The Slow Molecular Mobility in Semicrystalline Poly(Ethylene Oxide)

The thermally stimulated depolarization current (TSDC) technique has been used to study the slow molecular mobility in the amorphous part of the semicrystalline polymer, poly(ethylene oxide) (PEO). Experiments were carried out in the temperature range that includes the glassy state, the glass transformation region and the rubber state. The dipole moments in the polymeric main chain originated a broad and low intensity secondary relaxation in the temperature region from ?130°C up to the glass transition region; the activation energy of the motional modes of this secondary relaxation was in the range between 35 and 100 kJ mol^?1. The glass transition temperature of the PEO, provided by the TSDC technique, was T_g = ?53°C, and the fragility index was found to be m = 43. A strong relaxation above T_g was observed, whose molecular origin was discussed. The thermal behavior of the PEO was also characterized by differential scanning calorimetry.     

Transitions in glasses at low temperatures

Length-temperature measurements from ?180°C to the glass transition temperature have been made on a poly(vinyl alkyl ether) series, poly(ethylene terephthalate), and a tetrafluoroethylene-trifluoropropylene copolymer series.

Consistent with low frequency dynamic measurements, the poly(vinyl alkyl ethers) exhibit a glass-glass transition? Tgg [1] between Tg and Tg ?70°C with evidence of another at about ?160 to ?180°C. With increasing side-chain length, the expansion coefficient below Tg- and the magnitude of the g-g transition increase, and the value of the Simha-Boyer free-volume product decreases, suggesting retention of excess free volume by the flexible pendant group. This behavior is analogous to that observed for poly(alkyl methacrylates) except that the latter system exhibited two g-g transitions, the lower of which coincided with Tgg [1] observed here.

Poly(ethylene terephthalate) samples, both amorphous and crystalline, exhibit two T > Tg transitions at about ?85 and ?40°C. Dynamic results resolve only one relaxation in this temperature range.

The glass temperatures of the tetrafluoroethylene-trifluoropropylene copolymer series, as determined by both dilatometry and differential scanning calorimetry, extrapolate to a Tg, for 100% amorphous PTFE of 11-16°C. Two g-g transitions, present in each homo-polymer, persist in the copolymers, indicating that only a small number of molecular units are involved. The magnitude of these relaxations, however, as measured by the change in expansion coefficient, is dependent on copolymer composition.     

正二十四烷烃石蜡/膨胀石墨（EG）复合相变材料分子动力学模拟

相变材料(PCMs)在相变时的恒温、高能量密度等特性,经常应用于设备的热管理,但是PCMs导热系数低的缺点影响了其使用范围.本文采用分子动力学方法,模拟了在正二十四烷烃石蜡PCMs中添加不同结构(层状、交叉状)的膨胀石墨(EG)之后构成的复合PCMs的物性.文章通过径向分布函数(RDF)、声子态密度(PDOS)、比热容和导热系数这四个指标,分析了夹角为0°的层状结构,夹角为45°、90°的交叉状EG添加物对于石蜡热物性的影响. EG(0°、45°、90°)添加使得石蜡的原子分布在不同程度上变得更加均匀、紧密,使得石蜡的比热容有所增加.同时,两种类型的添加物提高了石蜡的PDOS,提高了导热系数.其中,EG(90°)添加物对于石蜡导热系数的提升最为明显,石蜡/EG(0°、45°、90°)模型中EG的含量分别为33.63 wt%、30.86 wt%和23.20 wt%,相比于的石蜡的导热系数分别提升了417.1%、345.7%和522.9%. EG的添加能够提高石蜡的导热系数,不同结构的EG对石蜡导热系数的影响有着较大的区别.     

Influence of heat treatment on structure and some physical properties of lithium boro-niobate glass

The glass composition (90?mol% Li₂B₄O₇–10?mol% Nb₂O₅) was prepared by the melt quenching technique. The quenched sample was heat treated at 480°C, 545°C and 630°C for 5?h and heat treated at 780°C with different time. The times were 5, 10, 15, 20, 28, and 36?h. The glass and glass ceramics were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and dc conductivity as a function of temperature. Lithium niobate (LiNbO₃) and lithium diborate (Li₂B₄O₇) were the main phases in glass ceramic addition to traces from LiNb₃O₈. Crystallite size of the main phases determined from the X-ray diffraction peaks are in the range <100?nm. The fraction of crystalline (LiNbO₃) phase increases with increase the heat treatment temperature and time. The relation between physical properties and structure were studied.     

Phase transitions in ferroelectric polymer films

Phase transitions in ferroelectric films of vinylidene fluoride-trifluoroethylene (70/30) copolymer are studied by differential scanning calorimetry (DSC). Films 40 nm thick are prepared from solution by centrifugation. DSC thermograms reveal peaks typical of the first-order phase transition that are associated with heat absorption and heat release, and the enthalpies of the transitions are determined. Upon cooling, a kink in the slope of the DSC curve that determines the temperature of the glass transition is observed at T = ?30°C.     

Investigation into the dielectric relaxation of vinylidene fluoride copolymers with hexafluoropropylene

Four relaxation processes and one ferroelectric-paraelectric phase transition are revealed in vinylidene fluoride-hexafluoropropylene copolymers with different ratios of the components in the temperature range from ?100 to 150°C. The relaxation process occurring at the lowest temperature is associated with the local mobility of the chains, whereas the relaxation process at a higher temperature is due to micro-Brownian motion of segments in the amorphous phase in the glass transition range. A smeared relaxor phase transition from the polar modification of the α phase of vinylidene fluoride units to the paraelectric phase is observed in the temperature range 50–70°C. At higher temperatures, there occurs an intensive relaxation process that can be attributed to space-charge relaxation or manifestation of the normal relaxation mode.     

Synthesis of Lignin-Based Thermoplastic Copolyester Using Kraft Lignin as a Macromonomer

Lignin-based thermoplastic copolyester was synthesized for eco-friendly polymers and composite applications using lignin as a macromonomer to form a high molecular weight polymer. Kraft lignin was polymerized with sebacoyl chloride in the presence of triethylamine in N,N-dimethylacetamide (DMAc), and the molecular weight of the synthesized polymer was controlled by the polymerization temperatures and [COCl]/[OH] ratios providing up to 39 000 corresponding to 4–5 repeating units of lignin macromonomers. The glass transition temperature of the synthesized polymer was difficult to measure due to the random distribution of functional groups and irregular configurational or conformational arrangement of natural lignin. Therefore, the complex electric modulus (CEM) technique was used to determine the glass transition of the synthesized polymer to give around 70°C measured by the peak of the imaginary part of CEM. The synthesized lignin-copolyester exhibited good thermal stability up to 200°C in TGA analysis and, thus, it was possible to shape the synthesized polymer using the solvent casting or hot-melt processing techniques at 120°C–140°C without generating odor, fume or irritation. Although the molecular weight should further be increased in the future, the developed methodology may help to exploit new applications for eco-friendly sustainable materials in various fields.     

An In situ Experimental Study on Solidification Kinetics of Polyolefins: Effect of Cooling Conditions

The solidification kinetics of polyolefins (PO) under three cooling conditions were investigated using an in situ measurement of the temperature decay within the PO resins. The phase-change temperature range of high-density polyethylene (HDPE) was located between 110 and 120°C, and those of low-density polyethylene (LDPE) and polypropylene (PP) were 90–110°C and 100–120°C, respectively. The cooling rate of the liquid-state stage is larger than that of the crystallization stage, primarily owing to the release of the latent heat of crystallization as well as the reduced temperature difference between the sample and cooling medium; they jointly slow down the cooling rate to an extent. The time with respect to phase transformation and its lasting period have close relations to the materials' molecular characteristics (e.g., Mw, MWD, LCB, etc.). Three empirical equations were proposed, and found to be applicable for the cooling analysis of the PO molten materials at relatively low cooling rates prior to crystallization.     

Investigation of ferroelectric phase transitions of water in nanoporous silicates in simultaneous electrical noise and calorimetric measurements

The phase transitions of water in the nanoporous silicate materials SBA-15 and MCM-41 with an ordered system of cylindrical pores have been investigated. Measurements of low-frequency electrical noises (Barkhausen noises) in the frequency range of 1–100 Hz have been performed simultaneously with relative calorimetric measurements. It has been found that the voltage of electrical fluctuations increases approximately 100 times in the temperature range from ?30 to ?50°C, which is associated with the first-order and second-order ferroelectric phase transitions. It has been assumed that the ferroelectric ice XI can be formed in capillary pores of the materials under investigations.     

Study of phase transition in a [CdHgI4 : 0.2AgI] mixed conducting composite system doped with KI and K2SO4

New composite superionic systems, [CdHgI₄?:?0.2AgI]?:?0.xKI and [CdHgI₄?:?0.2AgI]?:?0.xK₂SO₄ (x?=?0.2, 0.4, 0.6?mol. wt%), were prepared, using [CdHgI₄?:?0.2AgI] mixed composite system as the host. Electrical conductivity was measured to study the transition behavior at frequencies of 100?Hz, 120?Hz, 1?kHz, and 10?kHz in the temperature range from 150°C to 250°C using a GENRAD 1659 RLC Digibridge. A sharp increase in conductivity was observed during β?→?α phase transition. Upon increasing the dopant-to-host ratio, the conductivity of the superionic systems exhibited Arrhenius (thermally activated)-type behavior. Differential thermal analysis, differential scanning calorimetry, thermogravimetric analysis, and X-ray powder diffraction were performed to confirm the doping effect and transition in the host. The phase transition temperature increased with an increase in the dopant concentration. Activation energies in eV for pre- and post-transition phase behavior are reported.     

In situ Grafting onto Silica Surface with Epoxidized Natural Rubber via Solid State Method

An in situ solid state grafting reaction between epoxidized natural rubber (ENR) and silica was performed in a Haake internal mixer. Resulting ENR‐grafted silica was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) measurements. Based on these results, it was concluded the silanol groups (Si‐OH) of silica caused the ring opening of ENR oxirane rings so that ENR was grafted onto the silica surface. Transmission electron microscopy (TEM) photographs showed ENR‐grafted silica had better dispersibility and smaller aggregates compared with the original silica. Dynamical mechanical analysis (DMA) of vulcanized rubber compounds contained ENR‐grafted silica showed the glass transition temperature (T _g) of grafted ENR molecules shifted to higher temperature, from ?3°C to 20°C, indicating the mobility of ENR was greatly restricted. As a result, the compounds containing ENR‐grafted silica have higher hysteresis, and can be applied in a much wider field, such as damping materials, tires of racing cars, and so on.     

Structural and crystallization behavior of (Ba,Sr)TiO3 borosilicate glasses

Various glass samples were prepared by melt quench technique in the glass system [(Ba_{1? x} Sr _x ) TiO₃]–[2SiO₂–B₂O₃]–[K₂O] doped with 1?mole% of La₂O₃. Infrared spectra show the number of absorption peaks with different spliting in the wave number range from 450 to 4000?cm^?1. Absorption peaks occurs due to asymetric vibrational streching of borate by relaxation of the bond B–O of trigonal BO₃. Raman spectra show the Raman bands due to ring-type metaborate anions, symmetric breathing vibrations BO₃ triangles replaced by BO₄ tetrahedra, and symmetric breathing vibrations of six-member rings. The differential thermal analysis of a glass sample corresponding to composition x?=?0.0 shows crystallization temperature at 847°C and glass transition temperature at 688°C. X-ray diffraction (XRD) pattern of glass ceramic samples shows the major crystalline phase of BaTiO₃ whereas pyrochlore phases of barium titanium silicate. Scanning electron micrographs confirm the results of XRD as barium titanate is major crystalline phase along with pyrochlore phase of barium titanium silicate.     

Phase behavior of DODAB aqueous solution

Phase behavior of DODAB aqueous solution, prepared without sonication, was studied by adiabatic scanning calorimetry. Measurements revealed four phase transitions with the temperatures 35.2, 39.6, 44.6, and 52.4°C at heating and one transition at the temperature 40.4°C at cooling. The first three transitions at heating occur in unilamellar vesicles. The first and third transitions correspond to the subgel-gel and gelliquid phase transitions, corresponding enthalpy jumps are equal to 33 and 49 kJ/mol. The second transition appears after some aging and is similar to gel-ripple phase transition in a DPPC solution, with the enthalpy jump under the transition exceeding 7.4 kJ/mol. The transition occurs in unilamellar vesicles. The transition at the temperature 52.4°C occurs in another subsystem of the solution, which we believe to be multilamellar vesicles. The enthalpy jump at this transition is equal to 97 kJ/mol, and data analysis suggests that this is a subgel-liquid transition. The phase transition at cooling is the liquid-gel transition in unilamellar vesicles. During the measurements, a slow evolution of the solution occurs, consisting in a change of concentrations of unilamellar and multilamellar vesicles. This transformation mainly occurs at low temperatures.     

Measurements of the complex shear modulus of polymers under hydrostatic pressure usina the quartz resonator method

Abstract

The quartz resonator method measures the complex shear modulus or compliance of viscoelastic materials in the frequency range from 50 kHz to 140 MHz at temperatures between ?150°C and 300°C and pressures up to 1 GPa. This method can be applied to viscous fluids or polymer melts -even in their glassy or seminystalline regime.

The phase diagram of poly(diethylsiloxane) PDES (a mesophase polymer) was determined for two samples with different molecular weight at pressures up to 400 MPa and temperatures between 20°C and 100°C. Phase transitions are indicated by a sharp bend in the shear compliance although the volume effect of the mesophase-isotropic transition vanishes around 80 MPa.

The pressure dependence of the glass relaxation process (in PVAc), was studied by measuring the change of the complex shear modulus with pressure at constant temperatures between 95°C and 145°C and pressures up to 600 MPa. Additionally to the relaxation process, also the pressure dependence of the real part of the shear modulus in the glassy region can be determined for testing the dislocation concept in the meandermodell by W. Pechhold.     

Phase change behavior of polyethylene glycol in blends with cellulose

Thermodynamic properties and phase change behaviors of polyethylene glycol (PEG) in blends with cellulose (CELL) were found to be completely different than those of pure PEG. When the CELL fraction of the blend was larger than 5 wt%, PEG within the blend did not melt into a liquid state, as was the case with pure PEG, even at a temperature over 50°C above its melting point. Instead of fusion, a solid-solid phase transition was found in these PEG-CELL blends with an enthalpy as large as 100 J/g.     

Raman scattering from three phases in LiIO3

We studied the temperature dependence of the Raman spectrum of LiIO₃, from room temperature up to t ～ 350°C. Two discontinuous changes in the spectrum are observed as temperature increases. The first one is reversible and occurs in a temperature range between 215°C and 260°C, depending upon sample origin (single crystal or powder) and thermal history. The second occurs at t ? 290°C and becomes irreversible once the samples are heated above 340°C. Each phase has a characteristic spectrum, distinct from that of the other two. Although the occurence of these phase changes are in complete agreement with studies made with X-ray diffraction and differential thermal analysis (DTA), it is at variance with previous Raman and infrared work which report no qualitative change in spectrum at the α ? γ phase transition. We believe this disagreement comes about because our measurements are the first ones so far to have actually passed through the transition.     

Molecular order and dynamic mechanical behavior of polyurethanes based on liquid crystalline diol

Synthesis of the liquid crystalline (LC) diol 6,6′-[ethylenebis(l,4-phenylene-oxy)]-dihexanol (I) is described. The structure of polyurethanes prepared from diol I and 4,4′-methylenedi(phenyl isocyanate) (MDI), 4,4′-methylenedi(cyclohexyl isocyanate) (HMDI), or 2(4)-methyl-l,3-phenylene diisocyanate (TDI) at 1:1 molar ratios of isocyanate and hydroxy groups is studied by dynamic mechanical spectroscopy, differential scanning calorimetry (DSC), polarizing microscopy, and x-ray scattering. The polymer prepared from HMDI and the diol (I/HMDI) shows, on cooling, thermal behavior typical of amorphous polymers. A frequency-temperature superposition could be applied to the mechanical data, and the horizontal shift factor satisfied the Williams-Landel-Ferry (WLF) equation. A more-complex thermal behavior was found for I/HMDI polymer during subsequent heating; above 70°C, the formation of an ordered structure takes place, and this structure melts at about 120°C. Complex thermal behavior is exhibited by I/TDI polymer. On cooling its melt, the polymer forms a nematic phase at about 80°C, which freezes into the LC glassy state. On heating, the mesophase melts, and. subsequently, a better-ordered smectic phase is formed at 95°C, which melts at 120°C. This structure buildup is accompanied by a rapid increase in storage modulus G′, and the sample shows thermorheologically complex mechanical behavior. The polymer formed from the diol and MDI (I/MDI) exhibits a most-complex thermal behavior. On cooling and heating, four transitions can be detected in its thermal mechanical behavior, and the structure of the polymer is strongly dependent on its thermal history.     

Adhesive As-S-Se-I immersion lenses for enhancing radiation characteristics of mid-IR LEDs operating in wide temperature range

The influence of As-S-Se-I chalcogenide glass lenses on the integral and spectral power and pattern of LED radiation has been shown. Simulation of the influence of the refractive index on the integral power for two lens shapes has been performed. The wettability and adhesion force of As-S-Se-I melt has been determined for several electronic engineering materials. Mechanical stresses between chalcogenide glass and adjacent diode body materials have been calculated for −100 to 53 °C temperature range. Stability of the immersion lenses against cracking has been experimentally investigated for −150 to 53 °C temperature range.     

Interphase Transfer of Tackifier between Immiscible Rubbers

Interphase transfer of a coumarone-indene tackifier between natural rubber (NR) and poly(isobutylene) (PIB) was studied. The laminated sheets, composed of a sheet of NR with the tackifier and a sheet of PIB with the tackifier, were annealed at various temperatures to promote the interphase transfer of the tackifier. After separating the two sheets, the infrared spectra were measured to evaluate the tackifier content in each rubber sheet. It was found that a large amount of the tackifier resided in PIB after annealing at ?20°C, whereas the tackifier moved to NR at 40°C. Consequently, the NR sheet exhibited a lower glass transition temperature T_g after annealing at ?20°C and a higher T_g when annealed at 40°C. The differential scanning calorimetry measurements revealed that the crystallization of NR was responsible for the tackifier transfer. This phenomenon should be of interest because the tackifier transfer, which results in the T_g shift of each rubber, would also occur in a blend system. When NR is the matrix of the blend, it would be an ideal blend because the matrix would show a low T_g in winter and a high T_g in summer.     

Thermal,Mechanical, and Dielectric Properties of a Dielectric Elastomer for Actuator Applications

Dielectric elastomers (DE) are a new type of electro-active material, which is able to produce a large degree of deformation under electrical stimulation. The thermal, mechanical, and dielectric properties of the most widely used dielectric acrylic elastomer (VHB 4910), commercially available from the company 3M, were studied by differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and broadband dielectric spectroscopy (BDS) analyzer, respectively. DSC experiments on the VHB 4910 showed a glass transition at about ?40°C. VHB 4910 started to lose weight at about 250°C from the TGA study. The results of DMA indicated the storage modulus of VHB 4910 increased with frequency and had a strong temperature dependence of elasticity. The dielectric constant of VHB 4910 increased as a function of temperature up to 0°C, followed by a drop till 100°C. The mechanical and electrical efficiency of dielectric elastomer actuators (DEA) of VHB 4910 were analyzed. It was demonstrated that the actuation performance is dominated by the mechanical properties of the elastomer and is less influenced by the frequency and the temperature dependence of the dielectric properties; this may be used to guide the design of actuator configurations, as well as the choice of actuator materials.