Conducting polymer-carbon black nanocomposite sensor for volatile organic compounds and correlating sensor response by molecular dynamics

Volatile organic compounds (VOCs) are present in our every day used products such as plastics, cosmetics, air fresheners, paint, etc. The determination of amount of VOC present in atmosphere can be carried out via various sensors. In this work a nanocomposite of a novel thiophene based conducting polymer and carbon black is used as a volatile organic compound sensor. The fabricated 2 lead chemiresistor sensor was tested for vapours of toluene, acetone, cylcohexane, and carbon tetrachloride. The sensor responds to all the vapours, however, exhibit maximum response to toluene vapours. The sensor was evaluated for various concentrations of toluene. The lower limit of detection of the sensor is 15 +/- 10 ppm. The study of the effect of humidity on senor response to toluene showed that the response decreases at higher humidity conditions. The surface morphology of the nanocomposite was characterized by scanning electron microscopy. Diffuse reflectance spectroscopy was used to investigate the absorption of vapours by the nanocomposite film. Contact angle measurements were used to present the effect of water vapour on the toluene response of nanocomposite film. Solubility parameter of the conducting polymer is predicted by molecular dynamics. The sensing behaviour of the conducting polymer is correlated with solubility parameter of the polymer. Dispersion interaction of conducting polymer with toluene is believed to be the reason for the selective response towards toluene. (C) 2014 Elsevier B.V. All rights reserved.

Carbon-Nanohorn-Reinforced Polymer Matrix Composites: Synergetic Benefits in Mechanical Properties

Mechanical properties of single-walled carbon nanohoms (SWNH) and SWNH plus few-layer graphene (EG)-reinforced poly(vinyl alcohol) (PVA) matrix composites have been measured using the nanoindentation technique. The elastic modulus (E) and hardness (H) of PVA were found to improve by similar to 315% and similar to 135%, respectively, upon the addition of just 0.4 wt % SWNH. These properties were found to be comparable to those obtained upon the addition of 0.2 wt % single-walled nanotubes (SWNT) to PVA. Furthermore, upon binary addition of 0.2 wt % EG and 0.4 wt % SWNH to PVA, benefits in the form of similar to 400% and similar to 330% synergy in E and H, respectively, were observed, along with an increased resistance to viscoelastic deformation. The reasons for these improvements are discussed in terms of the dimensionality of nanocarbon, the effectiveness of nanocarbon and polymer matrix interaction, and the influence of nanocarbon on the degree of crystallinity of the polymer. The results from SWNH reinforcement in this study demonstrate the scope for a novel and, in contrast to SWNT composites, a commercially feasible opportunity for strengthening polymer matrices.

Statistical thermodynamics of polydisperse polymer systems in the framework of lattice fluid model: Effect of molecular weight and its distribution on the spinodal in polymer solution

With the aid of thermodynamics of Gibbs, the expression of the spinodal was derived for the polydisperse polymer-solvent system in the framework of Sanchez-Lacombe Lattice Fluid Theory (SLLFT). For convenience, we considered that a model polydisperse polymer contains three sub-components. According to our calculation, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights of the polydisperse polymer, but the z-average molecular weight ((M) over bar (z)) dependence on the spinodal is invisible. The dependence of free volume on composition, temperature, molecular weight, and its distribution results in the effect of (M) over bar (n) on the spinodal. Moreover, it has been found that the effect of changing (M) over bar (w) on the spinodal is much bigger than that of changing (M) over bar (n) and the extrema of the spinodal increases with the rise of the weight-average molecular weight of the polymer in the solutions with upper critical solution temperature (UCST). However, the effect of polydispersity on the spinodal can be neglected for the polymer with a considerably high weight-average molecular weight. A more simple expression of the spinodal for the polydisperse polymer solution in the framework of SLLFT was also derived under the assumption of upsilon(*)=upsilon(1)(*)=upsilon(2)(*) and (1/r(1)(0))-(1/r(2i)(0))-->(1/r(1)(0)).

Study on the kinetics of ferrocene derivatives in polymer electrolyte/electrode interface at microelectrode

Heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of the ferrocene and its derivatives. in a new synthetic comb polymer solvent, poly(dimethylsiloxane-g-monomethylether polyethylene glycol) (SCP), and several other polymer solvents were estimated by using microelectrodes. Also, the influence of various supporting electrolytes on k(s) and D of ferrocene was studied. It was shown that k(s) and D of ferrocene decreased with increasing anionic size of the supporting electrolyte, but k(s) tended to increase with increasing radius of the solvated cation. Also, the cationic size of the supporting electrolytes had little effects on D. The values of k(s) and D for the ferrocene derivatives in the polymer solvents were in sharp contrast to those in monomeric solvents. Thus. the k(s) values were proportional to D in the polymer solvents. which indicates that solvent dynamics control of the electrode reaction. The values of k(s) and D of ferrocene in SCP were larger than those in other polymer solvents indicating that SCP is a good polymer solvent. (C) 2000 Elsevier Science B.V. All rights reserved.

Studies of ferrocene derivative diffusion and heterogeneous kinetics in polymer electrolyte by using microelectrode voltammetry

The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .3. Effect of the polymer solvents

The diffusion coefficients(D-app) and the heterogeneous electron transfer rate constants(k(s)) for ferrocene in several polymer solvents were determined by using steady-state voltammetry. The temperature dependence of the two parameters indicates Arrhenius behavior, The polymer solvent effects on diffusion and electron transfer dynamics of ferrocene were discussed.

Study on the UCST and LCST in PHB/PBHE-solvent system

Upper and lower critical solution temperature (UCST and LCST) behaviours have been examined for solution of PHB/PBHE blends in chloroform and chlorobenzene. Polymer-Solvent systems prepared with various solvents and concentrations were found to possess UCST and LCST characteristics. PHB/PBHE solution in chloroform displayed greater miscibility temperature region than that of the blend in chlorobenzene, but the relative tendency of both UCST and LCST were similar.

Advanced polymer membrane development in pervaporation dehydration and lateral flow diagnostics

The work in this thesis concerns the advanced development of polymeric membranes of two types; pervaporation and lateral-flow. The former produced from a solution casting method and the latter from a phase separation. All membranes were produced from casting lacquers. Early research centred on the development of viable membranes. This led to a supported polymer blend pervaporation membrane. Selective layer: plasticized 4:1 mass ratio sodium-alginate: poly(vinyl-alcohol) polymer blend. Using this membrane, pervaporation separation of ethanol/water mixtures was carefully monitored as a function of film thickness and time. Contrary to literature expectations, these films showed increased selectivity and decreased flux as film thickness was reduced. It is argued that morphology and structure of the polymer blend changes with thickness and that these changes define membrane efficiency. Mixed matrix membrane development was done using spherical, discreet, size-monodisperse mesoporous silica particles of 1.8 - 2μm diameter, with pore diameters of ~1.8 nm were incorporated into a poly(vinyl alcohol) [PVA] matrix. Inclusion of silica benefitted pervaporation performance for the dehydration of ethanol, improving flux and selectivity throughout in all but the highest silica content samples. Early lateral-flow membrane research produced a membrane from a basic lacquer composition required for phase inversion; polymer, solvent and non-solvent. Results showed that bringing lacquers to cloud point benefits both the pore structure and skin layers of the membranes. Advancement of this work showed that incorporation of ethanol as a mesosolvent into the lacquer effectively enhances membrane pore structure resulting in an improvement in lateral flow rates of the final membranes. This project details the formation mechanics of pervaporation and lateral-flow membranes and how these can be controlled. The principle methods of control can be applied to the formation of any other flat sheet polymer membranes, opening many avenues of future membrane research and industrial application.

Ion transport in polymer electrolytes containing nanoparticulate TiO2 : The influence of polymer morphology

Recent studies have shown that composite polymer electrolytes, formed by dispersing nanosized ceramic particles in polyether-based electrolytes, have improved ion transport properties as compared to their unfilled analogues. In the present study polymer electrolytes with different loadings of nano-sized ceramic particles (TiO₂) and different polymer chemistry and morphology have been investigated. Of special interest are filler induced effects on polymer, solvent and cationic mobility. Partly crystalline polymer electrolytes based on poly(ethylene oxide) have been compared to fully amorphous polymer electrolytes based on a polyether urethane, as well as gel electrolytes based on PMMA. ⁷Li pfg-NMR, linewidth and spin–spin relaxation times as well as ¹H pfg-NMR and spin–spin relaxation times, were measured as a function of temperature and composition. The ¹H spin–spin relaxation measurements reveal increased average polymer mobility with the addition of filler up to a maximum at 4 and 8 wt.% TiO₂ for the fully amorphous and the partly crystalline electrolytes, respectively. The ⁷Li linewidth measurements for the fully amorphous system show a broadening of the linewidth with addition of filler. Based on variable temperature measurements this broadening is interpreted as a result of the inhomogeneity introduced by the filler particles. Pulsed field gradient (pfg) diffusion measurements were employed to determine ion and solvent self-diffusion coefficients. In the case of the PMMA-based gel electrolyte and the fully amorphous electrolytes enhanced cation self-diffusion was observed upon addition of TiO₂.

Positron annihilation lifetime spectroscopy as a probe of free volume in plasticized solid polymer electrolytes

A recent report on the correlation between enhanced polymer mobility and ionic conductivity at room temperature in plasticized polyether-urethane solid polymer electrolytes (Forsyth et al.[1]), has prompted the present investigation. Positron annihilation lifetime spectroscopy (PALS) has been used to study the effect of plasticizer addition on the room temperature free volume characteristics of the crosslinked polyether-urethane. The addition of low molecular weight plasticizers to the polyether-urethane results in a constant or decreasing mean free volume cavity radius, as measured by the orthoPositronium lifetime τ₃, and a decreasing relative concentration of free volume cavities as measured by the ortho-Positronium intensity, I₃. It is postulated that the plasticizers interrupt polymer-polymer interactions by occupying the inter- and intra-chain free volume. The plasticizer structure influences the polymerplasticizer interactions which affect inter- and intra-chain separation and hence the free volume of the system. The decrease in polymer-polymer interaction and the increase in polymer-plasticizer interaction in turn influence the glass transition temperature behaviour.

Structuring of polymer surface by evaporation of sessile microdrops

In this thesis, we investigated the evaporation of sessile microdroplets on different solid substrates. Three major aspects were studied: the influence of surface hydrophilicity and heterogeneity on the evaporation dynamics for an insoluble solid substrate, the influence of external process parameters and intrinsic material properties on microstructuring of soluble polymer substrates and the influence of an increased area to volume ratio in a microfluidic capillary, when evaporation is hindered. In the first part, the evaporation dynamics of pure sessile water drops on smooth self-assembled monolayers (SAMs) of thiols or disulfides on gold on mica was studied. With increasing surface hydrophilicity the drop stayed pinned longer. Thus, the total evaporation time of a given initial drop volume was shorter, since the drop surface, through which the evaporation occurs, stays longer large. Usually, for a single drop the volume decreased linearly with t1.5, t being the evaporation time, for a diffusion-controlled evaporation process. However, when we measured the total evaporation time, ttot, for multiple droplets with different initial volumes, V0, we found a scaling of the form V0 = attotb. The more hydrophilic the substrate was, the more showed the scaling exponent a tendency to an increased value up to 1.6. This can be attributed to an increasing evaporation rate through a thin water layer in the vicinity of the drop. Under the assumption of a constant temperature at the substrate surface a cooling of the droplet and thus a decreased evaporation rate could be excluded as a reason for the different scaling exponent by simulations performed by F. Schönfeld at the IMM, Mainz. In contrast, for a hairy surface, made of dialkyldisulfide SAMs with different chain lengths and a 1:1 mixture of hydrophilic and hydrophobic end groups (hydroxy versus methyl group), the scaling exponent was found to be ~ 1.4. It increased to ~ 1.5 with increasing hydrophilicity. A reason for this observation can only be speculated: in the case of longer hydrophobic alkyl chains the formation of an air layer between substrate and surface might be favorable. Thus, the heat transport to the substrate might be reduced, leading to a stronger cooling and thus decreased evaporation rate. In the second part, the microstructuring of polystyrene surfaces by drops of toluene, a good solvent, was investigated. For this a novel deposition technique was developed, with which the drop can be deposited with a syringe. The polymer substrate is lying on a motorized table, which picks up the pendant drop by an upward motion until a liquid bridge is formed. A consecutive downward motion of the table after a variable delay, i.e. the contact time between drop and polymer, leads to the deposition of the droplet, which can evaporate. The resulting microstructure is investigated in dependence of the processes parameters, i.e. the approach and the retraction speed of the substrate and the delay between them, and in dependence of the intrinsic material properties, i.e. the molar mass and the type of the polymer/solvent system. The principal equivalence with the microstructuring by the ink-jet technique was demonstrated. For a high approach and retraction speed of 9 mm/s and no delay between them, a concave microtopology was observed. In agreement with the literature, this can be explained by a flow of solvent and the dissolved polymer to the rim of the pinned droplet, where polymer is accumulated. This effect is analogue to the well-known formation of ring-like stains after the evaporation of coffee drops (coffee-stain effect). With decreasing retraction speed down to 10 µm/s the resulting surface topology changes from concave to convex. This can be explained with the increasing dissolution of polymer into the solvent drop prior to the evaporation. If the polymer concentration is high enough, gelation occurs instead of a flow to the rim and the shape of the convex droplet is received. With increasing delay time from below 0 ms to 1s the depth of the concave microwells decreases from 4.6 µm to 3.2 µm. However, a convex surface topology could not be obtained, since for longer delay times the polymer sticks to the tip of the syringe. Thus, by changing the delay time a fine-tuning of the concave structure is accomplished, while by changing the retraction speed a principal change of the microtopolgy can be achieved. We attribute this to an additional flow inside the liquid bridge, which enhanced polymer dissolution. Even if the pendant drop is evaporating about 30 µm above the polymer surface without any contact (non-contact mode), concave structures were observed. Rim heights as high as 33 µm could be generated for exposure times of 20 min. The concave structure exclusively lay above the flat polymer surface outside the structure even after drying. This shows that toluene is taken up permanently. The increasing rim height, rh, with increasing exposure time to the solvent vapor obeys a diffusion law of rh = rh0  tn, with n in the range of 0.46 ~ 0.65. This hints at a non-Fickian swelling process. A detailed analysis showed that the rim height of the concave structure is modulated, unlike for the drop deposition. This is due to the local stress relaxation, which was initiated by the increasing toluene concentration in the extruded polymer surface. By altering the intrinsic material parameters i.e. the polymer molar mass and the polymer/solvent combination, several types of microstructures could be formed. With increasing molar mass from 20.9 kDa to 1.44 MDa the resulting microstructure changed from convex, to a structure with a dimple in the center, to concave, to finally an irregular structure. This observation can be explained if one assumes that the microstructuring is dominated by two opposing effects, a decreasing solubility with increasing polymer molar mass, but an increasing surface tension gradient leading to instabilities of Marangoni-type. Thus, a polymer with a low molar mass close or below the entanglement limit is subject to a high dissolution rate, which leads to fast gelation compared to the evaporation rate. This way a coffee-rim like effect is eliminated early and a convex structure results. For high molar masses the low dissolution rate and the low polymer diffusion might lead to increased surface tension gradients and a typical local pile-up of polymer is found. For intermediate polymer masses around 200 kDa, the dissolution and evaporation rate are comparable and the typical concave microtopology is found. This interpretation was supported by a quantitative estimation of the diffusion coefficient and the evaporation rate. For a different polymer/solvent system, polyethylmethacrylate (PEMA)/ethylacetate (EA), exclusively concave structures were found. Following the statements above this can be interpreted with a lower dissolution rate. At low molar masses the concentration of PEMA in EA most likely never reaches the gelation point. Thus, a concave instead of a convex structure occurs. At the end of this section, the optically properties of such microstructures for a potential application as microlenses are studied with laser scanning confocal microscopy. In the third part, the droplet was confined into a glass microcapillary to avoid evaporation. Since here, due to an increased area to volume ratio, the surface properties of the liquid and the solid walls became important, the influence of the surface hydrophilicity of the wall on the interfacial tension between two immiscible liquid slugs was investigated. For this a novel method for measuring the interfacial tension between the two liquids within the capillary was developed. This technique was demonstrated by measuring the interfacial tensions between slugs of pure water and standard solvents. For toluene, n-hexane and chloroform 36.2, 50.9 and 34.2 mN/m were measured at 20°C, which is in a good agreement with data from the literature. For a slug of hexane in contact with a slug of pure water containing ethanol in a concentration range between 0 and 70 (v/v %), a difference of up to 6 mN/m was found, when compared to commercial ring tensiometry. This discrepancy is still under debate.

Relation Between the Diffusivity, Viscosity, and Ionic Radius of LiCl in Water, Methanol, and Ethylene Glycol: A Molecular Dynamics Simulation

A molecular dynamics (MD) investigation of LiCl in water, methanol, and ethylene glycol (EG) at 298 K is reported. Several; structural and dynamical properties of the ions as well as the solvent such as self-diffusivity, radial distribution functions, void and neck distributions, velocity autocorrelation functions, and mean residence times of solvent in the first solvation shell have been computed. The results show that the reciprocal relationship between the self-diffusivity of the ions and the viscosity is valid in almost all solvents with the exception of water. From an analysis of radial distribution functions and coordination numbers the nature of hydrogen bonding within the solvent and its influence on the void and neck distribution becomes evident. It is seen that the solvent solvent interaction is important in EG while solute solvent interactions dominate in water and methanol. From Voronoi tessellation, it is seen that the voids and necks within methanol are larger as compared to those within water or EG. On the basis of the void and neck distributions obtained from MD simulations and literature experimental data of limiting ion conductivity for various ions of different sizes we show that there is a relation between the void and neck radius on e one hand and dependence of conductivity on the ionic radius on the other. It is shown that the presence of large diameter voids and necks in methanol is responsible for maximum in limiting ion conductivity (lambda(0)) of TMA(+), while in water in EG, the maximum is seen for Rb+. In the case of monovalent anions, maximum in lambda(0) as a function ionic radius is seen for Br- in water EG but for the larger ClO4- ion in methanol. The relation between the void and neck distribution and the variation in lambda(0) with ionic radius arises via the Levitation effect which is discussed. These studies show the importance of the solvent structure and the associated void structure.

Avaliação da influência da interação polímero-solvente sobre a porosidade de copolímeros de acrilonitrila e divinilbenzeno obtidos por polimerização em suspensão

Neste trabalho, copolímeros à base de acrilonitrila e divinilbenzeno foram sintetizados, utilizando a técnica de polimerização em suspensão, na presença de três agentes porogênicos diferentes (álcool isoamílico, metil-etil-cetona e tolueno). Esses copolímeros foram caracterizados por meio da determinação da densidade aparente, do volume e diâmetro de poros, por microscopia ótica e microscopia eletrônica de varredura e foram avaliados quanto à capacidade de inchamento em heptano e tolueno. O principal intuito dessa pesquisa foi correlacionar a formação da estrutura porosa desses materiais com os principais parâmetros de síntese (grau de diluição dos monômeros, poder solvatante do diluente e teor do agente de reticulação). Desses parâmetros, o que mais influenciou na formação da estrutura porosa desses materiais foi o poder solvatante do diluente. A teoria dos parâmetros de solubilidade de Hansen e Hildebrand foi utilizada com o intuito de fazer uma previsão das características porosas dos copolímeros à base de acrilonitrila e divinilbenzeno sintetizados na presença de três diluentes diferentes. Dentre esses diluentes, o álcool isoamílico foi o pior solvente para os copolímeros de AN-DVB, em todos os teores de agente de reticulação e em todas as diluições utilizadas. O tolueno foi o melhor solvente para os copolímeros que contêm altos teores de agente de reticulação. Estas observações estão de acordo com as previsões dos parâmetros de solubilidade de Hansen e Hildebrand. A metil-etil-cetona foi o melhor solvente para os copolímeros que contêm teores intermediários de agente de reticulação. Esta observação só está condizente com o parâmetro de solubilidade de Hansen.

Determination of the standard heterogeneous rate constant in polyelectrolyte using steady state microdisk voltammograms

The steady state voltammogram at a microdisk electrode is used to measure the diffusion coefficient and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG + LiClO4. The k(s) obtained is smaller in polyelectrolyte than in liquid medium. It is proposed that the polymer solvent electron transfer dynamics are affected by the relaxation rates of the ether dipole sites on the polymer chains, which are in turn constrained by the rates of polymer chain segment, or local structure, relaxations. The dependence of k(s) on temperature is observed. The k(s) increases with increasing temperature.

Investigation of swelling and network parameters of poly(ethylene glycol)-crosslinked poly(methyl vinyl ether-co-maleic acid) hydrogels

The influence of poly(ethylene glycol) (PEG) plasticiser content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) was investigated using thermal analysis, swelling studies, scanning electron microscopy (SEM) and attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy. FTIR spectroscopy revealed a shift of the C{double bond, long}O peak from 1708 to 1731 cm, indicating that an esterification reaction had occurred upon heating, thus producing crosslinked films. Higher molecular weight PEGs (10,000 and 1000 Da, respectively), having greater chain length, producing hydrogel networks with lower crosslink densities and higher average molecular weight between two consecutive crosslinks. Accordingly, such materials exhibited higher swelling rates. Hydrogels crosslinked with a low molecular weight PEG (PEG 200) showed rigid networks with high crosslink densities and, therefore, lower swelling rates. Polymer:plasticizer ratio alteration did not yield any discernable patterns, regardless of the method of analysis. The polymer-water interaction parameter (?) increased with increases in the crosslink density. SEM studies showed that porosity of the crosslinked films increased with increasing PEG MW, confirming what had been observed with swelling studies and thermal analysis, that the crosslink density must be decreased as the M of the crosslinker is increased. Hydrogels containing PMVE/MA/PEG 10,000 could be used for rapid delivery of drug, due to their low crosslink density. Moderately crosslinked PMVE/MA/PEG 1000 hydrogels or highly crosslinked PMVE/MA/PEG 200 systems could then be used in controlling the drug delivery rates. We are currently evaluating these systems, both alone and in combination, for use in sustained release drug delivery devices. © 2008 Elsevier Ltd. All rights reserved.