High-pressure vibrational properties of polyethylene

The pressure evolution of the vibrational spectrum of polyethylene was investigated up to 50 GPa along different isotherms by Fourier-transform infrared and Raman spectroscopy and at 0 K by density-functional theory calculations. The infrared data allow for the detection of the orthorhombic Pnam to monoclinic P2(1)∕m phase transition which is characterized by a strong hysteresis both on compression and decompression experiments. However, an upper and lower boundary for the transition pressure are identified. An even more pronounced hysteresis is observed for the higher-pressure transition to the monoclinic A2/m phase. The hysteresis does not allow in this case the determination of a well defined P-T transition line. The ambient structural properties of polyethylene are fully recovered after compression/decompression cycles indicating that the polymer is structurally and chemically stable up to 50 GPa. A phase diagram of polyethylene up to 50 GPa and 650 K is proposed. Analysis of the pressure evolution of the Davydov splittings and of the anomalous intensification with pressure of the IR active wagging mode provides insight about the nature of the intermolecular interactions in crystalline polyethylene.     

Dimerization and polymerization of isoprene at high pressures

The high-pressure reactivity of isoprene has been studied at room temperature up to 2.6 GPa by using the diamond anvil cell technique in combination with Fourier transform infrared spectroscopy. Both dimerization and polymerization reactions take place above 1.1 GPa. At this pressure, the two processes are well separated in time, the dimerization being the only one occurring in the first 150 h. Both processes simultaneously occur as the pressure increases. The reaction product is composed of a volatile fraction, identified as sylvestrene, and a transparent rubberlike solid formed by cis-1,4- and 3,4-polyisoprene. The activation volume of the dimerization reaction has been obtained from the kinetic data. The photoinduced reaction, studied at room temperature for two different pressures, takes place through a two-photon absorption process, and the threshold pressure is lowered to 0.5 GPa. At this pressure, both the dimerization and polymerization processes occur, but the dimerization is not as selective as in the purely pressure-induced reaction. 4-Ethenyl-2,4-dimethylcyclohexene is obtained in addition to sylvestrene. By increasing the pressure, the photoinduced reaction becomes more selective, and the monomer is quantitatively transformed into the same polymer obtained in the purely pressure-induced reaction.     

Infrared dichroism of polyethylene crystallized by orientation and pressure in a capillary viscometer

Polarized infrared absorption spectra have been obtained by Fourier-transform spectroscopy for several crystalline and noncrystalline absorption bands of polyethylene crystallized by orientation and pressure in capillary viscometer. An analysis of data obtained at room temperature yielded degrees of crystallinity which are in good accord with values obtained from calorimetry and density measurements. The dichroism of the infrared absorption bands for the crystalline region revealed an extreme degree of orientation consistent with previous x-ray studies and also demonstrated that the degree of orientation is a good or better than that obtained from drawn polyethylene films with extension ratios of 20. Dichroism of bands from the amorphous phases revealed that the noncrystalline chain segments are in a comparatively relaxed state compared with results for drawn films having extension ratios of about 2 to 7. This is 1/10 to 1/3 the extension ratio of drawn polyethylene which shows maximum crystalline orientation. The results also indicated that the ratio of the GTG′ to GG segment conformations in the amorphous regions is larger than that of amorphous portions in unoriented polyethylene. The vinyl endgroups were shown to be highly oriented, while the main bulk of the amorphous polymer was fairly relaxed, i.e., of low orientation. It is concluded that the amorphous polyethylene state is strongly dependent on the nature of the crystalline–amorphous interface.     

Effects of ultra-high pressures (>3.6 GPa) on the electrical resistance of polyaniline by in situ FT-IR studies

Electrical resistance measurements and FT-IR spectroscopy of polyaniline were studied in situ under ultra-high pressures generated by a diamond anvil cell (DAC). The electrical resistance of polyaniline decreased as the pressure increased, exhibiting polaron conductor characteristics. Minimum electrical resistance was observed at 3.6 GPa, about three orders of magnitude smaller than that at 1.0 GPa. Changes in electrical resistance were reversible when the pressure was below 3.6 GPa. In situ FT-IR results showed that irreversible chemical changes of the quinoid units in polyaniline molecular chains took place when the pressure exceeded 3.6 GPa, giving rise to a huge increase in electrical resistance.     

Deterioration of polyethylene pipes exposed to water containing chlorine dioxide

Chlorine species used as disinfectants in tap water have a deteriorating effect on many materials including polyethylene. There are only very few scientific reports on the effect on polyethylene pipes of water containing chlorine dioxide. Medium-density polyethylene pipes stabilized with hindered phenol and phosphite antioxidants were pressure tested with water containing 4 ppm chlorine dioxide at 90 °C and pH = 6.8 as internal medium. The stabilizers were rapidly consumed towards the inner pipe wall; the rate of consumption was four times greater than in chlorinated water (4 ppm, pH = 6.8) at the same temperature. The depletion of stabilizer occurred far into the pipe wall. A supplementary study on a polymer analogue (squalane) containing the same stabilizer package showed that the consumption of the phenolic antioxidant was 2.5 times faster when exposed water containing chlorine dioxide than on exposure to chlorinated water. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that in the surface layer which came into contact with the oxidising medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. Scanning electron microscopy showed that propagation of cracks through the pipe wall was assisted by polymer degradation.     

Structural properties and phase transitions in a silica clathrate

Melanophlogite, a low-pressure silica polymorph, has been extensively studied at different temperatures and pressures by molecular dynamics simulations. While the high-temperature form is confirmed as cubic, the low-temperature phase is found to be slightly distorted, in agreement with experiments. With increasing pressure, the crystalline character is gradually lost. At 8 GPa, the radial distribution function is consistent with an amorphous state. Like pristine glass, the topology changes, plastic behavior, and permanent densification appear above ～12 GPa, triggered by Si coordination number changes. We predict that a partial crystalline and amorphous sample can be obtained by recovering the sample from a pressure of ～12-16 GPa.     

Synthesis of ZrSiO4 and Coesite in SiO2-ZrO2 System Under High Pressure

ZrSiO4 and coesite were obtained under high-pressure and high-temperature from the nano precursor of a-SiO2 and ZrO2. XRD and Raman measurements indicate that ZrSiO4 was formed at a temperature higher than 920 ℃ under a pressure of 3.6 GPa. As the pressure increased to 3.9 GPa, the ZrSiO4 formation temperature was reduced to 815 ℃. The formation temperature for coesite was 990 ℃ under 3.9 GPa. The lower formation temperature for ZrSiO4, as compared to that for coesite, provided an experimental evidence that the coesite in the Earth＇s surface usually occurs as inclusions in ZrSiO4.     

Determination of elastic shear constants of polyethylene at room temperature by inelastic neutron scattering

The elastic shear constants of both the amorphous and crystalline regions of polyethylene have been measured at room temperature. A newly developed method is used which allows the determination of elastic constants from the coherent inelastic neutron scattering of polycrystals. A deuterated and partially oriented sample is investigated on a triple-axis spectrometer and a time-of-flight instrument. The elastic constants of the crystalline regions of polyethylene are c₄₄ = 2.1 ± 0.3, c₅₅ = 2.2 ± 0.3, c₆₆ = 1.8 ± 0.2, and c′ = 1/4(c₁₁ + c₂₂ ? 2c₁₂) = 0.92 GPa. The shear modulus of the amorphous regions is obtained as G = 0.55 ± 0.03 GPa. In connection with other experimental results the elastic constant matrix is given and compared with theoretical estimates. With simple models, macroscopic moduli are calculated which are in good agreement with published experimental data.     

Mechanistic aspects of the solid-state transformation of ammonium cyanate to urea at high pressure

The chemical transformation of ammonium cyanate into urea has been of interest to many generations of scientists since its discovery by Friedrich W?hler in 1828. Although widely studied both experimentally and theoretically, several mechanistic aspects of this reaction remain to be understood. In this paper, we apply computational methods to investigate the behavior of ammonium cyanate in the solid state under high pressure, employing a theoretical approach based on the self-consistent-charges density-functional tight-binding method (SCC-DFTB). The ammonium cyanate crystal structure was relaxed under external pressure ranging from 0 to 700 GPa, leading to the identification of five structural phases. Significantly, the phase at highest pressure (above 535 GPa) corresponds to the formation of urea molecules. At ca. 25 GPa, there is a phase transition of ammonium cyanate (from tetragonal P4/nmm to monoclinic P21/m) involving a rearrangement of the ammonium cyanate molecules. This transformation is critical for the subsequent transformation to urea. The crystalline phase of urea obtained above 535 GPa also has P21/m symmetry (Z = 2). This polymorph of urea has never been reported previously. Comparisons to the known (tetragonal) polymorph of urea found experimentally at ambient pressure suggests that the new polymorph is more stable above ca. 8 GPa. Our computational studies show that the transformation of ammonium cyanate into urea is strongly exothermic (enthalpy change -170 kJ mol-1 per formula unit between 530 and 535 GPa). The proposed mechanism for this transformation involves the transfer of two hydrogen atoms of the ammonium cation toward nitrogen atoms of neighboring cyanate anions, and the remaining NH2 group creates a C-NH2 bond with the cyanate unit.     

Thermostimulated currents in low-density polyethylene and its blends with various components after high-pressure plastic deformation

It is established that the plastic deformation of low-density polyethylene (LDPE) under a pressure 0.5–2.0 GPa on a high-pressure apparatus of the Bridgman anvil type leads to the appearance of thermostimulated currents in samples, indicating that the samples contain trapped electrons. It is shown that two peaks are present on the temperature dependences of the currents; one of these is most probably related to the cold crystallization of the polymer, its structure being destroyed upon high-pressure deformation, while the other is related to the melting of the polymer. It is noted that the peaks were absent on temperature dependences of the currents for LDPE blends with some components; this could be due to the formation of a conducting state at interfaces. It is found that the electroconductivity of some blends after processing under pressure was higher than that in LDPE itself by a factor of 25.     

Thermodynamic properties of some polymeric forms of fullerite C<Subscript>60</Subscript> at temperatures ranging from 0 to 320 K

The temperature dependences of the heat capacityC ⁰ _p of fullerites C₆₀ were studied at temperatures ranging from 5 to 320 K in an adiabatic vacuum calorimeter with an accuracy of 0.4–0.2%. The fullerite C₆₀ samples were prepared by treating the starting fullerite C₆₀ under 8 GPa at 920 and 1270 K and “quenched” by a sharp decrease in pressure to −10⁵ Pa and in temperature to ∼300 K. Fullerite C₆₀(8 GPa, 920 K), a crystalline polymer with layered structure formed by polymerized fullerene C₆₀ molecules, was obtained at 920 K and 8 GPa. Fullerite C₆₀(8 GPa, 1270 K), a three-dimensional polymer with a graphite-like structure formed by fragments of decomposed C₆₀ molecules and containing many C(sp³)−C(sp³) bonds, was obtained at 1270 K and 8 GPa. Both polymers are metastable polymeric phases. The anomalous character of the temperature dependence of the heat capacity was revealed in the 49–66 K range for the polymer formed at 1270 K. The thermodynamic functions of the substances under study were calculated for the 0–320 K region along with entropies of their formation from graphite. The entropies of transformation of the starting fullerite C₆₀ into metastable phases and that of intertransformation of phases were estimated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 277–281, February, 2000.     

Physical and mechanical properties of ultra-oriented high-density polyethylene fibers

Ultra-oriented high-density polyethylene fibers (HDPE) have been prepared by solid-state extrusion over 60–140°C range using capillary draw ratios up to 52 and extrusion pressures of 0.12 to 0.49 GPa. The properties of the fibers have been assessed by birefringence, thermal expansivity, differential scanning calorimetry, x-ray analysis, and mechanical testing. A maximum birefringence of 0.0637 ± 0.0015 was obtained, greater than the calculated value of 0.059 for the intrinsic birefringence of the orthorhombic crystal phase. The maximum modulus obtained was 70 GPa. The melting point, density, crystallinity, and negative thermal expansion coefficient parallel to the fiber axis all increase rapidly with draw ratio and at draw ratios of 20–30 attain limiting values comparable with those of a polyethylene single crystal. The properties of the fibers have been analyzed using the simple rule of mixtures, assuming a two-phase model of crystalline and noncrystalline microstructure. The orientation of the noncrystalline phase with draw ratio was determined by birefringence and x-ray measurements. Solid-state extrusion of HDPE near the ambient melting point produced a c-axis orientation of 0.996 and a noncrystalline orientation function of 0.36. Extrusion 50°C below the ambient melting point produced a decrease in crystallinity, c-axis orientation, melting point, and birefringence, but the noncrystalline orientation increased at low draw ratios and was responsible for the increased thermal shrinkage of the fibers.     

Pressure-induced ordering in adamantane: a Monte Carlo simulation study

Isothermal-isobaric ensemble Monte Carlo simulation of adamantane has been carried out with a variable shape simulation cell. The low-temperature crystalline phase and the room-temperature plastic crystalline phases have been studied employing the modified Williams potential. We show that at room temperature, the plastic crystalline phase transforms to the crystalline phase on increase in pressure. Further, we show that this is the same phase as the low-temperature ordered tetragonal phase of adamantane. The high-pressure ordered phase appears to be characterized by a slightly larger shift of the first peak toward a lower value of r in C-C, C-H, and H-H radial distribution functions as compared to the low-temperature tetragonal phase. The coexistence curve between the crystalline and plastic crystalline phase has been obtained approximately up to a pressure of 4 GPa.     

Benzene under high pressure: a story of molecular crystals transforming to saturated networks, with a possible intermediate metallic phase

In a theoretical study, benzene is compressed up to 300 GPa. The transformations found between molecular phases generally match the experimental findings in the moderate pressure regime (<20 GPa): phase I (Pbca) is found to be stable up to 4 GPa, while phase II (P4(3)2(1)2) is preferred in a narrow pressure range of 4-7 GPa. Phase III (P2(1)/c) is at lowest enthalpy at higher pressures. Above 50 GPa, phase V (P2(1) at 0 GPa; P2(1)/c at high pressure) comes into play, slightly more stable than phase III in the range of 50-80 GP, but unstable to rearrangement to a saturated, four-coordinate (at C), one-dimensional polymer. Actually, throughout the entire pressure range, crystals of graphane possess lower enthalpy than molecular benzene structures; a simple thermochemical argument is given for why this is so. In several of the benzene phases there nevertheless are substantial barriers to rearranging the molecules to a saturated polymer, especially at low temperatures. Even at room temperature these barriers should allow one to study the effect of pressure on the metastable molecular phases. Molecular phase III (P2(1)/c) is one such; it remains metastable to higher pressures up to ～200 GPa, at which point it too rearranges spontaneously to a saturated, tetracoordinate CH polymer. At 300 K the isomerization transition occurs at a lower pressure. Nevertheless, there may be a narrow region of pressure, between P = 180 and 200 GPa, where one could find a metallic, molecular benzene state. We explore several lower dimensional models for such a metallic benzene. We also probe the possible first steps in a localized, nucleated benzene polymerization by studying the dimerization of benzene molecules. Several new (C(6)H(6))(2) dimers are predicted.     

Simulated pressure response of crystalline indole

The isostatic pressure response of crystalline indole up to 25 GPa was investigated through static geometry optimization using Tkatchenko-Scheffler dispersion-corrected density functional theory method. Different symmetries were identified in the structural evolution with increased pressure, but no motif transition was observed, owing to the stability of the herringbone (HB) motif for small polycyclic aromatic hydrocarbons. Hirshfeld surface analysis determined that there was an increase in the fraction of H···π and π···π contacts within the high pressure structures, while the fraction of H···H contacts was lowered via geometric rearrangements. It was found that isostatic pressure alone, up to 25 GPa, was not sufficient to induce a chemical reaction due to the poor π-orbital overlap existing within the HB motif. However, the applied pressure sets the stage for an activated chemical reaction when the molecules approach each other along the long molecular axis, with a reaction energy and reaction barrier of 1.05 eV and 1.80 eV per molecular unit, respectively.     

High-pressure induced conformational and phase transformations of 1,2-dichloroethane probed by Raman spectroscopy

1,2-Dichloroethane (DCE) was loaded into diamond anvil cells and compressed up to 30 GPa at room temperature. Pressure-induced transformations were probed using Raman spectroscopy. At pressures below 0.6 GPa, fluid DCE exists in two conformations, gauche and trans in equilibrium, which is shifted to gauche on compression. DCE transforms to a solid phase with exclusive trans conformation upon further compression. All the characteristic Raman shifts remain constant in fluid phase and move to higher frequencies in the solid phase with increasing pressure. At about 4-5 GPa, DCE transforms from a possible disordered phase into a crystalline phase as evidenced by the observation of several lattice modes and peak narrowing. At 8-9 GPa, dramatic changes in Raman patterns of DCE were observed. The splitting of the C-C-Cl bending mode at 325 cm-1, together with the observation of inactive internal mode at 684 cm-1 as well as new lattice modes indicates another pressure-induced phase transformation. All Raman modes exhibit significant changes in pressure dependence at the transformation pressure. The new phase remains crystalline, but likely with a lower symmetry. The observed transformations are reversible in the entire pressure region upon decompression.     

Optical microscopy and in situ Raman scattering of single crystalline ethylene hydrate and binary methane-ethylene hydrate at high pressures

Visual observations through a microscope and in situ Raman measurements have been made for single crystalline ethylene hydrate (EH) and binary methane-ethylene hydrate (MEH) at pressures up to 3.7 GPa and room temperature. Both hydrates showed pressure-induced phase transitions at 1.6, 2.0, and 3.0 GPa for EH and at 1.7, 2.1, and 3.3 GPa for MEH. The cubic sI phase of EH and MEH remains stable up to 1.6 and 1.7 GPa, respectively, which are more widely ranging values than the values for the methane hydrate sI phase. In this sI phase of binary MEH, the cage occupancies by methane and ethylene molecules are investigated from Raman spectra. Above P = 3.0 GPa for EH and 3.3 GPa for MEH, they decomposed by associating with the formation of the polyethylene.     

Two-phase simulation of the crystalline silicon melting line at pressures from -1 to 3 GPa

Results of a numerical investigation of crystalline silicon melting line within the range of pressures from -1 to 3 GPa are presented. A two-phase molecular dynamics method is applied to obtain temperature, pressure, and densities of solid and liquid phases on the melting line. Using a special procedure we ensure the strict control of the two-phase equilibrium in the simulation cell. To describe the interaction between the atoms four classic potentials have been chosen: the Stillinger-Weber one and three modified variants of the Tersoff potential. For the Stillinger-Weber and Tersoff potentials in the modification by Kumagai-Izumi-Hara-Sakai a good coincidence with experimental data on crystalline Si melting temperature is obtained within the range of pressure from 0 to 3 GPa. Calculations of the solid and liquid phase densities on the silicon melting line for the Stillinger-Weber potential are also in close agreement with experiments.     

Light‐Induced Catalyst and Solvent‐Free High Pressure Synthesis of High Density Polyethylene at Ambient Temperature

The combined effect of high pressure and electronic photo‐excitation has been proven to be very efficient in activating extremely selective polymerisations of small unsaturated hydrocarbons in diamond anvil cells (DAC). Here we report an ambient temperature, large volume synthesis of high density polyethylene based only on high pressure (0.4–0.5 GPa) and photo‐excitation (~350 nm), without any solvent, catalyst or radical initiator. The reaction conditions are accessible to the current industrial technology and the laboratory scale pilot reactor can be scaled up to much larger dimensions for practical applications. FTIR and Raman spectroscopy, and X‐ray diffraction, indicate that the synthesised material is of comparable quality with respect to the outstanding crystalline material obtained in the DAC. The polydispersity index is comparable to that of IV generation Ziegler‐Natta catalysts. Moreover the crystalline quality of the synthesised material can be further enhanced by a thermal annealing at 373 K and ambient pressure.

     

Electron spin resonance studies on radiation graft copolymerization. I. Grafting initiated by alkyl radicals trapped in irradiated polyethylene

The behavior of trapped radicals in polyethylene which is irradiated in air at room temperature, under grafting of methylmechacrylate or butadiene has been studied by electron spin resonance. Part of the alkyl radicals are converted to allyl radicals by reaction with double bonds and the others disappear by recombination under vacuum. The active species of grafting are alkyl radicals when the vapor pressure of monomers is relatively high, while at low pressure allyl radicals also play a role as well as alkyl radicals. In the grafting at 20°C, the grafting yields depend mainly on the decay rate of alkyl radicals which come out of the crystalline regions of polyethylene. The decay rate of alkyl radicals and the rate of grafting at the initial stage increase with decreasing crystallite size of polyethylene.