Effect of the type of polymer functional groups on the structure of its film formed on the alumina surface – Suspension stability

The effects of polymer functional group and solution pH on stability of colloidal Al₂O₃ water suspension were studied. Both the nonionic polymers: polyethylene glycol (PEG), polyethylene oxide (PEO) and the ionic ones: polyacrylic acid (PAA), polyacrylamide (PAM), polyvinyl alcohol (PVA) were used in the experiments. The following methods were applied: turbidimetry (stability measurements), spectrophotometry (determination of polymer adsorption), viscosimetry (thickness of polymer adsorption layer), potentiometric titration (solid surface charge density) and microelectrophoresis (potential zeta). It was shown that anionic polyacrylic acid is both the most effective stabilizer (at pH 9) and flocculant (at pH 3) of the alumina suspension. Its carboxyl groups have the greatest affinity for the surface active sites (the largest adsorption) of all functional groups present in the other examined polymers. The latter, i.e. hydroxyl (PEG, PEO, and PVA) and acetate (PVA) show a much lower affinity for the Al₂O₃ surface (negligible adsorption) and minimally affect the stability of the alumina-solution system.     

Control of the electric field–polymer solution interaction by utilizing ultra-conductive fluids

Dramatically raising the conductivity of a polymer solution by using a salt additive allows control over the electric field-induced jet feed rate when electrospinning from an unconfined fluid without altering the applied voltage. As the solution conductivity increases, the flow rate drops by an order of magnitude. At a high voltage level and fluid conductivity value, the jets undergo a whipping instability over almost the entire path from the source to the collector experiencing only a negligibly short linear region which, along with the flow rate data, indicates that the jet narrows due to the high conductivity. Under these conditions, even while possessing relatively large individual jet feed rates, thin diameter nanofibers (200–300 nm) are readily produced. In contrast with other approaches to obtain narrow fibers from unconfined fluids (e.g., voltage reduction to control feed rate), here the fiber forming jets are present indefinitely. Continuous, scaled up nanofiber production rate of >125× over the traditional single needle electrospinning method is observed from the presence of multiple jets, each possessing a relatively high solution feed rate. These fundamental experiments reveal new pathways for exploring novel electrospinning configurations where the jet feed rate can be controlled by manipulating the solution conductivity.     

Characteristics of electrochemically synthesized polymer electrodes in lithium cells—IV. Effects of the synthesis conditions on the performance of polypyrrole

The performance of polymer electrodes in lithium cells strongly depends on the conditions of electrosynthesis. In this work we describe the role of current density and of total charge of preparation on the cyclability of polypyrrole electrodes in a 1 M LiClO₄ solution in propylene carbonate.     

Effect of blend ratio on the dynamic mechanical and thermal degradation behavior of polymer–polymer composites from low density polyethylene and polyethylene terephthalate

Microfibrillar polymer–polymer composites (MFCs) based on low-density polyethylene (LDPE) and polyethylene terephthalate (PET) were prepared by cold drawing-isotropization technique. The weight percentage of PET was varied from 5 to 45 %. Microfibrils with uniform diameter distribution were obtained at 15 to 25 wt% of PET as evident from the scanning electron microscopy (SEM) results. Dynamic mechanical properties such as storage modulus (E′), loss modulus (E″) damping behavior (tan δ) were examined as a function of blend composition. The E′ values were found to be increasing up to 25 wt% of PET. An effort was made to model the storage modulus and damping characteristics of the MFCs using the classical equations used for short-fiber reinforced composites. The presence of PET microfibrils influenced the damping characteristics of the composite. The peak height at the β-transitions of loss modulus was lower for MFCs with 25 % PET, showing that they had superior damping characteristics. This phenomenon could be correlated with the PET microfibrils morphology. The thermal degradation characteristics of LDPE, neat blends and microfibrillar blends (MFBs) were compared. The determination of activation energy for thermal degradation was carried out using the Horowitz and Metzger method. The activation energy for thermal degradation of microfibrillar blends was found to be higher than that for the corresponding neat blends and MFCs. The long PET microfibrils present in MFBs could prevent the degradation and enhance the activation energy.     

Effects of amorphous silica nanoparticles and polymer blend compositions on the structural,thermal and dielectric properties of PEO–PMMA blend based polymer nanocomposites

The polymer nanocomposite (PNC) films consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrices dispersed with nanoparticles of amorphous silica (SiO₂) have been prepared by solution-cast method followed by melt-press technique. Effects of SiO₂ concentration (x?=?0, 1, 3 and 5 wt%) and PEO–PMMA blend compositional ratios (PEO:PMMA?=?75:25, 50:50, and 25:75 wt%) on the surface morphology, crystalline phase, polymer-polymer and polymer-nanoparticle interactions, melting phase transition temperature, dielectric permittivity, electrical conductivity, electric modulus and the impedance properties of the PNC films have been investigated. The crystalline phase of the PNC films decreases with the increase of PMMA contents which also vary anomalously with the increase of SiO₂ concentration in the films. The melting phase transition temperature and polymer-nanoparticle interactions significantly change with the variation in the compositional ratio of the blend polymers in the PNC films. It is observed that the effect of SiO₂ on the dielectric and electrical properties of these PNCs vary greatly with change in the compositional ratio of PEO and PMMA in the blends. The dielectric relaxation process of these films confirm that the polymers cooperative chain segmental dynamics becomes significantly slow when merely 1 wt% SiO₂ nanoparticles are dispersed in the polymer blend matrix.     

Doping behavior of water-soluble π-conjugated polythiophenes depending on pH and interaction of the polymer with DNA

Doping behavior of two kinds of water-soluble polythiophenes (PThs) (PTh with a CH₂CH₂CH₂SO₃M substituent at the 3-position, P3(RSO₃H)Th, and poly(ethylenedioxythiophene), PEDOTh) has been investigated spectroscopically at various pH under air. The p-doped (or oxidized) state of P3(RSO₃M)Th is stable at pH=1.0, whereas at pH levels higher than 4, the polymer is undoped. To the contrary, the p-doped state of PEDOTh is stable over a pH range of 1 to 7. Mixing of PEDOTh and a DNA (poly(G-C)₂) in a Tris buffer solution leads to a change of the UV-visible spectrum and precipitation of their adduct, supporting formation of an adduct between PEDOTh and poly(G-C)₂.     

The roles of the Trommsdorff–Norrish effect in phase separation of binary polymer mixtures induced by photopolymerization

Influence of the Trommsdorff–Norrish (T–N) effect on the phase separation of methyl methacrylate (MMA)/poly(ethyl acrylate) (PEA) mixtures undergoing photo-polymerization was examined by a combination of several experimental techniques. By FT-IR spectroscopy, it was found that the polymerization conversion explosively increases at the onset of this T–N effect. The characteristic irradiation time τ at which this effect occurs, strongly depends on the light intensity and gradually shifts to early time as the irradiation intensity increases. The shrinkage of the mixture observed in situ by laser-scanning confocal microscopy exhibits a transition at a particular irradiation time which is slightly longer than the characteristic time τ. By gel permeation chromatography (GPC), it was found that the molecular weight of the resulting PMMA was almost unchanged before τ and suddenly increases about an order of magnitude after the onset of the auto-acceleration effect. Finally, the characteristic length scales of the morphology also quickly increase with irradiation time and are eventually frozen by this T–N effect. These experimental results indicate that the Trommsdorff–Norrish effect plays an important role in the kinetic processes of polymerization-induced phase separation, suggesting an efficient tool to control the morphology of the polymerizing mixture.     

Conformation–function relationships for the comb-shaped polymer pOEGMA

Poly(oligo(ethylene glycol) methyl ether methacrylate) (pOEGMA) is a highly versatile polymer because manipulation of the dimensions of its comb-type structure has a predictable effect on the conformation of its main-chain and side-chains which can, together or independently, be either extended or collapsed. This control, and the distinctive physical–chemical characteristics of pOEGMA, are the common driving forces behind its tunable thermosensitivity properties, supramolecular assembly characteristics, and efficient protein repellency. Because of these interesting properties, pOEGMA is increasingly being used within functional coatings, biosensors, drug delivery systems, biomaterials, etc. This Trend article highlights the how to control (and factors influencing) pOEGMA main/side-chain conformations, and consequently exploit this polymer in several emerging areas of importance. This discussion integrates all current areas of application (i.e., in solution, within complex (bio)conjugates, and grafted to solids), in order to provide a common and general perspective on how this polymer can be most efficiently used in future applications.     

Active filler controlled polymer pyrolysis – A promising route for the fabrication of advanced ceramics

A novel polyborosiloxane (BoSiVi) containing methyl and vinyl groups with Titanium Silicide (TiSi₂) filler was employed for the preparation of silicon and titanium containing ceramic phases. Ceramic phase evolution was studied from the above mentioned preceramic system at 900, 1200, 1500, 1800 and 2000 °C respectively under argon atmosphere. Reactive nature of TiSi₂ with pyrolytic by-products of BoSiVi led to the formation of different ceramic phases at different firing temperatures. XRD analysis confirmed the evolution of carbide (TiC, TiB, SiC etc.) and oxide (TiOC, SiO₂ etc.) ceramic phases in the temperature regime of 900 °C to 1500 °C. FESEM-EDX analysis of the ceramic phases, heat treated at 1500 °C, proved the formation of Si-Ti-O-C ceramic nano-fibers by Vapor-Liquid-Solid (VLS) method. BoSiVi+TiSi₂ system heat treated at 1800 °C and 2000 °C exhibited the evolution of pure non-oxide ceramic phases along with Ti₃SiC₂ MAX phase.     

Resistivity–temperature characteristics of filler-dispersed polymer composites

Composites containing carbon nano tube (CNT) or carbon black (CB) conductive particle filler have the special characteristics of positive-temperature-coefficient (PTC) effects of resistivity. We quantitatively studied the relationship between poly(vinylidene fluoride) (PVDF) polymer's thermal volume expansion and the PTC effects of PVDF/CNT and PVDF/CB. The equation to revise filler content at each temperature due to the considerable thermal volume expansion rate of PVDF polymer indicates that filler content decreased with rising temperature. The graphs of filler content at room temperature plotted against apparent filler content with PTC effect were linear and their slopes were constant. From these graphs, we can determine the filler content necessary to occurring PTC effects. For example, the CNT content was 89% at room temperature, and the CB content was 93%. To our knowledge, this study is the first to report such phenomena.     

Properties of electrochemically synthesized polymers—V. The polymer electrode/polymer electrolyte interface

A solid-state lithium-polypyrrole cell having a polymeric electrolyte based on the lithium perchlorate—poly(ethylene oxide) complex, has been assembled. Results based on cyclic voltammetry, frequency response analyses and charge—discharge cycles, show that the polymer/polymer interface is characterized by favourable kinetics in the temperature range where the conductivity of the electrolyte is sufficiently high.Therefore using proper cell design, the solid-state polymeric systems may be considered for the realization of interesting devices, such as ultrathin batteries, electrochromic displays and thermal sensors.     

Optimization and simplification of polymer–fullerene solar cells through polymer and active layer design

Polymer–fullerene bulk heterojunction (BHJ) solar cells have consistently been at the forefront of the growing field of organic photovoltaics (OPV). The enduring vision of OPV is the promise of combining a simple, low-cost approach with an efficient, flexible, lightweight platform. While efficiencies have improved remarkably over the last decade through advances in device design, mechanistic understanding, and evolving chemical structural motifs, steps forward have often been tied to a loss of simplicity and a deviation from the central vision of OPV. Within the context of active layer optimization, our focus is to target high efficiency while maintaining simplicity in polymer design and active layer processing. To highlight this strategy, this feature article focuses on our work on random poly(3-hexylthiophene) (P3HT) analogs and their application in binary and ternary blend polymer–fullerene solar cells. These random conjugated polymers are conceptually based on combining simple monomers strategically to influence polymer properties as opposed to the synthesis of highly tailored and synthetically complex monomers. The ternary blend approach further exemplifies the focus on device simplicity by targeting efficiencies that are competitive with complex tandem solar cells, but within the confines of a single active-layer processing step. These research directions are described within the broader context of recent progress in the field of polymer–fullerene BHJ solar cells.     

A polymer complex solution process for the synthesis and characterization of Ni–YSZ cermet material

Ni–YSZ cermets for SOFC anodes were prepared by the Pechini-type reaction route. The initial polymer precursors were prepared with different citric acid/ethylene glycol (CA/EG) molar ratios. The properties of the samples at different stages of the preparation procedure were evaluated with regard to thermal decomposition (TG–DTA), crystallite size (XRD), surface area (BET), sinterability and phase distribution (SEM). The results showed that an increase of CA and EG in the starting solution increased the final temperature of the thermal decomposition of gels from 340 °C to 382 °C, and the specific surface area of calcined NiO–YSZ powders from 10 m² g⁻¹ to 27 m² g⁻¹. In parallel the sinterability of the samples increased. A distinct increase of CA in the predominantly aqueous solution diminished the nickel grain size in the final Ni–YSZ material. A shift from aqueous to organic media further reduced the nickel-rich regions to around 0.2 μm.     

The effect of stoichiometric ratio λ on the performance of a polymer electrolyte fuel cell

The effect of stoichiometric ratio λ on performance of a polymer electrolyte fuel cell is rationalized. λ→∞ corresponds to uniform oxygen concentration along the channel; the limiting current density then is determined by transport of oxygen across the cell. Finite λ corresponds to decreasing oxygen concentration along the channel. In that case j-axis of a voltage-current plot is “compressed” by a factor and apparent value of limiting current density appears to be f_λ times lower. The function f_λ→∞ as λ→1; physically, in this limit all available oxygen is consumed close to the channel inlet and apparent limiting current tends to zero. Recently derived expression for the voltage-current curve of the cell is extended to take into account the effect of λ. Fitting of experimental voltage-current curves with the new relation gives an estimate of basic parameters of the cell.     

Effect of polymer–nanoparticle interactions on the glass transition dynamics and the conductivity mechanism in polyurethane titanium dioxide nanocomposites

We report on the glass transition dynamics and the conductivity properties of a nanodielectric system composed of pre-synthesized TiO₂ nanoparticles embedded in thermoplastic polyurethane. Increase of TiO₂ loading results in enhanced segmental mobility of the composites and less steep temperature dependence, i.e., lower fragility index. The decrease in the fragility index and glass transition temperature is discussed based on the FTIR results. We observe different behavior of conductivity for temperatures above and below the glass transition temperature. At high temperatures the composites exhibit conductivity values more than 2 orders of magnitude higher than those in the pristine matrix. At the same time, at sub-T_g temperatures composites are characterized by superior electrical insulation properties compared to pristine matrix material. Such drastic temperature dependence of the conductivity/insulating ability of the flexible and light-weight, low-T_g composite material can be utilized in various applications including sensing and temperature switching materials.     

Effect of synthetic polymers on polymer–protein interaction

Synthetic polymers are often used for delivery of therapeutic drugs and proteins. We report the binding of milk β-lactoglobulin (β-LG) with poly(ethylene glycol) (PEG), methoxypoly(ethylene glycol) polyamidoamine (mPEG-PAMAM-G-3) and polyamidoamine (PAMAM-G4) nanoparticles in aqueous solution at pH 7.4, using Fourier Transform infrared (FTIR), circular dichroism (CD), fluorescence spectroscopic methods, transmission electron microscopy (TEM) and molecular modeling. Structural analysis showed that polymers bind β-LG via both hydrophilic and hydrophobic contacts with overall binding constants K_{PEG-8000-β-LG} = 4.8 (±0.4) × 10⁴ M⁻¹ and K_{mPEG-PAMAM-G3-β-LG} = 5.8 (±0.6) × 10⁵ M⁻¹ and K_{PAMAM-G4-β-LG} = 6.7 (±0.9) × 10⁴ M⁻¹. The number of binding sites were occupied by polymers on protein (n) was 0.3 for PEG-8000, 0.4 for mPEG–PAMAM-G3 and 0.4 for PAMAM-G4. The order of binding is mPEG-PAMAM-G3 > PAMAM-G4 > PEG-8000. Transmission electron microscopy showed significant changes in protein morphology as polymer–protein complexation progressed with major increase in the diameter of the protein aggregate (180%). Furthermore, modeling showed several H-bonding systems between PEG and different amino acids stabilize polymer–β-LG complexes. mPEG-PAMAM-G3 is a stronger protein binder than PAMAM-G4 and PEG-8000.     

Volumetric properties of polymer blends from Tao–Mason equation of state

The present study is an improvement of previous work (Yousefi and Karimi, Ionics 18:135–142, 17) concern to the assessment of the ability of the Tao–Mason equation of state to predict pressure–volume–temperature (PVT) of melting polymers. The present paper, focus on the modeling of volumetric properties of polymer blends based on melting temperature (T _m) and melting point density (ρ _m), as scaling constants. The calculation of second Virial coefficients (B ₂), effective van der Waals co-volume (b) and correction factor (α) are required for judgment about applicability of this model. The new correlations were used to predict the PVT behavior of polymer blends containing poly(propylene glycol) + poly(ethylene glycol) (PEG-200), poly(ethylene glycol) methyl ether(PEGME-350) + PEG-200, PEGME-350 + PEG-600, poly(2,6-dimethyl-1,4-phenylene oxide) + poly styrene(PS), and PS + poly(vinylmethylether) in different temperatures, pressures, and mole fractions. A collection of 5,397 data points has been examined for the aforementioned polymers in the temperature in the range of 298.15–605.05 K and pressures up to 200 MPa. The average absolute deviation between the calculated and experimental densities is of the order of 0.78 %.     

An imidazolium iodide–containing hyperbranched polymer ionic liquid that improves the performance of dye-sensitized solar cells

In this study, we synthesized an imidazolium iodide–containing hyperbranched polymer ionic liquid (HPIL) for use as the gel electrolyte of dye-sensitized solar cells (DSSCs). We incorporated HPIL at various contents (4, 8, and 15 wt%) in a solvent-free ionic liquid (1-propyl-2,3-dimethylimidazolium iodide and 1-ethyl-3-methylimidazolium tetrafluoroborate)–based quasi-solid gel electrolyte (IL-A) and a solvent (3-methoxypropionitrile)-based fluid gel electrolyte (IL-B). After fabricating N719 dye–based DSSCs incorporating the HPIL/IL-A and HPIL/IL-B gel electrolytes, we recorded the electrochemical impedance spectra and measured the photovoltaic (PV) performance of these devices. In the dark, the DSSCs incorporating HPIL exhibited higher charge recombination resistances at the interface between TiO₂/dye and the electrolyte. This high recombination resistance suppressed the dark current and improved the PV performance of the devices incorporating HPIL. The DSSCs fabricated from the HPIL/IL-B gel electrolyte displayed higher photo-conversion efficiency, while those fabricated from the HPIL/IL-A gel electrolyte provided superior operational stability. Under AM 1.5 illumination (100 mW cm^?2), we measured a photo-conversion efficiency of 7.18 %, a short-circuit current density of 16.09 mA cm^?2, an open-circuit voltage of 0.69 V, and a fill factor of 0.65 for the DSSC incorporating the gel electrolyte HPIL/IL-B (4:96, w/w). The DSSC incorporating the gel electrolyte HPIL/IL-A (15:85, w/w) exhibited good operational stability, retaining approximately 93 % of its original efficiency after 500 h.

Open image in new window

Graphical abstract An imidazolium iodide-containing hyperbranched polymer ionic liquid HPIL was synthesized for use as the gel electrolyte of dye-sensitized solar cells.