Structural ordering upon annealing of europium molybdate subjected to pressure treatment

It has been found that treatment of europium molybdate single crystals under high uniform pressure leads to radical changes of the IR reflectance spectra of the samples. Instead of a series of narrow lines, which are characteristic of the spectrum of the initial crystal, the spectrum of the sample subjected to pressure treatment exhibits broad bands. As follows from the results of X-ray diffraction measurements, this transformation of the IR spectra is associated with the fact that, after pressure treatment, the sample represents an amorphous matrix with inclusions of nanocrystals of the high-pressure phase. In the IR spectra, the high-pressure phase manifests itself in the form of a new line at approximately 600 cm⁻¹. After annealing of the sample with an increase of the temperature from 100 to 400°C, the high-pressure phase disappears. A further increase of the annealing temperature to 550°C leads to the recovery of the crystal structure of the initial β′ phase of europium molybdate and to the appearance of lines corresponding to the α phase.     

典型高分子材料的固体核磁共振研究

本论文通过固体核磁共振（NMR）谱及动力学参量的测量,并结合X-射线衍射技术和DSC测量等研究了两种典型高分子材料的相结构、链的运动以及相与相之间的关系.  乙烯-醋酸乙烯共聚物( EVA) 是最主要的乙烯共聚物之一. 研究发现,EVA的相组成非常复杂,共有5个不同的组分. 除了PE中所观察到的常规单斜晶相和刚性的正交晶相外,我们发现还存在第三个晶相分量－运动性较强的晶相（SOCP,可能是转动相）. 它不仅拥有自己的熔点,而且它的化学位移和分子运动性不同于刚性正交晶相（LOCP）. 另一方面,非晶相也由两种不同的分量组成：运动受限的各相异性的非晶界面相和高度可动的橡胶型的非晶相. 我们进一步详细研究了EVA中的晶区链动力学和非晶区的低温冻结行为. 实验发现,在正交晶相中,高分子链以180° flip-flop方式运动,同时伴随沿链方向的平移型跳跃运动,并引起正交晶相和非晶相之间的长程链扩散,通过NOE的测量证实了这种相间链扩散的存在,并进一步通过实验证实这种相间链扩散是一种受限扩散而不是自由扩散. 同时非晶相的两个组分具有不同的低温冻结行为：当温度低于-弛豫转变温度时,橡胶型的非晶相中的长程分子运动被冻结,但仍存在分子的局域运动;而界面非晶在低温时冻结成一种有序取向结构,并用质子自旋扩散实验证实该有序结构与正交晶相相邻近.  少量纳米级片层状粘土分散在聚合物中就可赋予材料许多优异的性能,我们用固体NMR技术对EVA/REC复合材料的结构和其中粘土的分散性质进行研究,发现上述复合材料中所形成的晶体类型不仅依赖于各组分的性质还依赖于所形成的复合材料的类型.  偏氟乙烯/三氟乙烯共聚物（P（VDF-TrFE））是最主要的铁电高聚物之一. 我们利用变温固体¹⁹F MAS NMR 谱及弛豫数据的测量详细研究了电子辐照对P(VDF-TrFE)共聚物的分子结构、构型、运动性以及相变等的影响. 发现,电子辐照不仅改变了分子链段的构型和运动性,同时也改变了局部分子化学结构. 电子辐照促使铁电相向顺电相(或者非晶相)转变,与此同时诱发了富含VDF和含-TrFE链段从全反式的构型到混合的反式-旁式构型的转变. 电子辐照加剧顺电区域中的分子运动而在高温熔融态中(>100 ℃）,分子的运动反而受限.     

Librational dynamics of nitroxide molecules in a molecular glass studied by echo-detected EPR

Nitroxides 2,2,6,6-tetramethyl-4-piperidone N-oxide (tempone), 3-carboxy-proxyl and potassium peroxylamine disulfonate (Fremy salt) in glycerol solution were studied in a wide temperature range near the glass transition temperatureT _g. The echo-detected (ED) electron paramagnetic resonance (EPR) lineshape reveals strong dependence on the time interval τ between the echo-forming microwave pulses which is readily explained by anisotropic phase relaxation. Employing a librational model of molecular motion and the Redfield relaxation theory, spectra were simulated for the τ’s varying in a large interval. The anisotropic relaxation rate increases with temperature increase and it is larger for nitroxide with a larger molecular size. The mean-squared amplitude of motion, obtained from reduced hyperfine splitting in continuous-wave EPR, near T_g linearly depends on temperature which is characteristic of harmonic solids. For tempone in a host crystal 2,2,4,4-tetramethyl-cyclobutan-1, 3-dione the anisotropic spin relaxation rate decreases with temperature increase so the found feature solely belongs to a glassy state. A new approach is proposed for modeling slow wobbling motion in a restricted angular space.     

Dielectric relaxation of poly(ethylenglycol)- b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers above the glass transition temperature

The complex dielectric permittivity has been measured for three poly(ethylenglycol)-b-poly(propylenglycol)-b-poly(ethylenglycol) copolymers with different content of poly(ethylenglycol) (15%, 33% and 80%), and increasing degree of crystallinity (0%, 10% and 20%, respectively). Only the non-crystalline sample shows the normal mode relaxation together with the segmental (α-relaxation) and the Johari-Goldstein (β-relaxation) modes. The crystalline samples show also polarization contributions due to the existence of interfaces between the crystallites and the amorphous phase. The relaxation times of the (α and normal modes can be described by a VFT equation with the same value of T₀. There is a slowing-down of the segmental mode due to the presence of crystallites. The temperature dependence of the α and β relaxations in the copolymers is very similar to that found in pure PPG, while there are significant differences in the case of the normal mode of the non-crystalline sample. The size of the cooperatively rearranging regions CRR, and the width of the glass transition region increase slightly with the degree of crystallinity. The temperature dependence of the size of CRRs is compatible with the prediction of fluctuation theory. No systematic effect of the degree of crystallinity on the β-relaxation has been found. Near T _g the β-relaxation time is close to the primitive time of the coupling model. Received: 31 May 2000     

Optical control of the coherent dynamics of a bismuth lattice at liquid-helium temperature at low and high excitation levels

The fully symmetric A_1g phonons of bismuth have been investigated at liquid-helium temperature by the coherent control method for various crystal excitation levels. It has been found that large-amplitude coherent phonons exhibit the “rigidity” of the phase, which is absent at a small amplitude. The impossibility of changing the phase of phonon oscillations appears at the excitation levels at which their amplitude relaxation law changes from exponential to power. The modification of the phase properties and relaxation law of the excitations of the crystal lattice can be understood in terms of the concept of the condensation of phonons, which occurs with an increase in the crystal excitation level.     

A comparison of the dynamic mechanical relaxation behavior of linear low- and high-density polyethylenes

The mechanical relaxation behaviors of oriented samples of a linear low-density polyethylene (LLDPE) and a high-density polyethylene (HDPE) were studied using tensile dynamic mechanical measurements. The anisotropy and activation energies of the relaxations were determined for several different samples to investigate why the α-relaxation in HDPE has characteristics similar in some respects to both the α- and β-relaxations in LLDPE. It is concluded that the anisotropy of the α-relaxation in LLDPE is determined by c-shear, whereas in HDPE it relates to interlamellar shear. The activation energy measurements, however, show that the thermally activated process for the α-relaxation in both the LLDPE and HDPE is c-shear. It is proposed that, in HDPE, c-shear has to occur before there is enough mobility at the fold surface for interlamellar shear. It is concluded that the β-relaxation is not observed in HDPE because the interlamellar regions are too constrained to allow interlamellar shear without c-shear.     

Substrate effect on mechanical relaxation of polystyrene in ultrathin films

Mechanical relaxation behavior in ultrathin polystyrene (PS) films supported on silicon oxide (SiO_x) and gold (Au) substrates has been studied by dynamic viscoelastic measurement. Based on the method, effects of free surface and substrate interface on the segmental dynamics were discussed. In the case of thin PS films with a thickness of approximately 200 nm, α_a-relaxation process corresponding to the segmental motion did not show any deviation from the bulk behavior. In contrast, for the films thinner than about 50 nm, the relaxation time distribution for the α_a-process became broader, probably due to a mobility gradient in the surface and interfacial regions. When we sandwiched an ultrathin PS film between SiO_x layers, another relaxation process, in addition to the original α_a-process, appeared at a higher temperature side that we assigned to the interfacial α_a-relaxation process. However, this was never seen for an ultrathin PS film between Au layers, implying that restriction from the substrate interface might be weak in this case.     

Low temperature thermal annealing-induced α-FeSi2 derived phase in an amorphous Si matrix

Thermal annealing-induced recrystallisation in Fe ion-implanted Si was investigated by transmission electron microscopy. Single crystals of Si(111) were implanted with 120 keV Fe ions to a fluence of 1.0×10¹⁷ cm^-2 at cryogenic temperature. A buried amorphous Fe-Si layer in an amorphous Si matrix was formed in the as-implanted sample. Nanobeam electron diffraction revealed that metastable α-FeSi₂ precipitates embedded in the amorphous Si matrix were formed after annealing at 350 °C for 8 h. The formation of this α-FeSi₂-derived phase was unusual, because it has been observed only in epitaxially grown thin films. Based on the Fe_1-xSi (0<x<0.5) phase with the CsCl structure, which is another metastable phase in the Fe-Si binary system, we discuss the formation process of the metastable α-FeSi₂ in the amorphous matrix. PACS 61.43.Dq; 61.14.Lj; 61.80.Jh     

Phosphorescence and phase structure of benzophenone—organomontmorillonite nanocomposites

We have investigated the temperature dependences (in the 4.2–180 K range) of the phosphorescence spectra of benzophenone (BP) in the presence of nanodisperse particles of the clay mineral montmorillonite (MMT) modified by different surface-active substances: dioctadecyldimethylammonium (DODM) and octadecylbenzyldimethylammonium (OBDM) chlorides. The MMT-OBDM sample has a stronger affinity for the given organic medium (BP) in the composite compared to the MMT-DODM sample due to the presence of a benzyl radical in the composition of the first modifier molecule. It has been shown that in the investigated heterosystems BP is present in both the crystal phase and the amorphous phase, and the latter thereby is formed in the near-surface layers of nanoparticles in the form of a thin shell due to the disordering action of inorganic particles on their adjacent BP layers. An increase in the chemical affinity between the organic clay surface and the BP molecules promotes the relaxation processes in the amorphous films of BP and increases the decay rate of its phosphorescence. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 809–814, November–December, 2005.     

Dielectric relaxation and dc conductivity on the PVOH-CF3COONH4 polymer system

In the present paper, the ionic conductivity and the dielectric relaxation properties on the poly(vinyl alcohol)-CF₃COONH₄ polymer system have been investigated by means of impedance spectroscopy measurements over wide ranges of frequencies and temperatures. The electrolyte samples were prepared by solution casting technique. The temperature dependence of the sample’s conductivity was modeled by Arrhenius and Vogel-Tammann-Fulcher (VTF) equations. The highest conductivity of the electrolyte of 3.41×10^− 3 (Ωcm)^− 1 was obtained at 423 K. For these polymer system two relaxation processes are revealed in the frequency range and temperature interval of the measurements. One is the glass transition relaxation (α-relaxation) of the amorphous region at about 353 K and the other is the relaxation associated with the crystalline region at about 423 K. Dielectric relaxation has been studied using the complex electric modulus formalism. It has been observed that the conductivity relaxation in this polymer system is highly non-exponential. From the electric modulus formalism, it is concluded that the electrical relaxation mechanism is independent of temperature for the two relaxation processes, but is dependent on composition.     

Atomic and Magnetic Structure of the Interface in Multilayers

Temperature dependence of the magnetic properties of Fe/Ag vacuum evaporated multilayers was studied in a wide range of layer thickness. For Fe thickness larger than 1 nm continuous magnetic layers can be found, but its hyperfine field is significantly lower than that of pure α-Fe at elevated temperatures. It is attributed to a decrease of the Curie temperature due to Ag impurities in the Fe layer. Below 1 nm Fe thickness magnetic relaxation and the formation of a granular alloy with 35 T average hyperfine field was observed. Magnetoresistance results indicate the presence of Fe clusters in the Ag matrix, as well. This revised version was published online in August 2006 with corrections to the Cover Date.     

Relaxation dynamics of poly(vinylidene fluoride) studied by dynamical mechanical measurements and dielectric spectroscopy

The aim of this study is to analyze the mobility of polymer chains in semicrystalline poly(vinylidene fluoride) (PVDF). PVDF crystallizes from the melt in the α crystalline phase. The transformation from the α phase to the electroactive β phase can be induced by stretching at temperatures in the range between 80 and 140 °C. The spherulitic structure of the crystalline phase is deformed during stretching to form fibrils oriented in the direction of the strain. The amorphous phase confined among the crystalline lamellae is distorted as well and some degree of orientation of the polymer chains is expected. Dynamic-mechanical and dielectric spectroscopy measurements were performed in PVDF films stretched to strain ratios up to 5 at temperatures between 80 and 140 °C. Dynamic-mechanical measurements were conducted between -60 °C and melting and in this temperature range the relaxation spectra show the main relaxation of the amorphous phase (called β-relaxation) and at higher temperatures a relaxation related to crystallites motions (α (c)-relaxation). Although the mean relaxation times of the β-relaxation are nearly equal in PVDF before and after crystal phase transformation, a significant change of shape of the relaxation spectrum proves the effect of chain distortion due to crystal reorganization. In stretched PVDF the elastic modulus of the polymer in the direction of deformation is significantly higher than in the transversal one, as expected by chain and crystals fibril orientation. The recovery of the deformation when the sample is heated is related with the appearance of the α (c)-relaxation. Dielectric spectroscopy spectrum shows the main relaxation of the amorphous phase and a secondary process (γ-relaxation) at lower temperatures. Stretching produces significant changes in the relaxation processes, mainly in the strength and shape of the main relaxation β. The Havriliak-Negami function has been applied to analyze the dielectric response.     

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.     

Plastic flow and fracture of amorphous intercrystalline layers in ceramic nanocomposites

A theoretical model has been proposed for describing the plastic flow and fracture of amorphous intercrystalline layers in ceramic nanocomposites. The mechanism of plastic deformation has been considered as homogeneous nucleation and growth of liquidlike phase inclusions subjected to plastic shear. It has been demonstrated using a nanoceramic material consisting of TiN nanocrystallites and Si₃N₄ amorphous layers as an example that, when the length of the amorphous layer is reached and a considerable dislocation charge is accumulated, these inclusions induce the formation and growth of Mode I–II cracks in neighboring amorphous layers. In this case, the possibility of opening and growing the crack depends very strongly on the test temperature, the layer orientation, and the size of nanoceramic grains. An increase in the temperature and the angle of orientation and a decrease in the size of nanoceramic grains favor an increase in the crack resistance.     

Relaxation processes in the incommensurate phase of a crystal with defects

The nature of the relaxation of the incommensurate superstructure of a ferroelectric to the equilibrium state is investigated experimentally. It is shown that near a phase transition the temperature dependence of the relaxation time of the incommensurate phase of the defective crystal is exponential. This law agrees qualitatively with the notion of domain wall motion in an inhomogeneous medium containing “random local phase-transition temperature” type defects. Fiz. Tverd. Tela (St. Petersburg) 41, 513–515 (March 1999)     

Direct-energy processes and phase transitions in silicon

Summary The phase transition of amorphous to single-crystal silicon has been investigated not only by conventional heating in a furnace but under direct-energy processes like pulsed-laser and ion beam irradiation. The first method allows the experimental determination of the free-energy-temperature diagram for amorphous, liquid and crystalline silicon. Due to the very fast heating and cooling the amorphous-to-liquid transition can be investigated in both directions. Ion beam irradiation induces either a layer-by-layer amorphization or crystallization by the movement of the initial α-Si/c-Si interface according to the substrate temperature. The two processes are governed by different types of defects created by the beam in the amorphous and in the crystalline side of the interface. The existence of a native-oxide layer at the interface between single crystal and deposited layer retards the ion beam crystallization until oxygen atoms are dispersed by beam mixing in the matrix. A recent alternative way of crystallizing deposited layers is by short high-temperature anneals obtained by incoherent-light irradiations. In this case the rupture of the native-oxide layer is achieved by the agglomeration of oxide into beads, thus allowing the realignment. This technique appears to be particularly promising for several technological applications. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

Internal friction in glassy semiconductors of the Ge-As-Se system

Relaxation processes in glasses of the Ge-As-Se system have been investigated by the internal friction technique. The process that can be classified as the β relaxation process has been revealed in the temperature range 180–280 K. The assumption has been made that a change in the magnitude of the internal friction maximum in the above temperature range with a change in the chemical composition is associated with the change in the concentration of structural units responsible for the β relaxation in these materials. It has been established that the activation energy for the α relaxation process in the glasses of the Ge-As-Se system under investigation increases considerably in the range of the average coordination number Z = 2.6.     

Nonlinear dielectric response of antiferroelectric liquid crystals in the smectic Cα * phase

Nonlinear dielectric response of antiferroelectric liquid crystals has been studied in the smectic C_α* (SmC_α*) phase. The linear dielectric spectrum shows a single relaxation of Debye type and its relaxation frequency is as high as one hundred kHz. The profile of the third-order nonlinear dielectric spectrum varies in complex fashion with temperature. In the vicinity of the SmA-SmC_α* phase transition, experimentally obtained nonlinear spectra are well described by those calculated with phenomenological theory of Landau type. The soft mode of the SmC_α* phase shows critical slowing-down near the transition temperature. In the lower-temperature region of the SmC_α* phase, the contribution from the soft mode of the SmC_α* phase reduces and the other relaxation mode with Debye-type spectrum appears at several hundred Hz in the nonlinear spectrum. The appearance of this low-frequency mode suggests that the cooperative fluctuation of directors over long range exists in the SmC_α* phase. Received 19 April 2002 and Received in final form 23 July 2002 RID="a" ID="a"e-mail: kimura@exp.t.u-tokyo.ac.jp     

Features of FMR spectra observed in granular films formed by Fe+ implantation into PMMA

Magnetic phase consisting of α-Fe particles arranged in a thin near-surface layer has been synthesized in modified phosphorus-containing polymethylmethacrylate by Fe⁺ implantation at an energy of 40 keV with a dose of 1.2⊙10¹⁷ ion/cm². The spectrum of magnetic resonance of the obtained samples is a superposition of a wide anisotropic absorption line and a set of reproducible lowintensity noiselike signals registered in a wide range of magnetic field. It has been established that a wide absorption line is due to particle conglomerates (larger than 200 nm), each behaving as a thin ferromagnetic film. Noiselike lines can be explained as resonance signals from separate oblate/prolate nanoparticles (50–200 nm in size) randomly oriented with respect to the irradiated surface. Such complicated nanostructures can be formed at an appropriate combination of properties of a polymer matrix, types of bombarded ions and implantation regimes.     

Experimental study of the amorphous phases of group-IV semiconductors by the119mSn Mössbauer probe

The amorphous phases of silicon, germanium, and -tin have been studied by Mössbauer emission spectroscopy on ion-implanted, radioactive^119mSn. Amorphous samples have been produced by ion implantations of various elements and by vacuumevaporation techniques. The same well-defined type of complex spectrum is observed for all investigated amorphous samples. These spectra are characterized by an increase in average isomer shift of (0.15±0.03) mm/s, a line broadening of 20±2%, and the same Debye temperature as compared with spectra of substitutional Sn in the respective crystalline host lattices. The spectra are proposed to originate from Sn atoms incorporated substitutionally in the amorphous host with distorted local surroundings. The recrystallization of the amorphous phase upon thermal and laser annealing has been monitored. After appropriate annealing, spectra characteristic of crystalline materials are observed for most samples. An exception are high-dose, inert-gas implanted samples where different complex defects seem to be formed in the annealing process.