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A compact setup for in situ solvothermal vapor annealing of thin polymer films in the temperature range from room temperature to 70 °C is presented. The design is optimized to avoid solvent condensation in tubes and other components. The setup consists of a chamber, a gas delivery system, a commercial film-thickness measuring device, and a solvent vapor concentration sensor. The chamber is equipped with heaters and thermometers and is thermally insulated. It has windows to allow for penetration of xrays together with a sample table with a gas distributer to ensure homogeneous swelling of the polymer film. The computer-controlled gas delivery system has two different components, which can be used separately or in parallel (for mixed gas solvent annealing): (a) mass flow controllers and a bubbler system and (b) a commercial "controlled evaporation and mixing" system. The film-swelling ratio is determined in situ using optical reflectometry, and the solvent concentration in the exhaust gas is continuously monitored by UV-absorption. Test results are presented where the setup is used for swelling of ∼100 nm thick polystyrene and polyisoprene homopolymer films with toluene and acetone, respectively. [ABSTRACT FROM AUTHOR]

The frequency-dependent dielectric constant, shear and adiabatic bulk moduli, longitudinal thermal expansion coefficient, and longitudinal specific heat have been measured for two van der Waals glass-forming liquids, tetramethyl-tetraphenyl-trisiloxane (DC704) and 5-polyphenyl-4-ether. Within the experimental uncertainties the loss-peak frequencies of the measured response functions have identical temperature dependence over a range of temperatures, for which the Maxwell relaxation time varies more than nine orders of magnitude. The time scales are ordered from fastest to slowest as follows: Shear modulus, adiabatic bulk modulus, dielectric constant, longitudinal thermal expansion coefficient, and longitudinal specific heat. The ordering is discussed in light of the recent conjecture that van der Waals liquids are strongly correlating, i.e., approximate single-parameter liquids. [ABSTRACT FROM AUTHOR]

Shear-mechanical and dielectric measurements on the two monohydroxy (monoalcohol) molecular glass formers 2-ethyl-1-hexanol and 2-butanol close to the glass-transition temperature are presented. The shear-mechanical data are obtained using the piezoelectric shear-modulus gauge method covering frequencies from 1 mHz to 10 kHz. The shear-mechanical relaxation spectra show two processes, which follow the typical scenario of a structural (alpha) relaxation and an additional (Johari–Goldstein) beta relaxation. The dielectric relaxation spectra are dominated by a Debye-type peak with an additional non-Debye peak visible. This Debye-type relaxation is a common feature peculiar to monoalcohols. The time scale of the non-Debye dielectric relaxation process is shown to correspond to the mechanical structural (alpha) relaxation. Glass-transition temperatures and fragilities are reported based on the mechanical alpha relaxation and the dielectric Debye-type process, showing that the two glass-transition temperatures differ by approximately 10 K and that the fragility based on the Debye-type process is a factor of 2 smaller than the structural fragility. If a mechanical signature of the Debye-type relaxation exists in these liquids, its relaxation strength is at most 1% and 3% of the full relaxation strength of 2-butanol and 2-ethyl-1-hexanol, respectively. These findings support the notion that it is the non-Debye dielectric relaxation process that corresponds to the structural alpha relaxation in the liquid. [ABSTRACT FROM AUTHOR]

A series of three homologous ABC miktoarm star terpolymers having a polyisoprene (PI), a polystyrene (PS) and a poly(methyl methacrylate) (PMMA) arm, is synthesized by living anionic polymerization. While the volume fraction of the PI and the PS blocks are kept equal and constant, the volume fraction of the PMMA block is varied. The room temperature bulk structure is characterized using small-angle X-ray scattering and transmission electron microscopy, while the structure of thin films is investigated using scanning electron microscopy, atomic force microscopy and X-ray reflectometry. For both bulk and thin films, it is found that the sample with the lowest volume fraction of PMMA has a morphology distinctly different from the two samples with larger PMMA volume fraction. All data for both bulk and thin film samples are consistent with an alternating lamellar structure for the lowest PMMA volume fraction sample. The two higher PMMA volume fraction samples show standing rod structure, however the details of the packing in the PMMA matrix differ depending on sample thickness. Overall, a structure with PI domains screened from interacting with PMMA by a PS shell is seen for both samples. In bulk, core-shell cylinders pack hexagonally, while a 100 nm thin film of the sample with the largest volume fraction of PMMA shows a square-lattice packing. The structuring is driven by two factors: i) the strong segregation of the PI-PMMA arm pair together with the weak segregation of the two arm pairs with a PS block and ii) the geometrical constraints resulting from the star architecture. No wetting layers are observed for any of the thin film samples, neither at the air-polymner surface or at the polymer-substrate interface. [Display omitted] • New coupling scheme for synthesizing PI-PS-PMMA miktoarm star terpolymers. • Homologous series of PI-PS-PMMA miktoarm star terpolymers investigated. • Short PMMA arm: alternate lamellar structure, longer PMMA arm: core-shell cylinder structures. • Increasing PMMA arm length lead to transition to core-shell cylinders on a square lattice. • Core-shell cylinders vertically aligned to substrate with no wetting layers formed. [ABSTRACT FROM AUTHOR]

We present shear mechanical and dielectric measurements taken on seven liquids: triphenylethylene, tetramethyltetra-phenyltrisiloxane (Dow Corning 704® diffusion pump fluid), polyphenyl ether (Santovac® 5 vacuum pump fluid), perhydrosqualene, polybutadiene, decahydroisoquinoline (DHIQ), and tripropylene glycol. The shear mechanical and dielectric measurements are for each liquid performed under identical thermal conditions close to the glass transition temperature. The liquids span four orders of magnitude in dielectric relaxation strength and include liquids with and without Johari-Goldstein beta relaxation. The shear mechanical data are obtained by the piezoelectric shear modulus gauge method giving a large frequency span (10-3–104.5 Hz). This allows us to resolve the shear mechanical Johari-Goldstein beta peak in the equilibrium DHIQ liquid. We moreover report a signature (a pronounced rise in the shear mechanical loss at frequencies above the alpha relaxation) of a Johari-Goldstein beta relaxation in the shear mechanical spectra for all the liquids which show a beta relaxation in the dielectric spectrum. It is found that both the alpha and beta loss peaks are shifted to higher frequencies in the shear mechanical spectrum compared to the dielectric spectrum. It is in both the shear and dielectric responses found that liquids obeying time-temperature superposition also have a high-frequency power law with exponent close to -1/2. It is moreover seen that the less temperature dependent the spectral shape is, the closer it is to the universal -1/2 power-law behavior. The deviation from this universal power-law behavior and the temperature dependencies of the spectral shape are rationalized as coming from interactions between the alpha and beta relaxations. [ABSTRACT FROM AUTHOR]

The Gemant-DiMarzio-Bishop model, which connects the frequency-dependent shear modulus to the frequency-dependent dielectric constant, is reviewed and a new consistent macroscopic formulation is derived. It is moreover shown that this version of the model can be tested without fitting parameters. The reformulated version of the model is analyzed and experimentally tested. It is demonstrated that the model has several nontrivial qualitative predictions: the existence of an elastic contribution to the high-frequency limit of the dielectric constant, a shift of the shear modulus loss peak frequency to higher frequencies compared with the loss peak frequency of the dielectric constant, a broader alpha peak, and a more pronounced beta peak in the shear modulus when compared with the dielectric constant. It is shown that these predictions generally agree with experimental findings and it is therefore suggested that the Gemant-DiMarzio-Bishop model is correct on a qualitative level. The quantitative agreement between the model and the data is on the other hand moderate to poor. It is discussed if a model-free comparison between the dielectric and shear mechanical relaxations is relevant, and it is concluded that the shear modulus should be compared with the rotational dielectric modulus, 1/(ε(ω)-n2), which is extracted from the Gemant-DiMarzio-Bishop model, rather than to the dielectric susceptibility or the conventional dielectric modulus M=1/ε(ω). [ABSTRACT FROM AUTHOR]

A longstanding problem in facility based experiments is the time one must wait whilst changing sample temperature. This issue is most often confronted at cryogenic temperatures above 100 K, where thermal response times can be very slow. These can be drastically reduced by minimising the amount of material being controlled to as little as possible beyond the sample itself. Peltier elements provide an effective way to achieve this, but are mostly used to regulate with respect to room temperature. We report on the Huginn sub-cryostat, a cryostat insert with dual Peltier regulation, useable down to 100 K, that enables large and rapid temperature jumps of up of 10 K to 20 K in minutes or less. Moreover, temperature stability is improved by an order of magnitude in the presence of a variable background temperature. [ABSTRACT FROM AUTHOR]

We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This "Thermalization Calorimetry" technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat conduction through an insulating material, i.e., is proportional to the temperature difference between sample and surroundings. The monitored signal reflects the sample's specific heat and is sensitive to exo- and endothermic processes. The technique is useful for studying supercooled liquids and their crystallization, e.g., for locating the glass transition and melting point(s), as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition. [ABSTRACT FROM AUTHOR]

Abstract: In order to describe relaxation the thermodynamic coefficient can be generalized into a complex frequency-dependent cross response function. We explore theoretically the possibility of measuring for a supercooled liquid near the glass transition. This is done by placing a thermistor in the middle of the liquid which itself is contained in a spherical piezoelectric shell. The piezoelectric voltage response to a thermal power generated in the thermistor is found to be proportional to but factors pertaining to heat diffusion and adiabatic compressibility κ S (ω) do also intervene. We estimate a measurable piezoelectric voltage of 1mV to be generated at 1Hz for a heating power of 0.3mW. Together with κ S (ω) and the longitudinal specific heat c l (ω) which may also be found in the same setup a complete triple of thermoviscoelastic response functions may be determined when supplemented with shear modulus data. [ABSTRACT FROM AUTHOR]

Abstract: The phenomenology of the beta relaxation process in the shear-mechanical response of glass-forming liquids is summarized and compared to that of the dielectric beta process. Furthermore, we discuss how to model the observations by means of standard viscoelastic modeling elements. Necessary physical requirements to such a model are outlined, and it is argued that physically relevant models must be additive in the shear compliance of the alpha and beta parts. A model based on these considerations is proposed and fitted to data for Polyisobutylene 680. [ABSTRACT FROM AUTHOR]

Abstract: A novel synchrotron-based technique “high angular resolution 3DXRD” is presented in detail, and applied to the characterization of oxygen-free, high-conductivity copper at a tensile deformation of 2%. The position and shape in reciprocal space of 14 peaks originating from deeply embedded individual subgrains is reported. From this dataset the density of redundant dislocations in the individual subgrains is inferred to be below 12×1012 m−2 on average. It is found that the subgrains on average experience a reduction in strain of 0.9×10−4 with respect to the mean elastic strain of the full grain, a rather wide distribution of the strain difference between the subgrains (twice the standard deviation is 2.9×10−4), and a narrow internal strain distribution (upper limit is 2.4×10−4 full width at half maximum). [Copyright &y& Elsevier]

During plastic deformation of metals and alloys, dislocations arrange in ordered patterns. How and when these self-organization processes take place have remained elusive, because in situ observations have not been feasible. We present an x-ray diffraction method that provided data on the dynamics of individual, deeply embedded dislocation structures. During tensile deformation of pure copper, dislocation-free regions were identified. They showed an unexpected intermittent dynamics, for example, appearing and disappearing with proceeding deformation and even displaying transient splitting behavior. Insight into these processes is relevant for an understanding of the strength and work-hardening of deformed materials. [ABSTRACT FROM AUTHOR]

A correction to the article "Dielectric and shear mechanical alpha and beta relaxations in seven glass-forming liquids," that was published in the 2005 issue is presented.

The frequency dependent specific heat has been measured under pressure for the molecular glass forming liquid 5-polyphenyl-4-ether in the viscous regime close to the glass transition. The temperature and pressure dependences of the characteristic time scale associated with the specific heat is compared to the equivalent time scale from dielectric spectroscopy performed under identical conditions. It is shown that the ratio between the two time scales is independent of both temperature and pressure. This observation is non-trivial and demonstrates the existence of specially simple molecular liquids in which different physical relaxation processes are both as function of temperature and pressure/density governed by the same underlying "inner clock." Furthermore, the results are discussed in terms of the recent conjecture that van der Waals liquids, like the measured liquid, comply to the isomorph theory. [ABSTRACT FROM AUTHOR]

This paper presents dielectric relaxation data for organic glass-forming liquids compiled from different groups and supplemented by new measurements. The main quantity of interest is the “minimum slope” of the α dielectric loss plotted as a function of frequency in a log-log plot, i.e., the numerically largest slope above the loss peak frequency. The data consisting of 347 spectra for 53 liquids show prevalence of minimum slopes close to -1/2, corresponding to approximate t dependence of the dielectric relaxation function at short times. The paper studies possible correlations between minimum slopes and (1) temperature (quantified via the loss peak frequency); (2) how well an inverse power-law fits data above the loss peak; (3) degree of time-temperature superposition; (4) loss peak half width; (5) deviation from non-Arrhenius behavior; (6) loss strength. For the first three points we find correlations that show a special status of liquids with minimum slopes close to -1/2. For the last three points only fairly insignificant correlations are found, with the exception of large-loss liquids that have minimum slopes that are numerically significantly larger than 1/2. We conclude that—excluding large-loss liquids—approximate t relaxation appears to be a generic property of the α relaxation of organic glass formers. [ABSTRACT FROM AUTHOR]

The piezoelectric shear gauge (PSG) [Christensen and Olsen, Rev. Sci. Instrum. 66, 5019 (1995)] is a rheometric technique developed to measure the complex shear modulus of viscous liquids near their glass transition temperature. We report recent advances to the PSG technique: (1) The data extraction procedure is optimized, which extends the upper limit of the frequency range of the method to between 50 and 70 kHz. (2) The measuring cell is simplified to use only one piezoelectric ceramic disk instead of three. We present an implementation of this design intended for liquid samples. Data obtained with this design revealed that a soft extra spacer is necessary to allow for thermal contraction of the sample in the axial direction. Model calculations show that flow in the radial direction is hindered by the confined geometry of the cell when the liquid becomes viscous upon cooling. The method is especially well-suited for—but not limited to—glassy materials. [ABSTRACT FROM AUTHOR]

In this article, we report on the design, manufacture, and testing of a high-pressure cell for simultaneous dielectric and neutron spectroscopy. This cell is a unique tool for studying dynamics on different time scales, from kilo- to picoseconds, covering universal features such as the α relaxation and fast vibrations at the same time. The cell, constructed in cylindrical geometry, is made of a high-strength aluminum alloy and operates up to 500 MPa in a temperature range between roughly 2 and 320 K. In order to measure the scattered neutron intensity and the sample capacitance simultaneously, a cylindrical capacitor is positioned within the bore of the high-pressure container. The capacitor consists of two concentric electrodes separated by insulating spacers. The performance of this setup has been successfully verified by collecting simultaneous dielectric and neutron spectroscopy data on dipropylene glycol, using both backscattering and time-of-flight instruments. We have carried out the experiments at different combinations of temperature and pressure in both the supercooled liquid and glassy state. [ABSTRACT FROM AUTHOR]

Interest in the optically stimulated luminescence (OSL) dating of rock surfaces has increased significantly over the last few years, as the potential of the method has been explored. It has been realized that luminescence-depth profiles show qualitative evidence for multiple daylight exposure and burial events. To quantify both burial and exposure events a new mathematical model is developed by expanding the existing models of evolution of luminescence–depth profiles, to include repeated sequential events of burial and exposure to daylight. This new model is applied to an infrared stimulated luminescence-depth profile from a feldspar-rich granite cobble from an archaeological site near Aarhus, Denmark. This profile shows qualitative evidence for multiple daylight exposure and burial events; these are quantified using the model developed here. By determining the burial ages from the surface layer of the cobble and by fitting the new model to the luminescence profile, it is concluded that the cobble was well bleached before burial. This indicates that the OSL burial age is likely to be reliable. In addition, a recent known exposure event provides an approximate calibration for older daylight exposure events. This study confirms the suggestion that rock surfaces contain a record of exposure and burial history, and that these events can be quantified. The burial age of rock surfaces can thus be dated with confidence, based on a knowledge of their pre-burial light exposure; it may also be possible to determine the length of a fossil exposure, using a known natural light exposure as calibration. [ABSTRACT FROM AUTHOR]

Understanding the origin of the dramatic temperature and density dependence of the relaxation time of glass-forming liquids is a fundamental challenge in glass science. The recently established 'density-scaling' relation quantifies the relative importance of temperature and density for the relaxation time in terms of a material-dependent exponent. We show that this exponent for approximate single-parameter liquids can be calculated from thermoviscoelastic linear-response data at a single state point, for instance an ambient-pressure state point. This prediction is confirmed for the van der Waals liquid tetramethyl-tetraphenyl-trisiloxane. Consistent with this, a compilation of literature data for the Prigogine-Defay ratio shows that van der Waals liquids and polymers are approximate single-parameter systems, whereas associated and network-forming liquids are not. [ABSTRACT FROM AUTHOR]