Blended polyethylene terephthalate and polyethylene naphthalate polymers for scintillation base substrates

Polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are both good candidates for use as scintillation base substrates. One advantage is their relatively high density of 1.33 g cm⁻³. To enhance their relative strengths and to mitigate their weaknesses, we blended PET and PEN 1:1 by weight and found that the overall characteristics are improved. The wavelength at maximum emission was 415 nm, the refractive index was 1.61, and the light yield was 0.85 times that of PEN. These results increase the available options for base materials to be used as scintillators.     

Infrared studies on the molecular interactions of polymer blends: polystyrenes and polycarbonates systems

Fourier—transform infrared (FT-IR) with digital subtraction method has been applied to investigate the molecular interactions of immiscible polystyrene (PS)/bisphenol A polycarbonate (PC) blends and miscible PS/tetra-methyl PC (TMPC) blends. The FT-IR results show that there are no interactions for PS/PC, and the miscibility of PS/TMPC blends is mainly due to the intermolecular interaction between the phenyl ring of PS and the carbonate group of TMPC. The phenyl ring band of PS is linearly shifted to higher wave number with increasing concentration of TMPC, and the bandwidth at half maximum intensity of the carbonyl band of TMPC is linearly decreased with increasing concentration of PS. The amplitude of the interactional bands is decreased with increasing temperature consistent with LCST behavior of the blend. The miscibility of PS/TMPC and immiscibility of PS/PC has also been discussed in terms of local free-volume, self-interactions, and intermolecular interactions based on the chemical structures of PC and TMPC. Furthermore, the immiscibility behavior for blends of methyl-substituted PS and TMPC, and blends of PS and halogen-substituted PC has been explained in terms of intra and intermolecular interactions caused by steric and/or induction effects.     

Interfacial activity of styrene-butadiene block copolymers in low-density polyethylene/polystyrene blends

The effect of molecular structure of styrene-butadiene (SB) block copolymers on their interfacial activity in low-density polyethylene/polystyrene (LDPE/PS) (4/1) blends was studied. It was found that addition of some SB copolymers, which are localized in brittle PS particles, leads to a decrease in the blend impact strength in spite of the fact that these SB improve the toughness of both the blend components. Comparison with our previous results showed that the distribution of SB copolymers between the interface and bulk phases and their supermolecular structure in LDPE/PS (4/1) blends strongly differs from those in LDPE/PS (1/4) blends.     

The compatibility and transesterification for blends of polyethylene terephthalate)/poly(bisphenol-A carbonate)

A study has been made of the influence of transesterification on the miscibility in binary blends of poly(ethylene terephthalate) and poly(bisphenol-A carbonate). The blends were melt mixed in the range 260–300°C and studied by differential scanning calorimetry, dynamic mechanic analysis, and by Fourier transform infrared spectrometry. It was found that copolymer produced by a transesterification reaction can enhance the miscibility of this system. The new compositions were uniquely identified by FTIR. Gel permeation chromatography showed that molecular weight decreases were not the origin of miscibility. The ester exchange reaction itself was found to be initiated by the residual catalyst in the commercial polymers selected for study. This has been shown by the absence of reaction after polymer purification by solution and reprecipitation prior to melt mixing.     

Deformation and annealing behavior. II. Thick polyethylene terephthalate films

Thick (5-30 mil) samples of polyethylene terephthalate (PET), drawn uniaxially and biaxially followed by thermal crystallization, were studied by replication electron microscopy and wide- and small-angle X-rays. Deformation of gold-decorated samples indicated that aggregates on the 200–500 Å scale move as units during deformation. Thermal crystallization of both uniaxially and biaxially drawn samples occurred with the formation of coarse 200–500 Å nodular aggregates, which, in turn, may consist of the 75–100 Å nodules observed by Yeh and Geil. At annealing temperatures above 180° C, fibrillar lamellae are formed, arranged perpendicular to the draw direction in uniaxially drawn samples and at random in biaxially drawn samples. Small-angle photographs and pole figures of uniaxially drawn and annealed samples can be explained in terms of a toroidal arrangement of poles centered about the draw direction.     

Morphology and micromechanical behavior of blends of ethene/1-hexene copolymers

Using (Me₅Cp)₂ZrCl₂ and Et(Ind)₂ZrCl₂ activated by methylaluminoxane (MAO), ethene/1-hexene copolymers of markedly different densities were produced under the same conditions. Binary blends were produced by melt blending of a high-density ethene/1-hexene copolymer with an elastomeric ethene/1-hexene copolymer. Transmission electron microscope (TEM) investigations of ultrathin sections of samples stained with ruthenium tetroxide revealed the morphology of the different blends. Depending on the blend composition, the degrees of segregation differed. An analysis of the TEM micrographs shows that increasing the segregation of the elastomeric blend component seems to be accompanied by an increase of the mean thickness of the crystalline lamellae of the matrix. Corresponding to the TEM results, typical morphological structures were also revealed by scanning force microscope (SFM) investigations using the tapping mode and a force modulation mode. Furthermore, these SFM techniques were applied to study in situ local deformations and changes in the morphological structures in a certain specimen position while the external stress was successively increased. Results of these experiments, as well as those from additional TEM in situ tensile tests of thin sections, show that the deformation that appears homogeneously down to the micron range is strongly inhomogeneous in the submicron range.     

Modification of polyethylene terephthalate by proton irradiation

Polyethylene terephthalate (PET) films were irradiated with 3 MeV proton beams at different fluences. The microhardness, electrical, thermal and structural studies were carried out using microhardness tester, LCR meter, thermogravimetric analysis (TGA) and FTIR spectroscopy. Vickers' hardness has been observed to increase with the fluence. The true bulk hardness of the film was obtained at loads greater than 400 mN. The AC electrical conductivity is practically unaffected by irradiation up to a frequency of 10 kHz, but it is found to increase exponentially at a frequency of 300 kHz. The loss factor and dielectric constant are observed to change appreciably with the fluence. It is observed that there is no significant change in the stability of the polymer up to the fluence of 10¹⁴ ions cm^?2 as revealed by TGA and FTIR spectroscopy.     

Thermodynamics of ion-containing polymer blends and block copolymers

We develop a theory for the thermodynamics of ion-containing polymer blends and diblock copolymers, taking polyethylene oxide (PEO), polystyrene and lithium salts as an example. We account for the tight binding of Li^{+} ions to the PEO, the preferential solvation energy of anions in the PEO domain, the translational entropy of anions, and the ion-pair equilibrium between EO-complexed Li^{+} and anion. Our theory is able to predict many features observed in experiments, particularly the systematic dependence in the effective χ parameter on the size of the anions. Furthermore, comparison with the observed linear dependence in the effective χ on salt concentration yields an upper limit for the binding constant of the ion pair.     

Surface characterization of polyethylene terephthalate/silica nanocomposites

Poly(ethylene terephthalate) (PET) based nanocomposites containing hydrophilic (i.e. Aerosil 200 or Aerosil TT 600) or hydrophobic (i.e. Aerosil R 972) nano-silica were prepared by melt compounding. Influence of nano-silica type on surface properties of the resultant nanocomposites was investigated by the use of Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), contact angle measurement (CAM), scanning electron microscopy (SEM) and reflectance spectroscopy (RS). The possible interaction between nano-silica particles and PET functional groups at bulk and surface were elucidated by transmission FTIR and FTIR-ATR spectroscopy, respectively. AFM studies of the resultant nanocomposites showed increased surface roughness compared to pure PET. Contact angle measurements of the resultant PET composites demonstrated that the wettability of such composites depends on surface treatment of the particular nano-silica particles used. SEM images illustrated that hydrophilic nano-silica particles tended to migrate to the surface of the PET matrix.     

Application of a new structural theory to polymers. ii. transition states for amorphous polymers and copolymers

A recently developed nonequilibrium thermodynamic theory of continuum rheology is combined with a generalized definition of thermomechanical transitions, to produce a single equation for interrelating the basic variables (stress o, strain rate ε, pressure p, temperature T, and structure ?) at a transition. Specialization of ? to represent uncrosslinked polymers leads to incorporation of molecular weight M as a variable. New predictions are thus made for the glass transition [T_g(M), T_g(p), T_g(ε) and others] and compared successfully with data. Particularly remarkable are the results that 1/T_g is a piecewise linear function of In M, and T is piecewise linear with p. Comparable results and confirmation with data arise when applying the theory to the liquid-liquid transition, T _ll (M). For random copolymers, application of a single mixing rule to the transition equation leads to a prediction of T_g as a function of composition and the T_gi for the homopolymers (components i). This relationship reduces, in various cases, to several familiar equations in which the parameters were simply empirical, thus providing an interpretation of those parameters and defining restrictions applicable to each case. Finally, an alternative interpretation of ? in terms of free volume allows the theory to be extended to other systems, including those with small molecules.     

Tensile drawing of high and low molecular weight polyethylene terephthalate

The tensile drawing of polyethylene terephthalate fibers spun from polymer of high and low molecular weight over a range of windup speeds has been studied. An analysis of the mechanical properties, orientation, and shrinkage behavior for different draw ratios leads to two conclusions. First, the network structure is the same for both polymers and the same as that described for a medium molecular weight polymer in an earlier paper. Secondly, an increase in molecular weight has an effect similar to an increase in the windup speed on the spun fiber molecular structure, which affects the ultimate mechanical properties obtainable by the chosen processing routes.     

SAXS studies of blends of high- and low-density polyethylene

It is shown that in blends of PE having different melting temperatures the morphology depends drastically on the cooling rate. In these heterogeneous PE, the correlation relationship L = r between the long period L of the solid state and the dimension of the coils r in the liquid state is observed only in rapidly quenched materials. In slowcooled materials the SAXS spectra are interpreted in terms of segregation of two types of PE, on a scale of the order of the dimension of the coils, the arrangement of the crystalline lamellae being paracrystalline and statistical.     

Heat capacities of solid polymers

The heat capacity of a solid polymer is governed by the manner in which the internal energy is distributed over the various degrees of freedom. If the internal energy manifests itself in harmonic oscillatory motions, the heat capacity is the sum of contributions of the normal modes of motion. In practice, full frequency data are not generally available for polymers. This paper proposes an empirical method for determining the heat capacities of linear high polymers by the addition of contributions from different chain segments. A survey of heat capacity data for 30 linear high polymers and several copolymer systems has revealed that additivity is usually valid for a temperature range from about 60°K to the glass-transition temperature. A table of heat capacity contributions of a number of polymer constituents is derived which permits the calculation of unknown heat capacities to an accuracy of ±5% or better. In addition, δC_p data for the increase of the heat capacity at the glass-transition temperature were found to agree with the rule of constant heat capacity increase per mole of “bead” proposed 8 years ago.     

Monomolecular film and absorption behavior of polymers having carboxyl groups

π-A isotherms of monolayers of various copolymers containing carboxyl groups derived from acrylic acid (AA) were measured. The conformation of polymer adsorbed on the water surface and interaction forces between polymer and water surface (considered to be a model for the surface of inorganic powders) owing to AA groups is discussed based on the π-A isotherms.

Polyacrylic esters having a small amount of AA groups formed the expanded type of monolayer. AA groups cause an increase in the interaction force between the polymer and water surface. Polymethyl methacrylate having a small amount of AA groups formed condensed-type monolayers, while with a large amount of AA groups it showed two types of monolayer collapse. Though polystyrene could not spread as a mono-layer, poly (styrene-acrylic acid) [p(St-AA)] copolymer formed a monolayer when the AA content was over 4 mol %. The adsorbance of P(St-AA) on water, calculated from π-A isotherm, is the same as that obtained on α-Fe₂O₃ independently. This means the conformation of the polymer on the solid surface and the interaction force can be discussed by using the π-A isotherm.     

Dual excimer and CO2 laser etching studies of polyethylene terephthalate

Polyethylene terephthalate (PET) films preheated with a pulsed CO₂ laser have been ablatively etched with an XeCl laser. The observed reduction in ablation threshold, from 170 to 140 mJ cm^–2, is consistent with a thermal mechanism for XeCl laser ablation of PET. Transient changes in the UV absorption coefficient of PET caused by heating with pulsed CO₂ laser radiation have also been studied and a significant increase in absorption observed at 308 nm. Permanent changes in the ultraviolet absorption of PET following exposure to low fluence XeCl laser radiation are also reported.     

Transesterification-Induced Evolution of Structure and Morphology in Poly(trimethylene terephthalate)/Poly(butylenes succinate) Blends

The evolution of the structure and morphology in poly(trimethylene terephthalate)/poly(butylene succinate) (PTT/PBS) blends induced by transesterification between PTT and PBS at different blending temperatures for 2 h and various times at 270°C was investigated. By control of the extent of transesterification, the degree of randomness, crystallization, morphology, and tensile properties of the blends could be modulated. The results indicated that the degree of randomness of the blends increased by increasing the blending temperature above 260°C and blending time, leading to the formation of copolyesters. The crystallization of the blends was restricted by the increase of blending temperature and time, shown by broad reflection peaks in X-ray spectra and less perfect spherulites as observed by polarized optical microscopy (POM), which was due to the increase of the degree of randomness. The elongation at break increased by increasing the blending time and temperature, accompanied by a decrease of tensile strength and elastic modulus, showing a dependence on the degree of randomness caused by the transesterification.     

Molecular dynamics simulation of gas diffusion behavior in polyethylene terephthalate/aluminium/polyethylene interface

Molecular dynamics (MD) simulations were performed to estimate the diffusion coefficients of O₂ and H₂O molecules in polyethylene terephthalate/aluminum/polyethylene interface at the temperature of 298 K. It came out that the diffusion coefficient of gasses in the interface is smaller than that of a single polymer, and the diffusion coefficients compare well with experimental data as well as previously published work. Furthermore, the diffusion coefficients of H₂O molecules in the interface are preferable to that of O₂ molecules. Interestingly, the largest diffusion coefficient was detected in the polyethylene terephthalate/aluminum(1 0 0)/polyethylene interface, while the smallest value of the diffusion coefficients was found in the polyethylene terephthalate/aluminum(1 1 1)/polyethylene interface. Calculation and analysis of the interaction between aluminum and polymers indicated that the interaction of polymer/aluminum(1 1 0) has the most interface strength, and crystal density of the metal surface has a definite effect on the planar interface energy. What’s more, the figure of gas molecule concentration is further resulted that the interface make contribution to adsorption of gas molecules. Moreover, the diffusion is belonging to the Einstein diffusion in the multilayer materials, and this work provides some key clues to improve the performance of polymer materials.     

SSIMS analysis of organics, polymer blends and interfaces

This paper gives a critical review on the applications of ToF SIMS in the areas of polymer additive characterization and in the study of polymer blends and interfaces. Polymer additives can readily be identified by ToF SIMS using their parent molecular ions or characteristic fragments. This analytical capability has been successfully applied to monitor the migration or segregation of additives during polymer processing. ToF SIMS is an ideal analytical tool for the study of polymer blends and interfaces because it is able to provide information on both surface composition and morphology. In combination with other analytical techniques such as AFM and XPS, ToF SIMS chemical imaging capability has opened up new horizons in the investigation of complex polymer blend systems. Finally the main advantages and limitations of ToF SIMS in these application areas are also discussed.     

纳秒脉冲放电对聚对苯二甲酸乙二酯憎水改性

基于自主研制的ns脉冲电源(上升沿约70ns,脉宽约100ns)激励介质阻挡放电产生大气压低温等离子体,在CF4气氛下对聚对苯二甲酸乙二酯(PET)表面进行了憎水改性处理,测量了改性前后的薄膜表面的水接触角,给出了CF4气流量、放电电压、处理时间和CF4比例等参数对改性效果的影响规律。结果表明,大气压ns脉冲DBD表面处理能够实现PET材料的憎水性,改性后的PET表面水接触角由66°提高到最大100°。