Johari-Goldstein Secondary Relaxation Research Articles

Mutual Information in Molecular and Macromolecular Systems.

The relaxation properties of viscous liquids close to their glass transition (GT) have been widely characterised by the statistical tool of time correlation functions. However, the strong influence of ubiquitous non-linearities calls for new, alternative tools of analysis. In this respect, information theory-based observables and, more specifically, mutual information (MI) are gaining increasing interest. Here, we report on novel, deeper insight provided by MI-based analysis of molecular dynamics simulations of molecular and macromolecular glass-formers on two distinct aspects of transport and relaxation close to GT, namely dynamical heterogeneity (DH) and secondary Johari–Goldstein (JG) relaxation processes. In a model molecular liquid with significant DH, MI reveals two populations of particles organised in clusters having either filamentous or compact globular structures that exhibit different mobility and relaxation properties. In a model polymer melt, MI provides clearer evidence of JG secondary relaxation and sharper insight into its DH. It is found that both DH and MI between the orientation and the displacement of the bonds reach (local) maxima at the time scales of the primary and JG secondary relaxation. This suggests that, in (macro)molecular systems, the mechanistic explanation of both DH and relaxation must involve rotation/translation coupling.

Achieving pronounced β-relaxations and improved plasticity in CuZr metallic glass

Johari-Goldstein secondary relaxation known as β-relaxation has long been considered to play a key role in mechanical behaviors of metallic glasses (MGs). CuZr alloys are typical MG system exhibits non-pronounced β-relaxation and poor ductility. In the present work, we showed that pronounced β-relaxation that only observed in few La- and Y-based MG systems could be achieved in Cu50Zr50 MG and effectively improve the plasticity of the CuZr alloys. Other than the well-documented strain-like motions, the simulation results and analysis indicated, higher degree heterogeneity generated in severe deformed region is responsible to the unusual pronounced β-relaxation. The outcomes of current work not only deepen understanding of the microstructural origin of β-relaxation, also path a new way to alter the β-relaxation and plastic deformation behaviors of MGs.

The α and Johari–Goldstein Relaxations in 1,4-Polybutadiene: Breakdown of Isochronal Superpositioning

Dielectric spectra were measured for 1,4-polybutadiene (PBD) at various temperatures and pressures corresponding to a constant value of the relaxation time, τα, for the local segmental dynamics (α-process). Given the relationship of the Johari–Goldstein secondary relaxation to the α-process, it is of interest to determine whether the frequency separation of the Johari–Goldstein secondary relaxation and the α relaxation remains essentially constant under isochronal conditions. We find for PBD this is not the case; the JG relaxation peak moves systematically to higher frequencies at constant τα with increasing temperature and pressure. We show using molecular dynamics simulations that the behavior of PBD, which differs from that reported previously for molecular liquids, is a consequence of the torsional inflexibility of the polymer backbone. This accentuates the effect of constraints from local intermolecular barriers, with consequent deviation in the response of the JG and α relaxations due to their diffe...

Dynamics of supercooled liquid and plastic crystalline ethanol: Dielectric relaxation and AC nanocalorimetry distinguish structural α- and Debye relaxation processes.

Physical vapor deposition has been used to prepare glasses of ethanol. Upon heating, the glasses transformed into the supercooled liquid phase and then crystallized into the plastic crystal phase. The dynamic glass transition of the supercooled liquid is successfully measured by AC nanocalorimetry, and preliminary results for the plastic crystal are obtained. The frequency dependences of these dynamic glass transitions observed by AC nanocalorimetry are in disagreement with conclusions from previously published dielectric spectra of ethanol. Existing dielectric loss spectra have been carefully re-evaluated considering a Debye peak, which is a typical feature in the dielectric loss spectra of monohydroxy alcohols. The re-evaluated dielectric fits reveal a prominent dielectric Debye peak, a smaller and asymmetrically broadened peak, which is identified as the signature of the structural α-relaxation and a Johari-Goldstein secondary relaxation process. This new assignment of the dielectric processes is supported by the observation that the AC nanocalorimetry dynamic glass transition temperature, Tα, coincides with the dielectric structural α-relaxation process rather than the Debye process. The combined results from dielectric spectroscopy and AC nanocalorimetry on the plastic crystal of ethanol suggest the occurrence of a Debye process also in the plastic crystal phase.

Changes in dynamics of the glass-forming pharmaceutical nifedipine in binary mixtures with octaacetylmaltose

Some molecular glass-formers can crystallize in the glassy state, some of which are van der Waals molecules and some are pharmaceuticals. The molecular mechanism responsible for this glass-to-crystal mode of crystallization is of interest to the glass transition research community as well as to the pharmaceutical industry because the effect is detrimental to stability of amorphous form of the drugs stored below the glass transition temperature. Two prominent models have been proposed for the molecular mechanism. In the homogeneous nucleation-based crystallization model, the molecular mechanism is the secondary relaxation, and the other model assumes that the molecular process responsible for crystal growth in the glassy state is from the local molecular motions. Crystal growth requires motion of the entire molecule, and in the glassy state the only such local molecular motion is engendered by the secondary relaxation of the Johari–Goldstein (JG) kind. While the JG secondary relaxation is the crux in the two models of glass-to-crystal growth, it has not been found in the glassy state of the pharmaceuticals studied so far. The examples include 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY), indomethacin (IMC) and nifedipine (NIF). In the absence of any evidence of the JG secondary relaxation, the conundrum is that the two models of glass-to-crystal growth cannot be validated. It turns out these pharmaceuticals all have structural α-relaxations with narrow frequency dispersion. Empirically, glass-formers with narrow α-dispersion have JG secondary relaxation with weak relaxation strength, not well separated from the α-relaxation, and hence cannot be resolved. Theoretically, the narrow width of the α-dispersion is due to weak intermolecular coupling. In this article we enhance the intermolecular coupling of NIF by mixing with octaacetylmaltose to enhance the intermolecular coupling of NIF. In this way we have successfully resolved the JG secondary relaxation in the dielectric loss spectra of the NIF component in the glassy state, and validated the two models of glass-to-crystal growth.

Density Scaling of the Structural and Johari–Goldstein Secondary Relaxations in Poly(methyl methacrylate)

Dielectric spectra were obtained on a low molecular weight poly(methyl methacrylate) (PMMA) over a range of temperatures (331 < T (K) < 386) at pressures approaching 0.8 GPa. The α relaxation times, τα, superpose when plotted versus T/ργ, where ρ is density and γ a material constant, in accord with results for many other van der Waals liquids and polymers. However, the Johari–Goldstein (JG) relaxation times, τJG, do not conform to this density scaling for the same value of the exponent γ. Likewise, the frequency separation of the α and JG loss peaks in the spectrum increases with pressure for constant τα; that is, state points having the same α relaxation time and same peak breadth have different τJG. Similar results were obtained on a lower molecular weight PMMA, for which there was less overlap of the two peaks. The implication is that density scaling of the segmental relaxation times originates in the glass transition dynamics, not, as recently suggested, in higher frequency secondary processes.

Relationship between structural and secondary relaxation in glass formers: Ratio between glass transition temperature and activation energy

The relationship between structural and secondary dynamics is one of the most recently considered and possibly important issues of the dynamics in glass formers. One relation of interest is the ratio between the activation energy of the secondary relaxation and RT g, where T g is the glass transition temperature, and R is the gas constant. This relationship has been recently rationalized by the Coupling Model in terms of many-body dynamics and was applied to the intermolecular Johari-Goldstein secondary relaxation. This article investigates the pressure dependence of this ratio and attempts to verify the validity of the Coupling Model predictions under such conditions.

Critical Issues of Current Research on the Dynamics Leading to Glass Transition

Glass transition is still an unsolved problem in condensed matter physics and chemistry. In this paper, we critically reexamine experimental data and theoretical interpretations of dynamic properties of various processes seen over a wide time range from picoseconds to laboratory time scales. In order of increasing time, the ubiquitous processes considered include (i) the dynamics of caged molecular units with motion confined within the anharmonic intermolecular potential and where no genuine relaxation has yet taken place; (ii) the onset of the Johari-Goldstein secondary relaxation involving rotation or translation of the entire molecular unit and causing the decay of the cages, to be followed by the cooperative and dynamically heterogeneous motions participated by increasing number of molecules or length scale; and (iii) the terminal primary alpha-relaxation with the maximum cooperative length-scale allowed by the intermolecular interaction and constraints of the glass former. Some general and important properties found in each of these processes are shown to be interrelated, indicating that the processes are connected, with one being the precursor of the other following it. Thus, a theory of glass transition is neither complete nor fundamental unless all of these processes and their inter-relations have been accounted. In addition to published data, new experimental data are reported here to provide a limited collection of critical experimental facts having an impact on current issues of glass transition research and servingas a guide for the construction of a complete and successful theory in the future.

Effect of temperature and pressure on the structural (α-) and the true Johari–Goldstein (β-) relaxation in binary mixtures

We investigated the microscopic origin of the excess wing through isothermal and isobaric dielectric relaxation measurements for the Quinaldine/tristyrene mixture. Our results show that the excess wing, characteristic of the high frequency side of the structural loss peak in neat Quinaldine, becomes a well resolved Johari–Goldstein secondary relaxation on mixing with the apolar tristyrene. Analyzing the temperature and pressure behavior of the two processes, a clear correlation has been found between the structural relaxation time, the Johari–Goldstein relaxation time and the dispersion of the structural relaxation (i.e. its Kohlrausch parameter). These results support the idea that the Johari–Goldstein relaxation acts as a precursor of the structural relaxation and therefore of the glass transition phenomenon.

The Challenging Problem of Glass Transition

The glass transition phenomena are observed in many different classes of materials and have been studied in various disciplines. It is a long-standing problem due to the increasing number of important and general experimental facts that challenge conventional theories to explain. A collection of such experimental facts on the structural relaxation is given here, together with the observation that they are either governed by or correlated with the time/frequency dispersion of the structural relaxation. There is a class of secondary relaxations (named after Johari-Goldstein (JG)) that are well-connected to the structural relaxation in many ways. Thus, a fully successful theory of glass transition must take into consideration the roles played by the dispersion of the structural relaxation and the JG secondary relaxation. The results from our study of mixtures of van der Waals liquids are presented to illustrate these points, and a satisfactory explanation of the data is given. The understanding of the component dynamics gained from the study of these ideal systems is used to elucidate and interpret the experimental data of aqueous mixtures and hydrated proteins, which are more complicated systems. This exercise illustrates the benefit of broadening the study of one class of glass-forming materials to another class normally investigated by workers in another discipline.

The Johari−Goldstein β-Relaxation of Water

There is a plethora of experimental data on the dynamics of water in mixtures with glycerol, ethylene glycol, ethylene glycol oligomers, poly(ethylene glycol) 400 and 600, propanol, poly(vinyl pyrrolidone), poly(vinyl methylether), and other substances. In spite of the differences in the water contents, the chemical compositions, and the glass transition temperatures Tg of these aqueous mixtures, a faster relaxation originating from the water (called the nu-process) is omnipresent, sharing the following common properties. The relaxation time tau(nu) has Arrhenius temperature dependence at temperatures below Tg of the mixture. The activation energies of tau(nu) all fall within a neighborhood of 50 kJ/mol. At the same temperature where mixtures are all in their glassy states, the values of tau(nu) of several mixtures are comparable. The Arrhenius temperature dependence of tau(nu) does not continue to higher temperatures and instead it crosses over to a stronger temperature dependence at temperatures above Tg. The dielectric relaxation strength of the nu-process, Deltaepsilon(nu)(T), has a stronger temperature dependence above Tg than below, mimicking the change of enthalpy, entropy, and volume when crossing Tg. These general property of the nu-process (except for the magnitude of the activation energy) had been found before in the secondary relaxation of the faster component in several binary nonaqueous mixtures. Other properties of the secondary relaxation in these nonaqueous mixtures have helped to identify it as the Johari-Goldstein (JG) secondary relaxation of the faster component. The similarities in properties lead us to conclude that the nu-processes in water mixtures are the JG secondary relaxations of water. The conclusion is reinforced by the processes behaving similarly to the nu-process found in 6 A thick water layer (two molecular layers) in fully hydrated Na-vermiculite clay, and in water confined in molecular sieves, silica hydrogels, and poly(2-hydroxyethyl methacrylate) hydrogels.

Why the glass transition problem remains unsolved?

Glass-forming substances are made of units having nontrivial mutual interactions. Therefore, structural relaxation of glass-formers is a many-body relaxation problem, which unfortunately is still an unsolved problem in statistical mechanics. Conventional theories and models of glass transition bypass solution of this problem, and hence glass transition also remains an unsolved problem. There are plenty of experimental evidences for the many-body relaxation dynamics, and some examples are given. The Coupling Model of the author is not a full solution of the many-body relaxation problem either. Nevertheless, its predictions can explain the properties of structural relaxation originating from many-body relaxation and their relations to its precursor, namely the Johari–Goldstein secondary relaxation. A demonstration of the utility of the Coupling Model is given here by solving two problems in glass transition that involve many-body relaxation. The problems are: (1) the breakdown of Stokes–Einstein and Debye–Stokes–Einstein relations in neat molecular glass-formers and colloidal suspension, and (2) the component dynamics of polymer blends and mixtures of non-polymeric glass-formers.

The True Johari−Goldstein β-Relaxation of Monosaccharides

Broadband isothermal dielectric relaxation measurements of anhydrous fructose, glucose, galactose, sorbose, and ribose were made at ambient pressure in their liquidus and glassy states. We found a new secondary relaxation in fructose and glucose that is slower than those seen before by others. This new secondary relaxation also appears in the dielectric spectra of galactose, sorbose, and ribose, and hence it is a general feature of the relaxation dynamics of the monosaccharides. Dielectric measurements at elevated pressure of fructose and ribose show that the new secondary relaxation shifts to lower frequencies with applied pressures, mimicking the behavior of the alpha-relaxation. In contrast, the faster secondary relaxation remains stationary on applying pressure. These results together with other inferences indicate that the slower secondary relaxation bears relations to the alpha-relaxation, and hence, it is the true Johari-Goldstein secondary relaxation of the monosaccharides.

Anomalous Narrowing of the Structural Relaxation Dispersion of Tris(dimethylsiloxy)phenylsilane at Elevated Pressures

Broadband dielectric relaxation measurements of tris(dimethylsiloxy)phenylsilane were made at ambient pressure and at elevated pressures. The data show an anomalous behavior not previously seen in any other glass-formers; namely, the structural alpha-relaxation loss peak narrows with increasing pressure and temperature at constant peak frequency. Interpreted by the coupling model, the effect is due to reduction of intermolecular coupling at elevated pressures. This interpretation has support from the observed decrease of the separation between the alpha-relaxation and the Johari-Goldstein secondary relaxation, as well as the smaller steepness or "fragility" index m of the data obtained at 1.7 GPa than at ambient pressure.

Emergence of the genuine Johari–Goldstein secondary relaxation in m-fluoroaniline after suppression of hydrogen-bond-induced clusters by elevating temperature and pressure

The dielectric spectra of the glass former, m-fluoroaniline (m-FA), at ambient pressure show the presence of a secondary relaxation, which was identified in the literature as the universal Johari-Goldstein (JG) beta relaxation. However, published elastic neutron scattering and simulation data [D. Morineau, C. Alba-Simionesco, M. C. Bellisent-Funel, and M. F. Lauthie, Europhys. Lett. 43, 195 (1998); D. Morineau and C. Alba-Simionesco, J. Chem. Phys. 109, 8494 (1998)] showed the presence of hydrogen-bond-induced clusters of limited size in m-FA at ambient pressure and temperature of the dielectric measurements. The observed secondary relaxation may originate from the hydrogen-bond-induced clusters. If so, it should not be identified with the JG beta relaxation that involves essentially all parts of the molecule and has certain characteristics [K. L. Ngai and M. Paluch, J. Chem. Phys. 120, 857 (2004)], but then arises the question of where is the supposedly universal JG beta relaxation in m-FA. To gain a better understanding and resolving the problem, we perform dielectric measurements at elevated pressures and temperatures to suppress the hydrogen-bond-induced clusters and find significant changes in the dielectric spectra. The secondary relaxation observed at ambient pressure in m-FA is suppressed, indicating that indeed it originates from the hydrogen-bond-induced clusters. The spectra of m-FA are transformed at high temperature and pressure to become similar to that of toluene. The new secondary relaxation that emerges in the spectra has properties of a genuine JG relaxation like in toluene.

Johari-Goldstein secondary relaxation in methylated alkanes

Dielectric relaxation measurements of the methylated alkanes, 3-methylpentane, 3-methylheptane, 4-methylheptane, 2,3-dimethylpentane, and 2,4,6-trimethylheptane by S. Shahriari, A. Mandanici, L-M Wang, and R. Richert [J. Chem. Phys. 121, 8960 (2004)] have found a primary $\ensuremath{\alpha}$ relaxation of these glass-forming liquids and a slow secondary $\ensuremath{\beta}$ relaxation that are in close proximity to each other on the frequency scale. These glass formers have one or more methyl groups individually attached to various carbons on the alkane chain. They cannot contribute to such a slow secondary relaxation. Hence the observed secondary relaxations is not intramolecular in origin and, similar to secondary relaxations found in rigid molecules by Johari and Goldstein, they are potentially important in the consideration of a mechanism for the glass transition. These secondary relaxations in the methylated alkanes are special and belong to the class of Johari-Goldstein in a generalized sense. The coupling model has predicted that its primitive relaxation time should be approximately the same as the relaxation time of the secondary relaxation if the latter is of the Johari-Goldstein kind. This prediction has been shown to hold in many other glass formers. The published data of the methylated alkanes provide an opportunity to test this prediction once more. The results of this work confirm the prediction.

Primary and secondary relaxations in bis-5-hydroxypentylphthalate

Broadband dielectric spectroscopy was used to study the relaxation dynamics in bis-5-hydroxypentylphthalate (BHPP) under both isobaric and isothermal conditions. The relaxation dynamics exhibit complex behavior, arising from hydrogen bonding in the BHPP. At ambient pressure above the glass transition temperature T(g), the dielectric spectrum shows a broad structural relaxation peak with a prominent excess wing toward higher frequencies. As temperature is decreased below T(g), the excess wing transforms into two distinct peaks, both having Arrhenius behavior with activation energies equal to 58.8 and 32.6 kJmol for slower (beta) and faster (gamma) processes, respectively. Furthermore, the relaxation times for the beta process increase with increasing pressure, whereas the faster gamma relaxation is practically insensitive to pressure changes. Analysis of the properties of these secondary relaxations suggests that the beta peak can be identified as an intermolecular Johari-Goldstein (JG) process. However, its separation in frequency from the alpha relaxation, and both its activation energy and activation volume, differ substantially from values calculated from the breadth of the structural relaxation peak. Thus, the dynamics of BHPP appear to be an exception to the usual correlation between the respective properties of the structural and the JG secondary relaxations.