Thermostimulated creep in amorphous polyolefins. II

The thermostimulated creep of three amorphous polyolefins having the repeating unit ─(CH₂)_mC(CH₃)(C₂ H₅)─, where m = 1, 2, and 3, was investigated from 77° K to 350° K. A broad relaxation process is observed around the glass transition temperature in each polyolefin. The corresponding TSC peaks have been resolved into elementary components with a relaxation time τ obeying a compensation law τ = τ_c exp {(ΔH/k)[1/T) —(1/T_c)], where T_c and T_c are characteristic of the polyolefin. From the TSC data, we have calculated, the mechanical loss peaks associated with the glass transition and we have compared them with the dielectric loss peaks.     

Low-temperature relaxations in amorphous polyolefins

The dynamic mechanical relaxation behavior (1cps) of two series of amorphous polyolefins, ─(CH₂)_mC(CH₃)₂─ and ─(CH₂)_mC(CH₃)(CH₂ CH₃)─ where m = 1, 2, 3 was investigated from 4.2°K to the glass transition. Most of the polymers show a damping maximum or pleateau in the 40 to 50°K region. Various mechanisms which have been suggested for cryogenic relaxations in amorphous polymers are considered as they might relate to the polyolefins. Two secondary relaxation processes above 80°K are distinguished. A relaxation at about 160°K (β) in the second and third member of each series is associated with restricted backbone motion. This process requires a certain degree of chain flexibility since it is not observed in the first member of each series. A lower Temperature process (γ) is observed in each member of the second series and is attributed to motion of the ethyl side group.     

Compensation temperature in amorphous polyolefins

The thermostimulated creep of two series of amorphous polyolefins, (CH₂)_mC(CH₃)₂ and (CH₂)_mC(CH₃)(CH₂CH₃) where m = 1, 2 and 3, was investigated from 77 to 350 K. The broad relaxation process observed around the glass transition in each polyolefin can be described by a distributed retardation time τ obeying a compensation law

$\text{τ=τ}{}_{\mathrm{c}}\text{exp}\text{δH}\text{k}\text{1}\text{T}\text{?}\text{1}\text{T}{}_{\mathrm{c}}$

where τ_c and T_c are characteristic of the polyolefin.     

Microwave absorption of alkylammonium carboxylate surfactants and their micelles in benzene solution

The microwave absorption of a series of solutions of n-octylammonium carboxylate surfactants [CH₃(CH₂)₇⁺NH^?₃O₂C(CH₂)_n CH₃; n=12, 14, 16 and 18] and n-octylammonium formate in benzene at concentrations below, at, and above the c.m.c. was studied at frequencies of 9.314, 16.2, 23.98, and 35.11 GHz, and in a few cases in the range 0.48 to 1.9 GHz, at 298 K. A wide distribution of relaxation times about a mean value is indicated which can be analyzed between two limiting values. The relaxation parameters display concentration dependence and reflect the relaxation of segments containing the ⁺NH₃^?O₂C group (τ_O? 10 ps) and probably a molecular process as the dominant relaxation modes in the unassociated ion—pairs. Above the c.m.c. similar intramolecular processes occur together with relaxation of the micelles. Information has been obtained on the c.m.c. values, and the microwave absorption and relaxation parameters have been related to the formation of reversed micelle types of aggregates.     

Ac-conductivity and dielectric relaxations above glass transition temperature for parylene-C thin films

45% semi-crystalline parylene-C (–H₂C–C₆H₃Cl–CH₂–) _n thin films (5.8 μm) polymers have been investigated by broadband dielectric spectroscopy for temperatures above the glass transition (T _g =90°C). Good insulating properties of parylene-C were obtained until operating temperatures as high as 200°C. Thus, low-frequency conductivities from 10⁻¹⁵ to 10⁻¹² S/cm were obtained for temperatures varying from 90 to 185°C, respectively. This conductivity is at the origin of a significant increase in the dielectric constant at low frequency and at high temperature. As a consequence, Maxwell–Wagner–Sillars (MWS) polarization at the amorphous/crystalline interfaces is put in evidence with activation energy of 1.5 eV. Coupled TGA (Thermogravimetric analysis) and DTA (differential thermal analysis) revealed that the material is stable up to 400°C. This is particularly interesting to integrate this material for new applications as organic field effect transistors (OFETs). Electric conductivity measured at temperatures up to 200°C obeys to the well-known Jonscher law. The plateau observed in the low frequency part of this conductivity is temperature-dependent and follows Arrhenius behavior with activation energy of 0.97 eV (deep traps).     

The microwave spectrum,structure, and dipole moment of the unstable molecule phosphaethene,CH2PH

A detailed rotational analysis of the microwave spectrum between 26.5 and 40 GHz of phosphaethene, CH₂PH, has been carried out. This molecule is the simplest member of a new class of unstable molecules—the phosphaalkenes. The species can be produced by pyrolysis of (CH₃)₂PH, CH₃PH₂ and also somewhat more efficiently from Si(CH₃)₃CH₂PH₂. Full first-order centrifugal distortion analyses have been carried out for both ¹²CH₂³¹PH and ¹²CH₂³¹PD yielding: A₀ = 138 503.20(21), B₀ = 16 418.105(26), and C₀ = 14 649.084(28) MHz for ¹²CH₂³¹PH. The 1₀₁-0₀₀μ_A lines have also been detected for ¹³CH₂PH, cis-CDHPH and trans-CHDPH. These data have enabled an accurate structure determination to be carried out which indicates: $\text{r(}\text{H}{}_{\mathrm{c}}\text{C}\text{) = 1.09 ± 0.015}\text{A}\text{?}\text{, ∠(}\text{H}{}_{\mathrm{c}}\text{CP}\text{) = 124.4 ± 0.8°; r(}\text{H}{}_{\mathrm{t}}\text{C}\text{) = 1.09 ± 0.015}\text{A}\text{?}\text{, ∠(}\text{H}{}_{\mathrm{t}}\text{CP}\text{) = 118.4 ± 1.2°; r(}\text{CP}\text{) = 1.673 ± 0.002}\text{A}\text{?}\text{, ∠(}\text{HCH}\text{) = 117.2 ± 1.2°; r(}\text{PH}\text{) = 1.420 ± 0.006}\text{A}\text{?}\text{, ∠(}\text{CPH}\text{) = 97.4 ± 0.4°}$. The dipole moment components have been determined as μ_A = 0.731 (2), μ_B = 0.470 (3), μ = 0.869 (3) D for CH₂PH; μ_A = 0.710 (2), μ_B = 0.509 (10), μ = 0.874 (7) D for CH₂PD.     

Semiconducting properties of CoO thin films

This paper reports electrical properties of CoO thin films of different thickness in the range 0.375 – 7.95 μm. Both electrical conductivity and thermopower were measured at elevated temperatures (1223 – 1423 K) and under controlled oxygen partial pressure (5 − 2.1x10⁴ Pa). It was found that at low p(O₂) the electrical conductivity decreases with film thickness. The activation energy of the electrical conductivity (E_a) in air decreases with the oxide thickness from 0.56 eV at 0.375 μm to 0.52 eV for massive CoO while at low p(O₂)=5 Pa the E_a is independent of the thickness (E_a = 0.46 eV). The reciprocal of the p(O₂) exponent of the electrical conductivity (n_δ) in the range 1223 K – 1373 K is close to four for the 7,95 μm film and is about 3.5–3.7 for the 0.375 μm film. The electrical properties of the CoO thin films are considered assuming different defect structures in the bulk phase and the surface layer.     

Phase transitions in [NH(CH3)3]2MeCl4 (Me = Cd,Zn,Cu) crystals

Dielectric properties of the new [NH(CH₃)₃]₂ZnCl₄ and [NH(CH₃)₃]₂CdCl₄ crystals from the [(CH₃) _n NH_4-n ]₂MeCl₄ group have been investigated in a wide temperature range (4.2–320 K). A series of phase transitions has been discovered at T₃ = 325 K,T₄ = 251 K,T₅ = 193 K, for [NH(CH₃)₃]₂CdCl₄ and at T₃ = 309 K, T₄ = 282 K, T₅ = 269 K for [NH(CH₃)₃]₂ZnCl₄. A ferroelectric phase has been discovered in the temperature interval T₄—T₅ from the temperature and frequency dependence of the dielectric permittivity ε(T, v). According to optical investigations the existence of ferroelastic phases in the temperature interval T₁ = 349 K–T₂ = 391 K and below T₅ for [NH(CH₃)₃]₂CdCl₄ and both above T₃ and below T₅ for [NH(CH₃)₃]₂ZnCl₄ has been ascertained.     

Magnetic annealing and crystallization kinetics of the metallic glass Fe5Co70Si15B10

Magnetic annealing and crystallization kinetics of amorphous ribbons of Fe₅Co₇₀Si₁₅B₁₀ were studied. For a toroid stress-relieved at 365°C for 2 h, the anistropy energy K_u obtained by cooling in a magnetic field from 300°C was ≈1.1 × 10³erg/cm³ at room temperature. The reorientation of induced anisotropy of this toroid followed the equation for first-order kinetics closely, yielding an activation energy ΔE = 1.9 eV and a pre-exponential frequency factor v₀ = 3.2 × 10¹³s^-1. Anisotropy reorientation in a toroid partially stress-relieved at 220°C, although was clearly reversible during 8 cycles of isothermal annealing in tranverse and in longitudinal field, exhibited significant deviations from the equation for first order kinetics. Treating the data in terms of the equation for first order kinetics, a narrow spectrum of activation energy from 1.2 to 1.8 eV, with corresponding frequency factors from 1.8 × 10⁸ s^-1 to 5.6 × 10¹² s^-1, was obtained. The difference in behavior between the two samples is discussed in the light of concepts in structural relaxation recently proposed by T. Egami. Crystallization kinetics was studied on a DSC apparatus, using Kissinger's method. At 10 K/min heating rate, the temperature of incipient crystallization was found to be 770 K. The activation energies found were in the range 4.8–4.2 eV.     

Structural and electrical characterization of the NASICON-type Li2FeZr(PO4)3 and Li2FeTi(PO4)3 compounds

In order to develop new electrolytes for all-solid-state rocking chair lithium batteries, the NASICON-type compounds Li₂FeZr(PO₄)₃ and Li₂FeTi(PO₄)₃ were investigated by powder X-ray diffraction technique and impedance spectroscopy. Li₂FeZr(PO₄)₃ is orthorhombic Pbna (a=8.706(3), b=8.786(2), c=12.220(5) Å) and Li₂FeTi(PO₄)₃ is orthorhombic Pbca (a=8.557(3), b=8.624(3), c=23.919(6) Å). They show no phase transitions from RT to 800 °C. In the same temperature range logσT vs. 1/T show no slope variations. The activation energies for the ionic conductivity were 0.62 and 0.64 eV for Li₂FeTi(PO₄)₃ and Li₂FeTi(PO₄)₃, respectively. In order to better evaluate the present results they were compared with those of α and β-LiZr₂(PO₄)₃ phases, which were also prepared and characterised. A change of activation energy from 0.47 eV to 1.03 eV was observed in the case of β phase, at about 300 °C; attributed to the β (orthorhombic) ? β′ (monoclinic) phase transition. In the α phase the activation energy 0.47 eV in the temperature range 150 – 850 °C. The Li₂FeZr(PO₄)₃ and Li₂FeTi(PO₄)₃ compounds can be interesting for applications as solid electrolytes in high temperature (>300 °C) lithium batteries.     

Proton magnetic resonance study of the phase transitions of [N(CH3)4]2BCl4 (B=Co, Cu, Zn, and Cd) single crystals

The proton spin-lattice relaxation rates in [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals grown using the slow evaporation method were investigated over the temperature range 120-400 K. It was found that the relaxation processes of ¹H for all the [N(CH₃)₄]₂BCl₄ crystals can be described with single exponential functions. The changes in the ¹H relaxation behavior in the neighborhood of the phase transition temperatures are used to detect changes in the state of internal motion. From the ¹H spin-lattice relaxation rate measurements for [N(CH₃)₄]₂BCl₄ crystals, the activation energies were calculated for each phase. The large values of the activation energies indicate that the N(CH₃)₄ groups are significantly affected during the transitions. Although these [N(CH₃)₄]₂BCl₄ crystals all belong to the group of A₂BX₄-type crystals, their ¹H spin-lattice relaxation rates have different temperature dependences and indicate the occurrence of different molecular motions within the crystals. We additionally show for the first time that the differences in ¹H spin-lattice relaxation rates among the [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals arise from differences in the electron structures of the metal ions within the series.     

ESR of Gamma Irradiation and Ultraviolet Photolysis Products in Some Tetrasubstituted Ammonium Compounds

Abstract

The electron spin resonance of gamma and ultraviolet irradiated tetrabutylammonium halides [CH₃(CH₂)₃]₄NX (X=I,Cl,Br), tetrabutylammonium hydrogen sulfate [CH₃(CH₂)₃]₄NHSO₄, tetrabutylammonium periodate [CH₃(CH₂)₃]₄NIO₄, and ultraviolet photolyzed tetramethylammonium iodide, (CH₃)₄NI, and tetramethylphosphonium iodide, (CH₃)₄PI have been investigated between 140 and 350 K. The gamma and ultraviolet irradiation damage centers in tetrabutylammonium compounds were attributed to CH₃—CH^…—CH^…—CH₂, radicals, and ultraviolet photolysis damage centers in tetramethylammonium and phosphonium iodides were attributed to ?H₃ radicals. The g values of both radicals are found to be isotropic and g = 2.0030 and 2.0037 respectively to the methylallyl and the methyl radicals. The hyperfine coupling constants of the free electron to the protons in the radicals are reported and discussed.     

Dielectric relaxation in ferroelectric (CH3)2NH2AL(so4)2 · 6H2O crystal

Abstract

This paper presents the results of the investigation of dielectric dispersion and ultrasonic velocity in the ferroelectric (CH₃)₂NH₂Al(SO₄)₂ · 6H₂O crystal. The crystal shows a critical slowing down process of polarization with an extremely long relaxation time of the dipole system (τ = 1.6 · 10^?7s at the phase transition point). The dielectric response over the frequency range up to 56 GHz in the paraelectric phase can be well described in terms of a monodispersive Debye-type formula. The activation energy of dipoles in the paraelectric phase is 0.11 eV = 8.5 kT_c . The results show that the proper ferroelectric phase transition is nearly critical and of the order-disorder type.     

Electron spectroscopy with excited atoms and photons.: X. Halogen-substituted methanes and methyl amines

Electron binding energy spectra have been measured for CH₃Cl, CH₃Br, CH₃I, CFCl₃, CF₂Cl₂, CF₃Cl, CF₄, CH₃NH₂, (CH₃)₂ NH and (CH₃)₃N. Measurements have been made using 584 Å (21.22 eV) photons as well as with 2³S(19.82 eV) and 2¹S(20.62 eV) metastable helium atoms. Relative spectral intensities are compared for photoionization and Penning ionization.     

Optical and magnetooptical properties of CoFeB/SiO<Subscript>2</Subscript> and CoFeZr/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> granular magnetic nanostructures

The optical and magnetooptical properties of the new granular nanocomposites (CoFeB)/(SiO₂) and (CoFeZr)/(Al₂O₃), which are grains of amorphous ferromagnetic alloys embedded in dielectric matrices, have been studied. The dependence of the optical, magnetooptical, and magnetic properties of the nanocomposites on their qualitative and quantitative composition, as well as on the conditions of their preparation, was investigated. Spectra of the dielectric functions ε = ε₁ ? iε₂ were obtained by the ellipsometric method in the range 0.6–5.4 eV. Above 4.2 eV, the absorption coefficient of the (CoFeB)/(SiO₂) composites was found to be close to zero for all magnetic-grain concentrations. The polar Kerr effect measured at a photon energy of 1.96 eV in dc magnetic fields of up to 15 kOe reaches values as high as 0.25°–0.3° for these nanocomposites and depends only weakly on the conditions of preparation. On the other hand, the (CoFeZr)/(Al₂O₃) nanostructures reveal a considerable difference in the concentration dependences of the Kerr effect between samples prepared in a dc magnetic field and in zero field.     

Laser Raman study of phase transformations in [N(CH3)4]2ZnCI4 single crystals

We report temperature-dependent Raman studies on single crystals of [N(CH₃)₄]₂ZnCI₄ from 300 to 10 K. The observed spectral features suggest that both the N(CH₃)₄ ⁺ and ZnCl^2- ₄ ions are distorted from their regular tetrahedral structure and occupy sites of C_s symmetry in the lattice at room temperature. From the variation of line width of some selected Raman bands and other spectral changes as a function of temperature, it is inferred that both the ZnCl^2- ₄ and—CH₃ groups have high motional freedom at room temperature and the different phase transitions up to 160 K are triggered by the gradual freezing-in of orientational freedom of these groups, while the N—C₄ tetrahedra do not play any significant role in these phase transitions. The monoclinic to orthorhombic superlattice phase transitions at 159 K is triggered by freezing-in of the orientational motions of both the ZnCl^2- ₄ and N(CH₃)⁺ ₄ groups in the lattice.     

Ultrasound attenuation in solid CH4

We have studied the attentuation of 4 and 12 MHz longitudinal sound in polycrystalline solid CH₄ from 4 to 77°K. Just above 20·48°K, the temperature of the known upper lambda transition, a broad attenuation maximum with significant structure is observed. A sharp peak at the transition temperature is attributable to anomalous thermal conduction in small crystallites; the remainder of the absorption is described by a simple relaxation process with characteristic time τ = τ₀ exp (180/T). No attenuation anomaly was observed near the temperature of a suspected lower transition, 8°K.     

The exciton absorption in deformed germanium

Absorption spectra at 77° K near the direct (κ = 0) exciton transition are reported for deformed and undeformed single-crystal films of n-type Ge oriented on (111); Elliott's theory is applied. The optical width of the forbidden band for this transition is found as E_{g 0} = (0.8821 ±±0.0002) eV, while the exciton binding energy is found as E_ex(0) = = (0.0016±0.0003) eV for undeformed Ge at 77 ° K. The mean temperature coefficient of E_g for κ = 0 in the range 77 °–297 ° K is (dE_g/ /dT)_p =?3.50 · 10^?4 eV/deg. The effects of thermoelastic deformation on the exciton spectrum give (dE_g/dT)_d = (?1.5±0.1) · 10^?4 eV/deg. The half-width σ ≈ 5 · 10^?4 eV of the exciton peak gives the exciton lifetime as gt ≥ 10^?12 sec.     

Chemisorption and decomposition reactions of oxygen-containing organic molecules on clean Pd surfaces studied by UV photoemission

We have used uv photoeinission (primarily at a photon energy hv = 40.8 eV) to study chemisorption and decomposition reactions of small oxygen-containing organic molecules on clean polycrystalline Pd surfaces at 120 and 300 K. These molecules include methanol (CH₃OH), dimethyl ether (CH₃OCH₃) formaldehyde (H₂CO), acetaldehyde [H(CH₃)CO], and acetone [(CH₃)₂CO]. Chemisorption bonding of these molecules to the Pd surface occurs primarily through the lone-pair orbitais associated with the oxygen atoms, as evidenced by chemical bonding shifts of these orbitais toward larger electron binding energy relative to the other adsorbate valence orbitals. At 300 K all the molecules studied decompose on the surface, resulting in chemisorbed CO. Since chemisorbed (as well as condensed) phases of some of these molecules (CH₃OH and H(CH₃)CO) are observed at low temperature, the decomposition to CO is a thermally-activated reaction. The observed orbital shifts associated with chemisorption bonding are used to make rough estimates of interaction strengths and chemisorption bond energies (within the framework of Mulliken's theory of electron donor-acceptor complexes as applied to chemisorption by Grimley). The resulting heats of chemisorption are consistent with the observed surface reactions.     

Gas‐phase oxidation of CH2 = C(CH3)CH2Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed

Relative kinetics of the reactions of OH radicals and Cl atoms with 3‐chloro‐2‐methyl‐1‐propene has been studied for the first time at 298 K and 1 atm by GC‐FID. Rate coefficients are found to be (in cm³ molecule^?1 s^?1): k₁ (OH + CH₂ = C(CH₃)CH₂Cl) = (3.23 ± 0.35) × 10^?11, k₂ (Cl + CH₂ = C(CH₃)CH₂Cl) = (2.10 ± 0.78) × 10^?10 with uncertainties representing ± 2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC‐MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2‐hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.