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.     

Thermostimulated creep in amorphous polyolefins. I

The thermostimulated creep of two amorphous polyolefins having the repeating unit ─(CH₂)_mC(CH₃)2─, where m = 2 and 3, was investigated from 77° to 350°. Two relaxation processes are distinguished: a secondary relaxation is observed at 138 and 113°, respectively, for m = 2 and m = 3; a primary relaxation is found around the glass transition. These relaxations have been resolved in their elementary components. From the data acquired, the mechanical losses have been calculated and compared with data from an inverted torsional pendulum. The activation energy found for the secondary relaxation—0.26 eV at 138° K for the amorphous polyolefin with m = 2 and 0.19 eV at 113° K for the polyolefin with m = 3—confirms that this relaxation mode is associated with restricted backbone motion.     

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 properties of Pr amorphous alloys

Starting from the Fert and Campbell Hamiltonian and assuming a suitable η-distribution, the magnetization and the specific heat for Pr amorphous alloys are evaluated in the molecular field approximation with ferromagnetic interaction.Recent low-temperature experimental data on the specific heat of Pr amorphous alloys are reasonably explained.     

Room temperature ferromagnetism in un-doped amorphous HfO_2 nano-helix arrays

Amorphous HfO2nano-helix arrays with different screw pitches were fabricated by the glancing angle deposition technique. Room temperature ferromagnetism was achieved in this undoped amorphous HfO2 nanostructure, which is attributed to singly charged oxygen vacancies. The different magnetic behavior and photoluminescence in flat film and nano-helix arrays originate from the distinction of defect components. This study could facilitate the understanding of ferromagnetism origin in undoped HfO2, it also suggests a possible way to alter the intrinsic defects in amorphous HfO2.     

The temperature dependence of the electrical conductivity in amorphous germanium

An investigation of the electrical conductivity in amorphous Ge has been made. It has been found that the temperature dependence of the conductivity can differ from the usually acceptedT ^–1/4 law. It has been shown that transition from the hopping-type conductivity can be influenced by the conductivity in extended states.Cukrovarnická 10, Praha 6, Czechoslovakia.We are grateful to dr. B. Velický for discussions about the subject matter of this paper and to Mr. J. Zemek for preparation of germanium samples.     

C NMR of polyolefins with a new high temperature 10 mm cryoprobe

Recently, a high temperature 10 mm cryoprobe was developed. This probe provides a significant sensitivity enhancement for ¹³C NMR of polyolefins at a sample temperature of 120–135 °C, as compared to conventional probes. This greatly increases the speed of NMR studies of comonomer content, sequence distribution, stereo- and regioerrors, saturated chain end, unsaturation, and diffusion of polymers. In this contribution, we first compare the ¹³C NMR sensitivity of this probe with conventional probes. Then, we demonstrate one of the advantages of this probe in its ability to perform 2D Incredible Natural Abundance Double Quantum Transfer Experiment (2D INADEQUATE) in a relatively short period of time. The 2D INADEQUATE has been rarely used for polymer studies because of its inherently very low sensitivity. It becomes even more challenging for studying infrequent polyolefin microstructures, as low probability microstructures represent a small fraction of carbons in the sample. Here, the 2D INADEQUATE experiment was used to assign the ¹³C NMR peaks of 2,1-insertion regioerrors in a poly(propylene-co-1-octene) copolymer.     

Thickness dependence of kink temperature and band bending in amorphous silicon

This paper reports the thickness and temperature dependence of the conductivity for dc glow-discharge amorphous silicon (a-Si : H) films. It is found that the kink temperature, at which an abrupt change of activation energy occurs, rapidly increases for the samples thinner than 0.24 μm and that this phenomenon can be used to determine the depth of surface band bending.     

The ratio of energy gap to transition temperature in amorphous superconductors

Using results of tunneling measurements, values of 2Δ(o)/kT_c for a number of amorphous transition-metal based superconductors are found to be 3.5±0.1 in agreement with the BCS theory in the weak-coupled limit unlike previously reported results suggesting strong electron-phonon coupling in amorphous non-transition metals such as Ga and Pb-Bi alloys. A comparison of our results with existing data for amorphous soft-metal alloys and A-15 compounds suggests that non-crystallinity alone does not give rise to a significantly enhanced electron-phonon interaction.     

Low temperature Mössbauer study of amorphous Fe-Ni-Cr-Mo-Si-B

Chromium containing amorphous alloys of composition $\text{Fe}{}_{\mathrm{<mtext>40?</mtext><mtext>x</mtext><mtext>2</mtext>}}\text{Ni}{}_{\mathrm{<mtext>40?</mtext><mtext>x</mtext><mtext>2</mtext>}}\text{Cr}{}_{\mathrm{x}}\text{Mo}{}_2\text{Si}{}_{10}\text{B}{}_8\text{, x=0,1,3,4,5,}$ have been studied by Mossbauer effect at 4.4 K. The results indicate that the large reductions in the saturation magnetisation observed in these alloys on addition of Cr may be largely due to the reduction of the Fe moment in the neighbourhood of Cr.     

Compensation of temperature drift in leaky-mode spectra for sensor applications

Leaky-mode spectroscopy enhanced with semitransparent metal films may be effectively used for optical gas detection. Most of the optical sensors show a large temperature drift which is detrimental for application purposes. In this paper a model for the compensation of a particular line shift in the leaky-mode spectrum is given and it is confirmed experimentally.     

Temperature and thickness dependence of low temperature transport in amorphous silicon thin films: A comparison to amorphous germanium

The temperature and thickness dependence of the low temperature electrical transport of amorphous silicon thin films measured in-situ in ultra-high vacuum are presented. As for a-Ge there is an extended range of $\text{ln ? ∝ T}{}^{\mathrm{<mtext>?1</mtext><mtext>4</mtext>}}$ for thick films with $\text{ln ? ∝ S}{}_2\text{T}{}^{\mathrm{<mtext>?1</mtext><mtext>3</mtext>}}$ for thin films with $\text{S}{}_2\text{∝ d}{}^{\mathrm{<mtext>?1</mtext><mtext>3</mtext>}}$ as expected from a variable range tunneling mechanism.     

Extraction of density-of-states in amorphous InGaZnO thin-film transistors from temperature stress studies

The instability of amorphous InGaZnO (a-IGZO) thin-film transistors (TFTs) with different active layer thicknesses under temperature stress has been investigated through using the density-of-states (DOS). Interestingly, the a-IGZO TFT with 22 nm active layer thickness showed a better stability than the others, which was observed from the decrease of interfacial and semiconductor bulk trap densities. The DOS was calculated based on the experimentally-obtained activation energy (E_A), which can explain the experimental observations. We developed the high-performance Al₂O₃ TFT with 22 nm IGZO channel layer (a high mobility of 7.4 cm²/V, a small threshold voltage of 2.8 V, a high I_on/I_off 1.8 × 10⁷, and a small SS of 0.16 V/dec), which can be used as driving devices in the next-generation flat panel displays.     

Substrate temperature influence on the trombogenicity in amorphous carbon nitride thin coatings

Carbon nitride thin films were obtained through plasma assisted physical vapor deposition technique by pulsed arc, varying the substrate temperature and investigating the influence of this parameter on the films hemocompatibility. For obtaining approaches of blood compatibility, environmental scanning electron microscopy (ESEM) was used in order to study the platelets adherence and their morphology. Moreover, the elemental chemical composition was determined by using energy dispersive spectroscopy (EDS), finding C, N and O. The coatings hemocompatibility was evaluated by in vitro thrombogenicity test, whose results were correlated with the microstructure and roughness of the films obtained.During the films growth process, the substrate temperature was varied, obtaining coatings under different temperatures, room temperature (T_room), 100 °C, 150 °C and 200 °C. Parameters as interelectrodic distance, voltage, work pressure and number of discharges, were remained constant. By EDS, carbon and nitrogen were found in the films.Visible Raman spectroscopy was used, and it revealed an amorphous lattice, with graphitic process as the substrate temperature was increased. However, at a critical temperature of 150 °C, this tendency was broken, and the film became more amorphous. This film showed the lowest roughness, 2 ± 1 nm. This last characteristic favored the films hemocompatibility. Also, it was demonstrated that the blood compatibility of carbon nitride films obtained were affected by the I_D/I_G or sp³/sp² ratio and not by the absolute sp³ or sp² concentration.     

Ni-Zr amorphous alloys: Low temperature specific heat and superconductivity

The specific heat (C_p) of the amorphous alloys Ni_100-xZr_x for x = 75, 65, 55 and 35 was measured from 0.8K to 40K and the composition trends of the transition temperature T_c, the enhanced density of states at the Fermi level N_γ(_F) and the Debye temperatures θ_D(0), θ_D(T) established. For the three superconducting compositions (x=75, 65, 55) N_γ(E_F increases rapidly with increasing [Zr] in agreement with the trend in amorphous Cu-Zr alloys. However, for the Zr-Ni alloys the bare density of states $\text{N}{}_0\text{(E}{}_{\mathrm{F}}\text{) =}\text{N}{}_{\mathrm{\gamma }}\text{(E}{}_{\mathrm{F}}\text{)}\text{(1 + λ}{}_{\mathrm{p}}\text{)}$ increases strongly with [Zr] in contrast to the Zr-Cu alloys where it is reported to be almost constant. We conclude that for the Ni-Zr alloys the electron-ion matrix element <I²> decreases with increasing [Zr]. Other results are related to recent photoemission studies of these alloys.     

Stress sensitivity coefficient in polycrystalline and amorphous ferromagnetic materials below room temperature

Summary The piezomagnetic coupling coefficient (the ?stress sensitivity?) is quantitatively investigated below room temperature and a comparison is made among polycrystalline samples and amorphous ones. The technique used is an original one. It experimentally consists in the measurement of the amplitude of magnetoelastic waves, their resonance frequency and differential susceptibility; theoretically, it consists in coupling Newton’s law of force with the piezomagnetic state equations. The results clearly show different responses of polycrystalline samples with respect to the amorphous ones; in particular the nonmonotonic behaviour of the ?stress sensitivity? for metallic glasses is interesting for establishing their actual magnetic states at low temperature.     

Resistivity variation near the critical temperature in some Ni-Fe base amorphous alloys

Accurate measurements of the electrical resistivity of three Ni_80?xFe_xP₁₄B₆ alloys (with x=10, 20 and 30) were performed in the temperature interval 1.5–500 K. Resistivity (ρ) and dρ/dT behaviours near T_c for the alloys with different x values are mutually very different. In particular $\text{dρ}\text{dT}$ variation near T_c for the alloys with x=10 and 20 is Ornstein-Zernicke like while for the alloy with x=30 is of more usual energy like type. A tentative explanation of this behaviour in terms of the influence of the percolation limit on the nature of the magnetic transition is offered.     

Electric-field-enhanced metal-induced crystallization of hydrogenated amorphous silicon at room temperature

A novel simple method of crystallization of hydrogenated amorphous silicon (a-Si:H) thin films is described. Namely, we studied a metal-induced crystallization enhanced by a dc electric field in sandwich p⁺–i–n⁺structures. The samples were fabricated from wide-bandgap a-Si:H with high hydrogen content (13–51 at. % H). Macroscopic islands of a-Si:H (up to ∼1 mm in diameter) in the region between upper (CrNi) and lower (ITO) contacts crystallize instantaneously when a sufficiently high dc electric field (≳10⁵ V cm^-1) is applied. The crystallization sets in at room temperature and ambient atmosphere and is spatially selective. A proposed microscopic mechanism of such an easy macroscopic crystallization consists in easy diffusion of Ni and/or Ni silicides (representing nucleation sites) through a dense network of voids in hydrogen-rich a-Si:H. Received: 30 November 2000 / Accepted: 3 May 2001 / Published online: 27 June 2001