene propylene copolymer-grafted-acrylic acid (EP-g-AA) were investigated by using differential scanning calorimetry (DSC). Compared with the ethylene propylene copolymer (EP), the peak values of the melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, the crystallization temperature (T-c) increased about 8-12 degrees C, and the melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of the ungrafted sample was 1.6-1.8, and that of grafted samples were all above 2, which indicated that the grafted monomer could become the crystal nuclei for the crystallization of propylene sequence. With increasing grafted monomer content, the crystallization rate of propylene sequence in grafted EP increased; it might be the result of rapid nucleation rate and crystal growth rate.

Thermal analysis of ethylene-propylene copolymer-grafted-glycidyl methacrylate

The thermal properties of ethylene-propylene copolymer grafted with glycidyl methacrylate (EP-g-GMA) were investigated by using differential scanning calorimetry (DSC). Compared to the plain ethylene-propylene copolymer (EP), peak values of melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, crystallization temperature (T-c) increased about 8-12 degrees C, and melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal and nonisothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of ungrafted sample is 1.6-1.8, and those of grafted samples are all above 2. The crystallization rates of propylene sequence in EP-g-GMA were faster than that in the plain EP and increased with increasing of grafted monomer content. It might be attributed to the results of rapid nucleation rate. (C) 1996 John Wiley & Sons, Inc.

Properties of ethylene-propylene copolymer/PA-1010 blends using ethylene-propylene copolymer-graft-acrylic acid as a compatibilizing agent

The modification of ethylene-propylene copolymer (EP) has been accomplished by radical EP-graft-acrylic acid (EP-g-AA) has been used to obtain ternary PA/EP/EP-g-AA blends by melt mixing. Different blend morphologies were observed by scanning electron microscopy; the domain size of the EP-dispersed phase in the polyamide 1010 matrix of compatibilized blends decreased compared with that of uncompatibilized blends. It is found that EP-g-AA used as the third component has a profound effect on the mechanical properties of the resulting blends. This behavior has been attributed to serious chemical interactions taking place between the two components. Thermal analysis shows that some thermal properties of PA in compatibilized PA/EP/EP-g-AA changed because of chemical reactions taken place during the blending process. Wide angle x-ray diffraction measurements also confirmed this result. (C) 1996 John Wiley & Sons, Inc.

THERMAL BEHAVIORS OF INTRINSIC POLYANILINE AND ITS DERIVATIVES

Thermal properties of polyaniline (PAn), polytoluidine(POT) and polyanisidine(PAs) were examined by TG and DSC techniques. The weight-uptake of POT at 200-300 degrees C was observed and carefully discussed.

STRUCTURES AND PROPERTIES OF DIALKYL FUMARATES POLYMERS

Polymers of methyl-iso-propyl fumarate, di-iso-propyl fumarate, di-t-butyl fumarate, di-s-butyl fumarate, di-s-amyl fumarate and di-cyclo-hexyl fumarate were prepared by radical polymerization. The structures of the polymers were examined by H-1-NMR, C-13-NMR and WAXD. Some properties of the polymers, including thermal properties, were examined.

ISOLATION AND PROPERTIES OF MOLYBDENUM SERIES OF HETEROPOLY BLUE WITH KEGGIN STRUCTURE

The present paper reports the methods for preparing and isolating 8 kinds of 1:12 molybdenum series of heteropoly blue complexes KyHzXMo12O40 . nH2O (X=Si, P, As, Ge). The products were characterized by elemental analyses, potential titration, polarograms, cyclic voltammetry, IR spectra, visible-UV spectra, X-ray powder diffraction, XPS and P-31 NMR. The single crystal structure of 4-electron molybdenum-silicon heteropoly blue was measured and the positions of reduced molybdenum atoms were determined, i.e. they were located at Mo(3), Mo(7), Mo(8) and Mo(10). The experimental results show that the heteropoly blue remains Keggin structure. ESR spectra of heteropoly blue solids were first studied, from which it was found that the delocalization extent of 2-electron heteropoly blue and 4-electron heteropoly blue is smaller than that of 1-electron heteropoly blue. The study of thermal properties shows that the thermal stability increases with the increase of the reduction extent of heteropoly blue. The study of redox properties shows that the oxidizing power order of heteropoly blue changes in different mediums, and the polarographic half-wave voltage is found to be dependent on the electronegativity of the hetero atom linearly. It is found that the phosphorus heteropoly blue and arsenic heteropoly blue show a strong anti-acid property.

Applications of finite element computer modelling and thermal infrared remote sensing to the study of geothermal anomalies

Buried heat sources can be investigated by examining thermal infrared images and comparing these with the results of theoretical models which predict the thermal anomaly a given heat source may generate. Key factors influencing surface temperature include the geometry and temperature of the heat source, the surface meteorological environment, and the thermal conductivity and anisotropy of the rock. In general, a geothermal heat flux of greater than 2% of solar insolation is required to produce a detectable thermal anomaly in a thermal infrared image. A heat source of, for example, 2-300K greater than the average surface temperature must be a t depth shallower than 50m for the detection of the anomaly in a thermal infrared image, for typical terrestrial conditions. Atmospheric factors are of critical importance. While the mean atmospheric temperature has little significance, the convection is a dominant factor, and can act to swamp the thermal signature entirely. Given a steady state heat source that produces a detectable thermal anomaly, it is possible to loosely constrain the physical properties of the heat source and surrounding rock, using the surface thermal anomaly as a basis. The success of this technique is highly dependent on the degree to which the physical properties of the host rock are known. Important parameters include the surface thermal properties and thermal conductivity of the rock. Modelling of transient thermal situations was carried out, to assess the effect of time dependant thermal fluxes. One-dimensional finite element models can be readily and accurately applied to the investigation of diurnal heat flow, as with thermal inertia models. Diurnal thermal models of environments on Earth, the Moon and Mars were carried out using finite elements and found to be consistent with published measurements. The heat flow from an injection of hot lava into a near surface lava tube was considered. While this approach was useful for study, and long term monitoring in inhospitable areas, it was found to have little hazard warning utility, as the time taken for the thermal energy to propagate to the surface in dry rock (several months) in very long. The resolution of the thermal infrared imaging system is an important factor. Presently available satellite based systems such as Landsat (resolution of 120m) are inadequate for detailed study of geothermal anomalies. Airborne systems, such as TIMS (variable resolution of 3-6m) are much more useful for discriminating small buried heat sources. Planned improvements in the resolution of satellite based systems will broaden the potential for application of the techniques developed in this thesis. It is important to note, however, that adequate spatial resolution is a necessary but not sufficient condition for successful application of these techniques.

Thermal conductivity measurement of liquids in a microfluidic device

A new microfluidic-based approach to measuring liquid thermal conductivity is developed to address the requirement in many practical applications for measurements using small (microlitre) sample size and integration into a compact device. The approach also gives the possibility of high-throughput testing. A resistance heater and temperature sensor are incorporated into a glass microfluidic chip to allow transmission and detection of a planar thermal wave crossing a thin layer of the sample. The device is designed so that heat transfer is locally one-dimensional during a short initial time period. This allows the detected temperature transient to be separated into two distinct components: a short-time, purely one-dimensional part from which sample thermal conductivity can be determined and a remaining long-time part containing the effects of three-dimensionality and of the finite size of surrounding thermal reservoirs. Identification of the one-dimensional component yields a steady temperature difference from which sample thermal conductivity can be determined. Calibration is required to give correct representation of changing heater resistance, system layer thicknesses and solid material thermal conductivities with temperature. In this preliminary study, methanol/water mixtures are measured at atmospheric pressure over the temperature range 30-50A degrees C. The results show that the device has produced a measurement accuracy of within 2.5% over the range of thermal conductivity and temperature of the tests. A relation between measurement uncertainty and the geometric and thermal properties of the system is derived and this is used to identify ways that error could be further reduced.

Experimental and Numerical Evaluation of Thermal Performance of Steered Fibre Composite Laminates

For Variable Stiffness (VS) composites with steered curvilinear tow paths, the fiber orientation angle varies continuously throughout the laminate, and is not required to be straight, parallel and uniform within each ply as in conventional composite laminates. Hence, the thermal properties (conduction), as well as the structural stiffness and strength, vary as functions of location in the laminate, and the associated composite structure is often called a “variable stiffness” composite structure. The steered fibers lead not only to the alteration of mechanical load paths, but also to the alteration of thermal paths that may
result in favorable temperature distributions within the laminate and improve the laminate performance. Evaluation of VS laminate performance under thermal loading is the focus of this chapter. Thermal performance evaluations require experimental and numerical analysis of VS laminates under different processing and loading conditions. One of the advantages of using composite materials in many applications is the tailoring capability of the laminate,
not only during the design phase but also for manufacturing. Heat transfer through variable conduction and chemical reaction (degree of cure) occurring during manufacturing (curing) plays an important role in the final thermal and mechanical performance, and shape of composite structures.

Thermo-Mechanical Properties of Poly ε-Caprolactone/Poly L-Lactic Acid Blends: Addition of Nalidixic Acid and Polyethylene Glycol Additives Journal of the Mechanical Behavior of Biomedical Materials

The search for ideal biomaterials is still on-going for tissue regeneration. In this study, blends of Poly ε-caprolactone (PCL) with Poly l-lactic acid (PLLA), Nalidixic Acid (NA) and Polyethylene glycol (PEG) were prepared. Mechanical and thermal properties of the blends were investigated by tensile and flexural analysis, DSC, TGA, WXRD, MFI, BET, SEM and hot stage optical microscopy. Results showed that the loading of PLLA caused a significant decrease in tensile strength and almost total eradication of the elongation at break of PCL matrix, especially after PEG and NA addition. Increased stiffness was also noted with additional NA, PEG and PLLA, resulting in an increase in the flexural modulus of the blends.
Isothermal degradation indicated that bulk PCL, PLLA and the blends were thermally stable at 200°C for the duration of 2h making extrusion of the blends at this temperature viable. Morphological study showed that increasing the PLLA content and addition of the very low viscosity PEG and powder NA decreased the Melt Flow Indexer and increased the viscosity.
At the higher temperature the PLLA begins to soften and eventually melts allowing for increased flow and, coupling this with, the natural increase in MFI caused by temperature is enhanced further. The PEG and NA addition increased dramatically the pore volume which is important for cell growth and flow transport of nutrients and metabolic waste.

Optimisation of a two-liquid component pre-filled acrylic bone cement system: A design of experiments approach to optimise cement final properties

The initial composition of acrylic bone cement along with the mixing and delivery technique used can influence its final properties and therefore its clinical success in vivo. The polymerisation of acrylic bone cement is complex with a number of processes happening simultaneously. Acrylic bone cement mixing and delivery systems have undergone several design changes in their advancement, although the cement constituents themselves have remained unchanged since they were first used. This study was conducted to determine the factors that had the greatest effect on the final properties of acrylic bone cement using a pre-filled bone cement mixing and delivery system. A design of experiments (DoE) approach was used to determine the impact of the factors associated with this mixing and delivery method on the final properties of the cement produced. The DoE illustrated that all factors present within this study had a significant impact on the final properties of the cement. An optimum cement composition was hypothesised and tested. This optimum recipe produced cement with final mechanical and thermal properties within the clinical guidelines and stated by ISO 5833 (International Standard Organisation (ISO), International standard 5833: implants for surgery—acrylic resin cements, 2002), however the low setting times observed would not be clinically viable and could result in complications during the surgical technique. As a result further development would be required to improve the setting time of the cement in order for it to be deemed suitable for use in total joint replacement surgery.

A comparative study on the thermophysical properties for two bis[(trifluoromethyl)sulfonyl]imide-based ionic liquids containing the trimethyl-sulfonium or the trimethyl-ammonium cation in molecular solvents

Herein, we present a comparative study of the thermophysical properties of two homologous ionic liquids, namely, trimethyl-sulfonium bis[(trifluoromethyl) sulfonyl]imide, [S₁₁₁][TFSI], and trimethyl-ammonium bis[(trifluoromethyl)sulfonyl]imide, [HN₁₁₁][TFSI], and their mixtures with propylene carbonate, acetonitrile, or gamma butyrolactone as a function of temperature and composition. The influence of solvent addition on the viscosity, conductivity, and thermal properties of IL solutions was studied as a function of the solvent mole fraction from the maximum solubility of IL, x_s, in each solvent to the pure solvent. In this case, x_s is the composition corresponding to the maximum salt solubility in each liquid solvent at a given temperature from 258.15 to 353.15 K. The effect of temperature on the transport properties of each binary mixture was then investigated by fitting the experimental data using Arrhenius' law and the Vogel-Tamman-Fulcher (VTF) equation. The experimental data shows that the residual conductivity at low temperature, e.g., 263.15 K, of each binary mixture is exceptionally high. For example, conductivity values up to 35 and 42 mS·cm^-1 were observed in the case of the [S ₁₁₁][TFSI] + ACN and [HN₁₁₁][TFSI] + ACN binary mixtures, respectively. Subsequently, a theoretical approach based on the conductivity and on the viscosity of electrolytes was formulated by treating the migration of ions as a dynamical process governed by ion-ion and solvent-ion interactions. Within this model, viscosity data sets were first analyzed using the Jones-Dole equation. Using this theoretical approach, excellent agreement was obtained between the experimental and calculated conductivities for the binary mixtures investigated at 298.15 K as a function of the composition up to the maximum solubility of the IL. Finally, the thermal characterization of the IL solutions, using DSC measurements, showed a number of features corresponding to different solid-solid phase transitions, T_S-S, with extremely low melting entropies, indicating a strong organizational structure by easy rotation of methyl group. These ILs can be classified as plastic crystal materials and are promising as ambient-temperature solid electrolytes. © 2013 American Chemical Society.

The Influence of Cation Structure on the Chemical-Physical Properties of Protic Ionic Liquids

In this study we investigated the influence of five different cations on the physical-chemical properties of protic ionic liquids (PILs) based on bis(trifluoromethanesulfonyl)imide (TFSI-). We showed that the viscosities, ionic conductivities, densities and thermal properties of these PIL are strongly affected by the structure of the protic cation. Furthermore, the influence of the cation structure on the lithium coordination was investigated by Raman spectroscopy for all investigated PIL-based electrolytes for lithium-ion batteries (LIBs). This investigation clearly demonstrates, that the lithium average coordination number in PIL-based electrolytes is strongly affected by (ring) size and the number of protons on the cations structure and, more importantly, it might be significantly lower (more than 60 of that of electrolytes containing aprotic ionic liquids (AILs). Electrochemical performances of these PILs-based electrolytes were then also investigated to dress some conclusion on their applicability for LIB.

Phonon spectra and thermodynamic properties of rare gas solids based on empirical and semi-empirical (ab initio) two-body potentials : a comparative study /

We study the phonon dispersion, cohesive and thermal properties of raxe gas solids Ne, Ar, Kr, and Xe, using a variety of potentials obtained from different approaches; such as, fitting to crystal properties, purely ab initio calculations for molecules and dimers or ab initio calculations for solid crystalline phase, a combination of ab initio calculations and fitting to either gas phase data or sohd state properties. We explore whether potentials derived with a certain approaxih have any obvious benefit over the others in reproducing the solid state properties. In particular, we study phonon dispersion, isothermal ajid adiabatic bulk moduli, thermal expansion, and elastic (shear) constants as a function of temperatiue. Anharmonic effects on thermal expansion, specific heat, and bulk moduli have been studied using A^ perturbation theory in the high temperature limit using the neaxest-neighbor central force (nncf) model as developed by Shukla and MacDonald [4]. In our study, we find that potentials based on fitting to the crystal properties have some advantage, particularly for Kr and Xe, in terms of reproducing the thermodynamic properties over an extended range of temperatiures, but agreement with the phonon frequencies with the measured values is not guaranteed. For the lighter element Ne, the LJ potential which is based on fitting to the gas phase data produces best results for the thermodynamic properties; however, the Eggenberger potential for Ne, where the potential is based on combining ab initio quantum chemical calculations and molecular dynamics simulations, produces results that have better agreement with the measured dispersion, and elastic (shear) values. For At, the Morse-type potential, which is based on M0ller-Plesset perturbation theory to fourth order (MP4) ab initio calculations, yields the best results for the thermodynamic properties, elastic (shear) constants, and the phonon dispersion curves.