Retraction of "Fe3O4 Nanoparticles Grown on Cellulose/GO Hydrogels as Advanced Catalytic Materials for the Heterogeneous Fenton-like Reaction".

[This retracts the article DOI: 10.1021/acsomega.9b00170.].

Predicting the Density-Scaling Exponent of a Glass-Forming Liquid from Complex Dielectric Permittivity Measurements.

One of the challenging problems related to the liquid-glass transition phenomenon is establishing a link between the character of intermolecular interactions and the behavior of molecular dynamics. Introducing the density scaling concept, according to which dynamic quantities, e.g., viscosity or structural relaxation time (τ_{α}) measured at different thermodynamic conditions are expressed as a single universal curve if plotted against ρ^{γ}/T, led to significant progress in solving this problem since the scaling exponent γ defines the steepness of the repulsive part of the intermolecular potential. Herein, we found that relaxation dynamics of van der Waals and H-bonding glass formers, for which the Kirkwood factor (g_{K}) is an isomorph-invariant quantity, satisfy an alternative scaling, logτ_{α} vs T(Δϵ_{s}T)^{-γ}. As a result, the exponent γ is determined from the temperature and pressure evolutions of τ_{α} and dielectric relaxation strength Δϵ-both obtained in a single dielectric experiment, which makes the γ coefficient to be accessed in the future for an extensive database of glass-forming liquids.

CuxCo1-xFe2O4 (x = 0.33, 0.67, 1) Spinel Ferrite Nanoparticles Based Thermoplastic Polyurethane Nanocomposites with Reduced Graphene Oxide for Highly Efficient Electromagnetic Interference Shielding.

CuxCo1-xFe2O4 (x = 0.33, 0.67, 1)-reduced graphene oxide (rGO)-thermoplastic polyurethane (TPU) nanocomposites exhibiting highly efficient electromagnetic interference (EMI) shielding were prepared by a melt-mixing approach using a microcompounder. Spinel ferrite Cu0.33Co0.67Fe2O4 (CuCoF1), Cu0.67Co0.33Fe2O4 (CuCoF2) and CuFe2O4 (CuF3) nanoparticles were synthesized using the sonochemical method. The CuCoF1 and CuCoF2 exhibited typical ferromagnetic features, whereas CuF3 displayed superparamagnetic characteristics. The maximum value of EMI total shielding effectiveness (SET) was noticed to be 42.9 dB, 46.2 dB, and 58.8 dB for CuCoF1-rGO-TPU, CuCoF2-rGO-TPU, and CuF3-rGO-TPU nanocomposites, respectively, at a thickness of 1 mm. The highly efficient EMI shielding performance was attributed to the good impedance matching, conductive, dielectric, and magnetic loss. The demonstrated nanocomposites are promising candidates for a lightweight, flexible, and highly efficient EMI shielding material.

High-Performance, Lightweight, and Flexible Thermoplastic Polyurethane Nanocomposites with Zn2+-Substituted CoFe2O4 Nanoparticles and Reduced Graphene Oxide as Shielding Materials against Electromagnetic Pollution.

The development of flexible, lightweight, and thin high-performance electromagnetic interference shielding materials is urgently needed for the protection of humans, the environment, and electronic devices against electromagnetic radiation. To achieve this, the spinel ferrite nanoparticles CoFe2O4 (CZ1), Co0.67Zn0.33Fe2O4 (CZ2), and Co0.33Zn0.67Fe2O4 (CZ3) were prepared by the sonochemical synthesis method. Further, these prepared spinel ferrite nanoparticles and reduced graphene oxide (rGO) were embedded in a thermoplastic polyurethane (TPU) matrix. The maximum electromagnetic interference (EMI) total shielding effectiveness (SET) values in the frequency range 8.2-12.4 GHz of these nanocomposites with a thickness of only 0.8 mm were 48.3, 61.8, and 67.8 dB for CZ1-rGO-TPU, CZ2-rGO-TPU, and CZ3-rGO-TPU, respectively. The high-performance electromagnetic interference shielding characteristics of the CZ3-rGO-TPU nanocomposite stem from dipole and interfacial polarization, conduction loss, multiple scattering, eddy current effect, natural resonance, high attenuation constant, and impedance matching. The optimized CZ3-rGO-TPU nanocomposite can be a potential candidate as a lightweight, flexible, thin, and high-performance electromagnetic interference shielding material.

Highly Tunable Piezoresistive Behavior of Carbon Nanotube-Containing Conductive Polymer Blend Composites Prepared from Two Polymers Exhibiting Crystallization-Induced Phase Separation.

Conductive polymer composites (CPCs) are suitable as piezoresistive-sensing materials. When using CPCs for strain sensing, it is still a big challenge to simultaneously improve the piezoresistive sensitivity and linearity along with the electrical conductivity and mechanical properties. Here, highly tunable piezoresistive behavior is reported for multiwalled carbon nanotube (CNT)-filled CPCs based on blends of two semicrystalline polymers poly(vinylidene fluoride) (PVDF) and poly(butylene succinate) (PBS), which are miscible in the melt. When cooling the homogeneous mixture of the blend components, successive crystallization of PVDF and PBS occurs, creating complex crystalline structures in a mixed amorphous phase. The morphology of the blend matrix, the crystallinity of the blend components, and the dispersion and location of the CNTs in the blend depend on the CNT content and the blend composition. Compared with PVDF/CNT composites, the substitution of 10 to 50 wt % PVDF by PBS in the composites shifts the electrical percolation concentration Φc from 0.79 wt % to filler contents as low as 0.50 wt % while improving the stretchability. The piezoresistive behavior is highly tunable by changing the PVDF/PBS ratio. The ternary composites with matrix compositions of PVDF (90 wt %)/PBS (10 wt %) and PVDF (50 wt %)/PBS (50 wt %) show either higher piezoresistive sensitivity or linearity, respectively, caused by the differences in the microstructure of the CPCs. For example, the crystallinity of PBS in the ternary composites increased from 19.8% to 52.0% as the PBS content increased from 10 wt % to 50 wt %, which is connected with altered CNT distribution and conductive network structure and substantial improvement of the linearity of the electrical response to strains up to >20%. Our findings highly contribute to the understanding of the piezoresistive properties of CPCs based on two semicrystalline polymers and are important for future studies to tune the piezoresistive behavior to achieve simultaneously improved sensitivity and linearity.

Tuning the Piezoresistive Behavior of Poly(Vinylidene Fluoride)/Carbon Nanotube Composites Using Poly(Methyl Methacrylate).

In conductive polymer composites (CPCs), which can be used as both strain sensors and materials with self-diagnosis capabilities for structural health monitoring, the piezoresistive sensitivity can be tuned by changing the electrical filler network structure, mainly influenced by the conductive filler content. Typically, the electrical resistance increases exponentially with strain, and the piezoresistive sensitivity and linearity cannot be improved simultaneously. In this work, we report a facile method to tune the piezoresistive behavior of melt-mixed poly(vinylidene fluoride) (PVDF)/carbon nanotube (CNT, 0.75-2.0 wt %) composites using blending with poly(methyl methacrylate) (PMMA, 5-30 wt %). PVDF and PMMA are completely miscible in the melt state regardless of the proportion. For PVDF-rich blends, the crystallization of PVDF induces separation of the PVDF crystal region from the miscible PVDF/PMMA amorphous blend part during the cooling process. Addition of PMMA tuned the piezoresistive strain behavior and improved the electrical conductivity and toughness at the same time. The PVDF/PMMA/CNT composites show higher sensitivity at low strains than their PVDF/CNT counterparts with comparable initial resistivity. For example, ΔR/R0 at 5% strain is 18.6% for the PVDF(80)/PMMA(20) blend containing 0.75 wt % CNT versus 11.0% for PVDF containing 1 wt % CNT, both having a volume resistivity of around 104 Ω·cm. The PVDF/PMMA/CNT blend composites also show a less steep exponential increase in the sensing response at higher strains, indicating better linearity. These differences are due to the altered microstructure of the composites and the more homogeneous distribution of CNTs between the smaller and less numerous PVDF crystallites when PMMA is added. The concept of modifying the composite microstructure by adding another commercially available miscible polymer offers a simple and effective way to tune the piezoresistive behavior and improve mechanical properties of CPC sensor materials.

Aerogels Based on Reduced Graphene Oxide/Cellulose Composites: Preparation and Vapour Sensing Abilities.

This paper reports on the preparation of cellulose/reduced graphene oxide (rGO) aerogels for use as chemical vapour sensors. Cellulose/rGO composite aerogels were prepared by dissolving cellulose and dispersing graphene oxide (GO) in aqueous NaOH/urea solution, followed by an in-situ reduction of GO to reduced GO (rGO) and lyophilisation. The vapour sensing properties of cellulose/rGO composite aerogels were investigated by measuring the change in electrical resistance during cyclic exposure to vapours with varying solubility parameters, namely water, methanol, ethanol, acetone, toluene, tetrahydrofuran (THF), and chloroform. The increase in resistance of aerogels on exposure to vapours is in the range of 7 to 40% with methanol giving the highest response. The sensing signal increases almost linearly with the vapour concentration, as tested for methanol. The resistance changes are caused by the destruction of the conductive filler network due to a combination of swelling of the cellulose matrix and adsorption of vapour molecules on the filler surfaces. This combined mechanism leads to an increased sensing response with increasing conductive filler content. Overall, fast reaction, good reproducibility, high sensitivity, and good differentiation ability between different vapours characterize the detection behaviour of the aerogels.

Tuning the Structure and Performance of Bulk and Porous Vapor Sensors Based on Co-continuous Carbon Nanotube-Filled Blends of Poly(vinylidene fluoride) and Polycarbonates by Varying Melt Viscosity.

This work describes a new concept of porous vapor sensor materials based on co-continuous polycarbonate/poly(vinylidene fluoride)/multiwalled carbon nanotube (PC/PVDF/MWCNT) blend composites. The blend composites were fabricated by melt mixing in a one-step mixing process, and the MWCNT containing component (here PC) was extracted, leaving a MWCNT network on the continuous surface of the remaining component (here PVDF). First, by selecting three PCs with different molecular weights, the blend viscosity ratio and blend fineness and interfacial area were varied. At the chosen blend composition of 40/60 wt %, the desired co-continuous structure was achieved with MWCNTs selectively localized in PC. The conductive polymer composites (CPCs) with low-viscosity PC had the highest conductivity due to a combination of the best MWCNT dispersion and the coarsest blend morphology. The vapor sensing of CPC sensor materials with 1 wt % MWCNT was tested using saturated vapors of dichloromethane, acetone, tetrahydrofuran, and ethyl acetate, showing good interaction with PC. The compact compression molded CPC materials with low-viscosity PC showed the lowest relative resistance changes (Rrel) during the cyclic sensing tests, but a better recovery compared to corresponding CPCs with medium and high viscosity PC. The porous CPC sensors showed remarkable vapor sensing performance compared to the corresponding compact sensors with better sensing stability, reproducibility, and reversibility. Scanning electron microscopy (SEM) confirmed that a fraction of the nanotubes remained on the surface of the continuous, nonsoluble PVDF after PC extraction. The porous sensor material from which the low-viscosity PC was extracted showed the highest Rrel (e.g., around 1300% after 100 s immersion in acetone vapor) compared to all other organic vapors investigated. The difference in vapor measurement between compact and porous sensor materials was attributed to the different sensing mechanisms of polymer swelling for the compact and vapor absorption on the free CNT networks for the porous samples.

Multifunctional Cellulose/rGO/Fe3O4 Composite Aerogels for Electromagnetic Interference Shielding.

Cellulose/reduced graphene oxide (rGO)/Fe3O4 aerogels exhibiting strong electromagnetic wave absorption were prepared by a green, simple, and scalable coprecipitation process. With rGO loading of 8 wt % and Fe3O4 content of approx. 15 wt %, the electromagnetic interference shielding effectiveness (EMI SE) of the cellulose/rGO/Fe3O4 aerogel with 0.5 mm thickness reached 32.4-40.1 dB at 8.2-12.4 GHz. The EMI shielding performance of cellulose/rGO/Fe3O4 aerogels was higher for larger rGO loading (varied between 3 and 8 wt %) and greatly improved on increasing the sample thickness (varied between 0.5 and 2 mm). At 2.0 mm thickness, SE values of 49.4-52.4 dB were reached. Absorption plays a major role in the EMI shielding mechanism of cellulose/rGO/Fe3O4 aerogels. The multireflection of microwaves and impedance matching provides the highly efficient EMI shielding caused by the combined effects of the porous structure, rGO sheets, and Fe3O4 nanoparticles. The results demonstrate that these lightweight aerogels are suitable for EMI shielding.

Fe3O4 Nanoparticles Grown on Cellulose/GO Hydrogels as Advanced Catalytic Materials for the Heterogeneous Fenton-like Reaction.

Cellulose/graphene oxide (GO)/iron oxide (Fe3O4) composites were prepared by coprecipitating iron salts onto cellulose/GO hydrogels in a basic solution. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared, and X-ray diffraction characterization showed that Fe3O4 was successfully coated on GO sheets and cellulose. Cellulose/GO/Fe3O4 composites showed excellent catalytic activity by maintaining almost 98% of the removal of acid orange 7 (AO7) and showed stability over 20 consecutive cycles. This performance is attributable to the synergistic effect of Fe3O4 and GO during the heterogeneous Fenton-like reaction. Especially, the cellulose/GO/Fe3O4 composites preserve their activity by keeping the ratio of Fe3+/Fe2+ at 2 even after 20 catalysis cycles, which is supported by XPS analysis.

Determination of Pressure Dependence of Polymer Phase Transitions by pVT Analysis.

Glass transitions, melting, crystallization, and the isotropization of polymers are connected with changes in the density, respectively the specific volume (Vsp), which can be analyzed by dilatometric methods. Here, the pressure dependence of such transitions is determined by pressure volume temperature (pVT) analysis for different thermoplastic polymers in the pressure range of 10 to 200 MPa, and the temperature range from room temperature to 350 °C. The values for ambient pressure are extrapolated. It is shown that polymer transitions always increase with pressure, and that the melting temperature and glass transition temperature are nearly linearly dependent on pressure. This information, as well as the observed density changes with pressure and temperature, is very important for the processing of thermoplastics, including their simulation, as well as for the thermodynamic interpretations of the transition's nature.

Adam-Gibbs model in the density scaling regime and its implications for the configurational entropy scaling.

To solve a long-standing problem of condensed matter physics with determining a proper description of the thermodynamic evolution of the time scale of molecular dynamics near the glass transition, we have extended the well-known Adam-Gibbs model to describe the temperature-volume dependence of structural relaxation times, τα(T, V). We also employ the thermodynamic scaling idea reflected in the density scaling power law, τα = f(T(-1)V(-γ)), recently acknowledged as a valid unifying concept in the glass transition physics, to differentiate between physically relevant and irrelevant attempts at formulating the temperature-volume representations of the Adam-Gibbs model. As a consequence, we determine a straightforward relation between the structural relaxation time τα and the configurational entropy SC, giving evidence that also SC(T, V) = g(T(-1)V(-γ)) with the exponent γ that enables to scale τα(T, V). This important findings have meaningful implications for the connection between thermodynamics and molecular dynamics near the glass transition, because it implies that τα can be scaled with SC.

Recent Advances in Preparation, Structure, Properties and Applications of Graphite Oxide.

Graphite oxide, also referred as graphitic oxide or graphitic acid, is an oxidized bulk product of graphite with a variable composition. However, it did not receive immense attention until it was identified as an important and easily obtainable precursor for the preparation of graphene. This inspired many researchers to explore facts related to graphite oxide in exploiting its fascinating features. The present article culminates up-dated review on different preparative methods, morphology and characterization of physical/chemical properties of graphite oxide by XRD, XPS, FTIR, Raman, NMR, UV-visible, and DRIFT analyses. Finally, recent developments on intercalation and applications of GO in multifaceted areas of catalysis, sensor, supercapacitors, water purification, hydrogen storage and magnetic shielding etc. has also been reviewed.

Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C8MIM][NTf2].

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Volume shrinkage and rheological studies of epoxidised and unepoxidised poly(styrene-block-butadiene-block-styrene) triblock copolymer modified epoxy resin-diamino diphenyl methane nanostructured blend systems.

Styrene-block-butadiene-block-styrene (SBS) copolymers epoxidised at different epoxidation degrees were used as modifiers for diglycidyl ether of the bisphenol A-diamino diphenyl methane (DGEBA-DDM) system. Epoxy systems containing modified epoxidised styrene-block-butadiene-block-styrene (eSBS) triblock copolymer with compositions ranging from 0 to 30 wt% were prepared and the curing reaction was monitored in situ using rheometry and pressure-volume-temperature (PVT) analysis. By controlling the mole percent of epoxidation, we could generate vesicles, worm-like micelles and core-shell nanodomains. At the highest mole percent of epoxidation, the fraction of the epoxy miscible component in the triblock copolymer (epoxidised polybutadiene (PB)) was maximum. This gave rise to core-shell nanodomains having a size of 10-15 nm, in which the incompatible polystyrene (PS) becomes the core, the unepoxidised PB becomes the shell and the epoxidised PB interpenetrates with the epoxy phase. On the other hand, the low level of epoxidation gave rise to bigger domains having a size of ∼1 µm and the intermediate epoxidation level resulted in a worm-like structure. This investigation specifically focused on the importance of cure rheology on nanostructure formation, using rheometry. The reaction induced phase separation of the PS phase in the epoxy matrix was carefully explored through rheological measurements. PVT measurements during curing were carried out to understand the volume shrinkage of the blend, confirming that shrinkage behaviour is related to the block copolymer phase separation process during curing. The volume shrinkage was found to be maximum in the case of blends with unmodified SBS, where a heterogeneous morphology was observed, while a decrease in the shrinkage was evidenced in the case of SBS epoxidation. It could be explained by two effects: (1) solubility of the epoxidised block copolymer in the DGEBA leads to the formation of nanoscopic domains upon reaction induced phase separation and (2) the plasticisation effect of the epoxidised block copolymer in the epoxy resin.

Free volume in ionic liquids: a connection of experimentally accessible observables from PALS and PVT experiments with the molecular structure from XRD data.

In the current work, free volume concepts, primarily applied to glass formers in the literature, were transferred to ionic liquids (ILs). A series of 1-butyl-3-methylimidazolium ([C4MIM](+)) based ILs was investigated by Positron Annihilation Lifetime Spectroscopy (PALS). The phase transition and dynamic properties of the ILs [C4MIM][X] with [X](-) = [Cl](-), [BF4](-), [PF6](-), [OTf](-), [NTf2](-) and [B(hfip)4](-) were reported recently (Yu et al., Phys. Chem. Chem. Phys., 2012, 14, 6856-6868). In this subsequent work, attention was paid to the connection of the free volume from PALS (here the mean hole volume, ) with the molecular structure, represented by volumes derived from X-ray diffraction (XRD) data. These were the scaled molecular volume Vm,scaled and the van der Waals volume V(vdw). Linear correlations of at the "knee" temperature ((T(k))) with V(m,scaled) and V(vdw) gave good results for the [C4MIM](+) series. Further relationships between volumes from XRD data with the occupied volume Vocc determined from PALS/PVT (Pressure Volume Temperature) measurements and from Sanchez-Lacombe Equation of State (SL-EOS) fits were elaborated (V(occ)(SL-EOS) ≈ 1.63 V(vdw), R(2) = 0.981 and V(occ)(SL-EOS) ≈ 1.12 V(m,scaled), R(2) = 0.980). Finally, the usability of V(m,scaled) was justified in terms of the Cohen-Turnbull (CT) free volume theory. Empirical CT type plots of viscosity and electrical conductivity showed a systematic increase in the critical free volume with molecular size. Such correlations allow descriptions of IL properties with the easily accessible quantity V(m,scaled) within the context of the free volume.

Free volume and phase transitions of 1-butyl-3-methylimidazolium based ionic liquids from positron lifetime spectroscopy.

Positron annihilation lifetime spectroscopy (PALS) was used to study a series of ionic liquids (ILs) with the 1-butyl-3-methylimidazolium cation ([C4MIM](+)) but different anions [Cl](-), [BF4](-), [PF6](-), [OTf](-), [NTf2](-), and [B(hfip)4](-) with increasing anion volumes. Changes of the ortho-positronium (o-Ps) lifetime parameters with temperature were observed for crystalline and amorphous (glass, supercooled, and normal liquid) states. Evidence for distinct phase transitions, e.g. melting, crystallization and solid-solid transitions, was observed in several PALS experiments. The o-Ps mean lifetime τ3 showed smaller values in the crystalline phase due to dense packing of the material compared to the amorphous phase. The o-Ps lifetime intensity I3 in the liquid state is clearly smaller than in the crystallized state. This behaviour can be attributed to a solvation of e(+) by the anions, which reduces the Ps formation probability in the normal and supercooled liquid. These phenomena were observed for the first time when applying the PALS technique to ionic liquids by us in one preliminary and in this work. Four of the ionic liquids investigated in this work ([BF4](-), [NTf2](-), [PF6](-) and [Cl](-) ILs) exhibit supercooled phases. The specific hole densities and occupied volumes of those ILs were obtained by comparing the local free volume with the specific volume from pressure-volume-temperature (PVT) experiments. From the o-Ps lifetime, the mean size vh of free volume holes of the four samples was calculated and compared with that calculated according to Fürth's hole theory. The hole volumes from both methods agree well. From the Cohen-Turnbull fitting of viscosity and conductivity against PALS/PVT results, the influence of the free volume on molecular transport properties was investigated.

Dynamics of phase separation in poly(acrylonitrile-butadiene-styrene)-modified epoxy/DDS system: kinetics and viscoelastic effects.

The dynamics of phase separation and final morphologies of poly(acrylonitrile-butadiene-styrene) (ABS)-modified epoxy system based on diglycidyl ether of bisphenol A (DGEBA) cured with 4,4'-diaminodiphenylsulfone (DDS) have been monitored in situ throughout the entire curing process by using optical microscopy (OM), differential scanning calorimetry (DSC), rheometry, and small-angle laser light scattering (SALLS). The evolution of phase separation and final morphologies with substructures were explored by OM. The final morphologies of the blend cured at 150 and 165 °C are of phase-inverted type and are quite different from the final morphologies of the same blend cured at 180 °C, in which the final morphologies are cocontinuous. AFM observations of the fully cured sample confirmed the existence of three different phases, the epoxy continuous phase, SAN (styrene/acrylonitrile) continuous phase, and PB droplets at the interface, with a strong tendency to stay at SAN continuous phase. Furthermore, the continuous epoxy phase contains SAN particles and the continuous SAN phase contains epoxy particles. Cure kinetics and rheological results correspond well with the viscoelastic phase separation revealed by OM. The SALLS results display clearly that the phase separation takes place according to nucleation and growth mechanism followed by spinodal decomposition. The development of light scattering patterns during the second stage phase separation follows the Cahn-Hilliard model of spinodal demixing. Furthermore, the evolution of the scattering vector follows a Maxwell-type relaxation equation establishing the viscoelastic behavior of phase separation. The relaxation time of phase separation can be described by the Williams-Landel-Ferry equation for viscoelasticity. As a whole, the dependence of phase separation on cure temperature and the development of final morphologies and the associated mechanisms were explored in detail for the complex epoxy/ABS system.

Subnanometre size free volumes in amorphous Verapamil hydrochloride: a positron lifetime and PVT study through T(g) in comparison with dielectric relaxation spectroscopy.

Positron annihilation lifetime spectroscopy (PALS), a method well established for the study of polymers, is employed to characterize the temperature dependence of the free volume through T(g) in the amorphous pharmaceutical Verapamil hydrochloride. From the PALS spectra analyzed with the routine LifeTime9.0 the size (volume) distribution of local free volumes (subnanometre-size holes), its mean, v(h), and mean dispersion, sigma(h), were calculated. A comparison with the macroscopic volume from PVT-experiments delivered the hole density and the hole free volume fraction and in that way a complete characterization of the free volume microstructure. These data are used in correlation with structural (alpha-) relaxation data from broad-band dielectric spectroscopy in terms of the Cohen-Turnbull free volume model. An extension of this model, distinctions in the free volume behaviour of the glassy and supercooled-liquid state and different ways of extrapolating the equilibrium part of the free volume into the temperature range of the glass are discussed. The potential of the PALS method for the study of pharmaceuticals is briefly reviewed and some recently developed applications (analysis of density fluctuations) are illuminated.