Damage processes in Fe 3 O 4 magnetic insulator irradiated by swift heavy ions. Experimental results and modelisation

The behavior of the magnetic properties of magnetite Fe₃O₄ irradiated by swift heavy ions is investigated by magnetization measurements. Although there is no induced structural phase transformation, both coercive field and saturation magnetization are sensitive to ion irradiation and exhibit different behaviors depending on the ion fluence range. In the low fluence regime, the coercive field increases, which is evidence for a strong pinning of magnetic domain boundaries by the induced defects. The magnetization shows a decrease in the saturation value and tends to reorient perpendicularly to the ion track axis. At high fluence, the initial magnetic properties of the sample are nearly restored. The changes in the magnitude and the direction of magnetization are interpreted by magnetostrictive effects related to the stress induced by irradiation. A phenomenological model is applied to reproduce the fluence evolution of the saturation magnetization, assuming relaxation of the stress induced around the core of defects of the tracks by overlapping effects at high fluence. The results are compared to those obtained in the case of yttrium iron garnet Y₃Fe₅O₁₂. Received 18 April 2001 and Received in final form 24 July 2001     

Factory-roof-shaped phase front at the paraelectric-ferroelectric transition in KD PO : an incoherent interface

The phase front during the 218 K transition in KD₂PO₄ crystals under a thermal gradient perpendicular to the c ferroelectric axis is observed to have a factory-roof shape. This shape is studied versus the magnitude of G_e in samples cut with faces in (100), (010), (001) planes or in ( 0), (110), (001) ones. A geometric approach as well as the calculation of the elastic-strain energy caused by lattice misfits along the phase front demonstrate the incoherent interface nature of the phase front. Furthemore, the results and their interpretation allow to predict the sign of the lattice deformation u _xx ( > 0). Received 25 April 2002 Published online 29 November 2002     

Thermophysical properties of fluorinated acrylate homopolymers: Mixing and phase separation

The thermophysical properties of fluorinated acrylate homopolymers are investigated by differential scanning calorimetry (DSC) and optical microscopy and discussed in terms of relative lengths of the fluorinated chain and the hydrocarbon spacer between the acrylate moiety and the fluorinated chain. These compounds exhibit an intrinsic microphase-separation (Isotropic+Isotropic morphology) occurring between the fluorinated chains and the acrylate polymer backbone. It is shown that the enthalpy of mixing is a function of the length of the lateral fluorocarbon chains. The thermophysical behaviour of these materials may be regarded as demixed systems exhibiting an Upper Critical Solution Temperature. The photopolymerization process of one of the monomer is studied by isothermal photocalorimetry. High acrylate double-bond conversion and fast curing rates were obtained thus demonstrating the promising use of these materials for coating and film processing applications using UV-curing techniques. Received 30 January 2002     

Adsorption of a random heteropolymer with random self-interactions onto an interface

We consider the adsorption of a random heteropolymer onto an interface within the model of Garel et al. [#!gareletal89!#] by taking into account random self-interactions and ternary repulsive interactions between the monomers. Within the replica trick and by using a self-consistent preaveraging procedure we map the adsorption problem onto the problem of binding state of a quantum mechanical Hamiltonian. The analysis of the latter is treated within the variational method based on the 2nd Legendre transform. Our study reveals a complex behaviour of the localization of the heteropolymer. In particular, we predict a reentrant localization transition for moderate values of the asymmetry of the distribution function of the monomer sequences along the heteropolymer. Received 9 October 2001 and Received in final form 27 February 2002 Published online 6 June 2002     

The mechanisms of recrystallization after melting in syndiotactic polypropylene and isotactic polystyrene

Several semicrystalline polymers show a recrystallization after melting during a heating scan. We have studied the mechanisms of such recrystallization processes for two different polymers, namely syndiotactic polypropylene (sPP) and isotactic polystyrene (iPS). This was done by monitoring the structure evolution during the recrystallization process and its changes during a subsequent heating scan via time- and temperature-dependent SAXS measurements, respectively. The results of this study showed that the sPP samples exhibited a recrystallization mechanism similar to the multi-stage route found upon initial crystallization of semicrystalline polymers from an entangled melt. Meanwhile, a different recrystallization mechanism was shown by the iPS samples. In this case, the recrystallization process proceeded as a direct growth into the melt in a one-step process. This is the first time we have observed such a mechanism which resembles the picture presented by the classical models for crystallization from an entangled polymer melt. The reason for such different mechanisms may be related to the initial melt state prior to crystallization. It seems as though, when crystallization sets in an entangled polymer melt, it follows the multi-stage route, whereas if the melt is locally disentangled, it proceeds by a direct growth mechanism. Received 23 July 2001 and Received in final form 4 October 2001     

From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: A major route followed in polymer crystallization?

Based on broad and detailed evidence from a large variety of experiments on several polymer systems carried out by other authors and ourselves, a novel concept for understanding the crystallization of polymers from the melt is developed. The experiments generally indicate that the formation and growth of the lamellar crystallites is a multi-step process passing over intermediate states. We suggest a specific route which is compatible with the observations. It is proposed that the initial step is always the creation of a mesomorphic layer which spontaneously thickens, up to a critical value, where it solidifies through a cooperative structural transition. The transition produces a granular crystalline layer, which transforms in the last step into homogeneous lamellar crystallites. The model leads to predictions about the temperature dependencies of the crystal thickness and the growth rate which are at variance with conventional views but in agreement with findings in recent experiments. Received 17 February 2000 and Received in final form 30 March 2000     

Effect of physical ageing in thin glassy polymer films

We have studied the effect of physical ageing in thin supported glassy polystyrene films by using ellipsometry to detect overshooting in the expansivity-temperature curve upon heating of aged samples. Films with thickness 10-200 nm have been aged at 70^° C and 80^° C (below the bulk glass transition temperature). We observe clear relaxation peaks in the expansivity-temperature curve for films thicker than 18 nm but not for the 10 nm film. The intensity of the relaxation peak is inversely proportional to the film thickness, while the temperatures characteristic to the relaxation peak are almost independent of the film thickness. These observations are successfully interpreted by the idea that the surface layer of the order of 10 nm has liquid-like thermal properties. Received 28 October 2002 / Published online: 1 April 2003 RID="a" ID="a"Present address: Yokohama Research Center, Mitsubishi Chemical Corporation, 1000 Kamoshida-chou, Aoba-ku, Yokohama 227-8502, Japan; e-mail: kawana@rc.m-kagaku.co.jp     

Structural stability and structural imitation of (M = Mn,Mo, Nb,Ti, V,Al, Cr,Ni and Si)

The structural stability of La₂Co_17-xM_x (M = Mn, Mo, Nb, Ti, V, Al, Cr, Ni and Si) based on the interatomic potential has been studied. The calculated site preference of the third element M is found to be the 6c site, which is in agreement with the experiments. In the calculations, if the crystal cohesive energy of La₂Co₁₆Mn is taken as the highest one in the crystallization of La₂Co_17-xM_x, the lowest content x of the third element M (M = Mn, Mo, Nb, Ti and V) required to stabilize La₂Co_17-xM_x, is near that found in the experiments. The differences of the cell parameters between the calculated and the experimental values are less than 0.4%. The differences of the atomic parameters for Co (or M) between the calculated and the experimental values are about or even smaller than 1%, and that of La is about 3%. Because the energies of La(Co_1-xAl_x)₁₃ are lower than those of La₂(Co_1-xAl_x)₁₇, La₂(Co_1-xAl_x)₁₇ could not be formed in the experiments. In the calculations, with either a range of deformation of the structure or the reconstruction of the initial structure La₂Co₁₇ from LaCo₅, the same results including the cohesive energy curves and the crystallographic parameters can be retrieved after the action of the interatomic potentials. Received 1st November 2002 / Received in final form 17 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: hchang@aphy.iphy.ac.cn     

Radiation defects in nano-structured materials

We investigated defect formation within nanostructured materials using a transmission electron microscope (TEM) and ion accelerators. Controlling diffusion coefficient of the defects we have first observed changes in pattern of defect clusters, namely, the diffusion-limited reaction of defects in nanocrystals. Received 30 November 2000     

Some relevant parameters affecting the glass transition of supported ultra-thin polymer films

We have measured, the thickness dependence of the glass transition temperature T(g)( h), using ellipsometry at variable temperature, for poly(methyl-methacrylate) (PMMA) of various tacticity in confined geometry. We report that several factors significantly affect T(g)( h): i) polymer microstructure (stereoregularity of PMMA) related to local dynamics; ii) interfacial interactions; iii) conformation of the polymer chains. These results raise many fundamental questions on the origin of the thickness-dependent glass transition. Why and how do the interactions with the substrate significantly affect T(g)( h)? Does T(g)( h) depend on the modifications of conformational parameters of the chains (their entropy)? What is the correlation between local dynamics and T(g)( h) in thin films? The aim of this paper is to summarise these open questions, which should stimulate further investigations in the thin polymer film scientific community.     

Pressure amorphization through displacive disorder

After classifying amorphous materials according to their topology, we review a recently proposed theory of pressure amorphization (PA) that arises from some degree of displacive disorder while retaining a crystalline topology. That theory is based on the notion that one or more branches of the phonon spectrum become soft and flat with increasing pressure and is illustrated by a simple model that possesses the range of features displayed by many of the materials which undergo PA with displacive disorder. We report the results of Langevin simulations of the simple model which show how the probability of amorphization increases with the number of unit cells in the system and support our theory. We comment on how to generalize the model for the study of real systems. Received 29 march 2002     

Nematic order-disorder state transition in a liquid crystal analogue formed by oriented and migrating amoeboid cells

In cell culture, liquid crystal analogues are formed by elongated, migrating, and interacting amoeboid cells. An apolar nematic liquid crystal analogue is formed by different cell types like human melanocytes (=pigment cells of the skin), human fibroblasts (=connective tissue cells), human osteoblasts (=bone cells), human adipocytes (=fat cells), etc. The nematic analogue is quite well described by i) a stochastic machine equation responsible for cell orientation and ii) a self-organized extracellular guiding signal, E₂, which is proportional to the orientational order parameter as well as to the cell density. The investigations were mainly made with melanocytes. The transition to an isotropic state analogue can be accomplished either by changing the strength of interaction (e.g. variation of the cell density) or by influencing the cellular machinery by an externally applied signal: i) An isotropic gaseous state analogue is observed at low cell density (melanocytes/mm^2) and a nematic liquid crystal state analogue at higher cell density. ii) The nematic state analogue disappears if the bipolar shaped melanocytes are forced to become a star-like shape (induced by colchicine or staurosporine). The analogy between nematic liquid crystal state analogue formed by elongated, migrating and interacting cells and the nematic liquid crystal phase formed by interacting elongated molecules is discussed. Received 2 August 1999 and Received in final form 5 January 2000     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Stabilisation of fcc cobalt layers by 0.4 nm thick manganese layers in Co/Mn superlattices

Epitaxial Co/Mn multilayers (0.75 to 6 nm Co, 0.4 nm Mn layer thickness) have been grown on mica substrates covered by a (0002) Ru buffer layer. The structural properties of these layers have been studied using X-ray diffraction, nuclear magnetic resonance (NMR), and high resolution transmission electron microscopy (HRTEM). The Co layers, grown as face centred cubic (fcc), were found to be stabilised by the very thin Mn layers. Data obtained using X-ray diffraction and NMR were analysed and found to be in good agreement, while Monte-Carlo simulations were used to interpret the data and calculate the expected diffracted intensity and NMR spectra. The HRTEM data show that the Mn layers give rise to a large strain contrast extending, in the growth direction, over a distance which exceeds the thickness of the Mn layers. The superlattices could be described as having an fcc structure containing randomly located stacking faults with varying densities. The results verify the presence of a dominant, almost perfect phase of fcc stacking, and of a faulted hcp phase, while the number of defects increases with the Co layer thickness. Received 27 October 1999 and Received in final form 29 May 2000     

Interplay of charge exchange and projectile excitation in the stopping of swift heavy ions

The electronic energy loss of a dressed ion penetrating through matter is commonly considered as being synonymous with the sum of the excitation energies of the target and the projectile in atomic collisions undergone during the passage. We show that this is not justified in projectile-ionizing collisions and discuss some consequences. Received 23 October 2002 / Received in final form 1st December 2002 Published online 18 February 2003     

Are changes in morphology clear indicators for the glass transition in thin polymer films? Tentative ideas

I present some tentative ideas on the possibility of plastic deformation which might be relevant in ultra-thin polymer films at temperatures close but below the glass transition temperature. Several possible sources for sufficiently strong forces are discussed. The relevance of such forces in experiments aiming at determining thin-film properties like the glass transition temperature, thermal expansion or surface morphology is discussed. Received 19 September 2001 and Received in final form 5 December 2001     

Observation of a re-entrant kinetic glass transition in a micellar system with temperature-dependent attractive interaction

We detect in a tri-block co-polymer micellar system an ergodic-to-nonergodic-to-ergodic transition, as a function of temperature, in a range of concentrations, by photon correlation measurements. The shear viscosity is also shown to jump two order of magnitude at these transition temperatures. Surprisingly, the structure factor as measured by small angle neutron scattering shows a marked narrowing at the structural arrest state. Rationalization of these results with the existence of an attractive branch in the phase diagram of an attractive colloid system predicted by mode coupling theory is made. Received 9 Aprile 2002     

Simple Landau model of the smectic- A-isotropic phase transition

A simple Landau-type free energy function is presented to describe the smectic-A-isotropic phase transition. Varying the coupling between orientational and positional order parameters, a smectic-A-isotropic or a nematic-isotropic phase transition occurs. Within this model the smectic-A-isotropic phase transition is found to be always more strongly first order than the nematic-isotropic phase transition. The theoretical results are found to be in good agreement with all published experimental results. Received 27 June 2000     

Specific heats of the charge density wave compounds o-TaS and (TaSe ) I

Specific heats of the charge-density-wave compounds o-TaS₃ and (TaSe₄)₂I have been measured over the wide temperature interval 10 K-300 K. Both systems exhibit strong non-Debye behavior. Very weak and broad anomalies are observed at the Peierls transition temperatures. For o-TaS₃, the change in the curvature of the specific heat occurs at temperature of 40 K where glass transition has been deduced from dielectric measurements, and an extended scaling analysis suggests that the glass transition is associated with a dynamical cross over in length scales. We briefly discuss the characteristics and physical origins of the anomalies at both the Peierls and glass transitions. Received 5 April 2002 / Received in final form 28 June 2002 Published online 17 September 2002