Crystal-amorphous interphases in binary semicrystalline/amorphous polymer blends

Crystal-amorphous interphases in binary polymer blends that are miscible in the melts but phase separate due to crystallization of one polymer have been investigated theoretically by employing lattice models and experimentally by dielectric spectroscopy measurements. Theory predicts the extent of tight adjacent re-entry to depend strongly on the energy E_q disfavoring the tight-fold conformations and to increase slightly with favorable interaction energy - χ_AB in the blends. The interfacial region of varying composition is predicted to depend strongly on χ_AB, with the interfacial thickness varying with the reciprocal of |χ_AB|^1/2. Therefore, in the limit χ_AB → 0 the amorphous polymer, which is miscible in the melt, is predicted to be completely excluded from the interlamellar region, in agreement with experimental results. Dielectric relaxation experiments on semicrystalline blends of poly(vinylidene fluoride) (PVDF) with poly(methyl methacrylate) (PMMA) or poly(vinyl pyrrolidone) (PVP) show the existence of nearly pure PVDF interphase which is not penetrated by PMMA or PVP, despite their strongly favorable interactions with PVDF. These experimental results are discussed and compared with theoretical predictions.     

Enhanced β‐phase in PVDF polymer nanocomposite and its application for nanogenerator

Harvesting energy from the ambient mechanical energy by using flexible piezoelectric nanogenerator is a revolutionary step toward achieving reliable and green energy source. Polyvinylidene fluoride (PVDF), a flexible polymer, can be a potential candidate for the nanogenerator if its piezoelectric property can be enhanced. In the present work, we have shown that the polar crystalline β‐phase of PVDF, which is responsible for the piezoelectric property, can be enhanced from 48.2% to 76.1% just by adding ZnO nanorods into the PVDF matrix without any mechanical or electrical treatment. A systematic investigation of PVDF‐ZnO nanocomposite films by using X‐ray diffractometer, Fourier transform infrared spectroscopy, and polarization‐electric field loop measurements supports the enhancement of β‐phase in the flexible nanocomposite polymer films. The piezoelectric constant (d₃₃) of the PVDF‐ZnO (15 wt%) film is found to be maximum of approximately −1.17 pC/N. Nanogenerators have been fabricated by using these nanocomposite films, and the piezoresponse of PVDF is found to enhance after ZnO loading. A maximum open‐circuit voltage ~1.81 V and short‐circuit current of 0.57 μA are obtained for 15 wt% ZnO‐loaded PVDF nanocomposite film. The maximum instantaneous output power density is obtained as 0.21 μW/cm² with the load resistance of 7 MΩ, which makes it feasible for the use of energy harvesting that can be integrated to use for driving small‐scale electronic devices. This enhanced piezoresponse of the PVDF‐ZnO nanocomposite film‐based nanogenerators attributed to the enhancement of electroactive β‐phase and enhanced d₃₃ value in PVDF with the addition of ZnO nanorods.     

Thin poly(ionic liquid) and poly(vinylidene fluoride) blend films with ferro‐ and piezo‐electric polar γ‐crystals

Ferro‐ and piezo‐electric poly(vinylidene fluoride) (PVDF) thin film is reported to be obtained by using a poly(ionic liquid) (PIL) [poly(2‐(dimethylamino)ethyl methacrylate) methyl chloride quaternary salt] through solution route. The short range interactions between localized cationic ions of PIL and polar >CF₂ of PVDF are responsible for modified polar γ‐PVDF (T₃GT₃Ḡ) formation. Modification in chain conformation of PVDF is confirmed by FTIR, XRD, and DSC studies suggesting the miscible PVDF–PIL (PPIL) blend. Up to 40 wt % loading of PIL in PVDF matrix enhances relative intensity of γ‐phase up to 50% in the entire crystalline phase. The P‐E hysteresis loop of PVDF‐PIL blends at 25 wt % PIL loading (PPIL‐25) thin film at sweep voltage of ±50 V shows excellent ferroelectric property with nearly saturated high remnant polarization ∼6.0 µC cm⁻² owing to large proportion of γ‐PVDF. However, non‐polar pure PVDF thin film shows unsaturated hysteresis loop with 1.4 µC cm⁻² remnant polarization. The operation voltage decreases effectively because of the polar γ‐phase formation in PPIL blended film. High‐sensitivity piezo‐response force microscopy shows electromechanical switching property at low voltages in PPIL‐25 thin films through local switching measurements, making them potentially suitable as ferroelectric tunnel barriers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 795–802     

Molecular miscible blend of poly(2-cyano-1,4-phenyleneterephthalamide) and polyvinylpyrrolidone characterized by two-dimensional correlation FTIR and solid state C NMR spectroscopy

Miscibility of blends of poly(2-cyano-1,4-phenyleneterephthalamide/polyvinylpyrrolidone) (CN-PPTA/PVP) was investigated by dilute solution viscometry, two-dimensional (2D) correlation Fourier transformed infrared (FTIR) spectroscopy and solid state ¹³C NMR spectroscopy. It was shown that a large proportion of the PVP, the water-soluble component, could not be removed from CN-PPTA by extraction with water, and even with boiling water for blend films, suggesting that the flexible aliphatic PVP chain forms a blend with the rigid aromatic CN-PPTA chain through strong intermolecular interaction making it too difficult to dissolve even in boiling water. Viscometry on a polymer mixture of dilute solution showed that [η]_exp exhibited larger value than [η]_theo in all mixtures used in this experiment, suggesting occurrence of a strong attractive interaction between the two polymers. 2D correlation FTIR spectroscopy revealed that the carbonyl absorption band of PVP at 1675 cm⁻¹ shifted to a new low frequency absorption band at 1640 cm⁻¹ with a change of 35 cm⁻¹, suggesting strong hydrogen bonding with NH (amide II) proton of CN-PPTA. Another new absorption band at 1685 cm⁻¹ was due to the carbonyl absorption band of CN-PPTA shifting to a higher frequency than that at 1662 cm⁻¹, indicating that some of the carbonyl groups in the CN-PPTA components of the blends were in a free state or in a non-hydrogen bonded state as a consequence of the participation of NH proton of CN-PPTA in hydrogen bonding, resulting in the absorption bands of NH bend deformation of CN-PPTA at 1542 and 1313 cm⁻¹ being shifted to higher wavenumber of 1556 and 1324 cm⁻¹, respectively. Solid state ¹³C NMR spectroscopy revealed a chemical shift for CO of the PVP component in the blend fiber changing down-field (shift to left) at 177.346 ppm with a difference of 1.812 ppm; this was due to a lower electron density around the carbon atom of CO of lactam via hydrogen bonding with NH proton of amide in the CN-PPTA component, suggesting that a homogeneous blend of the CN-PPTA and PVP was produced on a molecular scale via hydrogen bonding.     

Preparation and characterization of PVDF‐based blend membranes as polymer electrolyte membranes in fuel cells: Study of factor affecting the proton conductivity behavior

There is a huge demand especially for polyvinylidene fluoride (PVDF) and its copolymers to provide high performance solid polymer electrolytes for use as an electrolyte in energy supply systems. In this regard, the blending approach was used to prepare PVDF‐based proton exchange membranes and focused on the study of factor affecting the ir proton conductivity behavior. Thus, a series of copolymers consisting of poly (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), and poly(2‐acrylamido‐2‐methyl‐l‐propanesulfonic acid) (PAMPS) as sulfonated segments were synthesized and blended with PVDF matrix in order to create proton transport sites in PVDF matrix. It was found that addition of PMMA‐co‐PAMPS and PAN‐co‐PAMPS copolymers resulted in a significant increase in porosity, which favored the water uptake and proton transport at ambient temperature. Furthermore, crystallinity degree of the PVDF‐based blend membranes was increased by addition of the related copolymers, which is mainly attributed to formation of hydrogen bonding interaction between PVDF matrix and the synthesized copolymers, and led to a slight decrease in proton conductivity behavior of blend membranes. From impedance data, the proton conductivity of the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes increases to 10 and 8.4 mS cm⁻¹ by adding only 50% of the related copolymer (at 25°C), respectively. Also, the blend membranes containing 30% sulfonated copolymers showed a power density as high as 34.30 and 30.10 mW cm⁻² at peak current density of 140 and 79.45 mA cm⁻² for the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes, respectively. A reduction in the tensile strength was observed by the addition of amphiphilic copolymer, whereas the elongation at break of all blend membranes was raised.     

Investigations on electrical properties of PVP:KIO4 polymer electrolyte films

Solid polymer electrolytes based on poly(vinyl pyrrolidone) (PVP) complexed with potassium periodide (KIO₄) salt at different weight percent ratios were prepared using solution-cast technique. X-ray diffraction (XRD) results revealed that the amorphous nature of PVP polymer matrix increased with the increase of KIO₄ salt concentration. The complexation of the salt with the polymer was confirmed by Fourier transform infrared (FTIR) spectroscopy studies. The ionic conductivity was found to increase with the increase of temperature as well as dopant concentration. The maximum ionic conductivity (1.421 × 10⁻⁴ S cm⁻¹) was obtained for 15 wt% KIO₄ doped polymer electrolyte at room temperature. The variation of ac conductivity with frequency obeyed Jonscher power law. The dynamical aspects of electrical transport process in the electrolyte were analyzed using complex electrical modulus. The peaks found in the electric modulus plots have been characterized in terms of the stretched exponential parameter. Optical absorption studies were performed in the wavelength range 200–600 nm and the absorption band energies (direct band gap and indirect band gap) values were evaluated. Using these polymer electrolyte films electrochemical cells were fabricated and their discharge characteristics were studied.     

Dielectric spectroscopy of nanocomposites based on iPP and aPS treated in the water solutions of alkali metal salts

In this paper, a new simple and environmentally friendly treatment technique for obtaining polymer nanocomposites with appropriate dielectric properties has been presented. Sheets of isotactic polypropylene and atactic polystyrene were immersed in 3 saturated water solutions of alkali metal salts (LiCl, NaCl, and KCl) at 2 fixed temperatures (23°C and 90°C), and 3 DC electrical potentials (+4 kV, −4 kV, and ground potential) were applied. A quantification of alkali metals in the polymer sheets was conducted by inductively coupled plasma optic emission spectrometry. The obtained concentration values were from 7.38·10⁻⁹ mol/cm³ to 1.25·10⁻⁷ mol/cm³. The qualitative analysis of potassium distribution in the polymer matrix was conducted by time‐of‐flight secondary ion mass spectrometry cross‐sectional record. The relative dielectric constant (ε′) of samples was investigated in the frequency range from 20 Hz to 9 MHz at the constant temperature of 22°C. Stable values of ε′ in fully measured frequency range were observed for both pure and treated samples. Next, the results of the dielectric spectroscopy measurements were compared and established the kind of treatment that provided the highest value of ε′. The relationship between the concentrations of alkali metals and the values of relative dielectric constant was determined for the samples obtained by a treatment at 90°C and +4 kV.     

EPR spectroscopy of multicomponent,multispin molecular system obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon

Complex multicomponent, multispin molecular system, consisting of a septet trinitrene, two quintet dinitrenes, and three triplet mononitrenes, was obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon. To identify these paramagnetic products, electron paramagnetic resonance spectroscopy in combination with line-shape spectral simulations and density functional theory calculations was used. The products of the photolysis was found to be triplet 2,4-diazido-3-cyano-5-fluoropyridyl-6-nitrene (D_T = 1.000 cm⁻¹, E_T = 0), triplet 2,4-diazido-3-cyano-5-fluoropyridyl-2-nitrene (D_T = 1.043 cm⁻¹, E_T = 0), triplet 2,6-diazido-3-cyano-5-fluoropyridyl-4-nitrene (D_T = 1.128 cm⁻¹, E_T = 0 cm⁻¹), quintet 4-azido-3-cyano-5-fluoropyridyl-2,6-dinitrene (D_Q = 0.211 cm⁻¹, E_Q = 0.0532 cm⁻¹), quintet 2-azido-3-cyano-5-fluoropyridyl-4,6-dinitrene (D_Q = 0.208 cm⁻¹, E_Q = 0.0386 cm⁻¹), and septet 3-cyano-5-fluoropyridyl-2,4,6-trinitrene (D_S = −0.1017 cm⁻¹, E_S = −0.0042 cm⁻¹) in a 38:4:7:22:14:4 ratio, respectively.     

Nanocomposites induced by two-dimensional titanium carbide nanosheets for highly efficient energy storage

Surface group-rich titanium carbide nanosheets (TCNSs) were successfully fabricated by simply etching Ti₃AlC₂ powders and used as dielectric fillers to promote the dielectric and energy storage performances of poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)-based composites. The PVDF-HFP/TCNS composites realize a high dielectric constant and low dielectric loss of 16.3 and 0.034 at 10² Hz, respectively. Importantly, a high energy storage density (U_e) of 0.367 J cm⁻³ at 900 kV cm⁻¹ and a high energy storage efficiency (η ≥ 78.9%) at a TCNS content of only 0.5 wt% are obtained, which indicates that incorporating TCNS is an efficient route in enhancing U_e while maintaining a high level η of the PVDF-HFP-based composites. According to detailed characterization results, a mechanism related to the reduction of lamellar crystals in the PVDF-HFP matrix is suggested. The above mechanism restricts the movement of polymer chains near the filler-matrix interface and is proposed to be responsible for the outstanding dielectric and energy storage performances. Consequently, this work provides a simple and effective method for fabricating highly efficient energy storage nanocomposites.     

Porous Cyclodextrin Polymer Enables Dendrite-Free and Ultra-Long Life Solid-State Zn-I2 Batteries

Zn-I₂ batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD-Si) by nucleophilic reaction of β-cyclodextrin with SiCl₄, and CD-Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD-Si) to solve above-mentioned problems. Through the anchoring of the CD-Si, a conductive network with dual transmission channels was successfully constructed. Due to the non-covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10⁻³ S cm⁻¹ at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite-free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm⁻² and 1200 h at 20 mA cm⁻²). The solid-state Zn-I₂ battery shows an ultra-long life of over 35,000 cycles at 2 A g⁻¹. Molecular dynamics simulations are performed to elucidate the working mechanism of CD-Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn-I₂ batteries.     

Polymer electrolyte membranes by in situ polymerization of poly(ethylene carbonate‐co‐ethylene oxide) macromonomers in blends with poly(vinylidene fluoride‐co‐hexafluoropropylene)

Salt‐containing membranes based on polymethacrylates having poly(ethylene carbonate‐co‐ethylene oxide) side chains, as well as their blends with poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP), have been studied. Self‐supportive ion conductive membranes were prepared by casting films of methacrylate functional poly(ethylene carbonate‐co‐ethylene oxide) macromonomers containing lithium bis(trifluorosulfonyl)imide (LiTFSI) salt, followed by irradiation with UV‐light to polymerize the methacrylate units in situ. Homogenous electrolyte membranes based on the polymerized macromonomers showed a conductivity of 6.3 × 10^?6 S cm^?1 at 20 °C. The preparation of polymer blends, by the addition of PVDF‐HFP to the electrolytes, was found to greatly improve the mechanical properties. However, the addition led to an increase of the glass transition temperature (T_g) of the ion conductive phase by ～5 °C. The conductivity of the blend membranes was thus lower in relation to the corresponding homogeneous polymer electrolytes, and 2.5 × 10^?6 S cm^?1 was recorded for a membrane containing 10 wt % PVDF‐HFP at 20 °C. Increasing the salt concentration in the blend membranes was found to increase the T_g of the ion conductive component and decrease the propensity for the crystallization of the PVDF‐HFP component. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 79–90, 2007     

Mechanical and dielectric behavior of poly(vinylidene)–poly(arylene ether nitrile) composites as film capacitors for energy storage applications

Novel polymer composites PEN/PVDF were prepared from poly(arylene ether nitrile) (PEN) and poly(vinylidene fluoride) (PVDF) via solution mixing. Due to the toughening effect of PVDF, PEN/PVDF blends with 5 wt % PVDF exhibit higher tensile strength (106 MPa) and breaking elongation (8.09%) than pure PEN does. Because of introduction of PVDF and interfacial polarization, the dielectric constant of PEN/PVDF blends at 1 kHz and room temperature increases from 3.3 to 4.5 with increasing content of PVDF. The dissipation factor (tanδ) of PEN/PVDF blends is relatively low (<0.04) in a very wide frequency range from 250 Hz to 100 kHz. The PEN/PVDF blends show certain piezoelectric behavior (d ₃₃ from 0.9 to 1 pC/N) due to the contribution of PVDF. After polarization, the piezoelectric coefficient d ₃₃ somewhat increases. The results suggest that PEN/PVDF blends will have potential application in electronic information fields, especially in film capacitors.     

The mechanism of α-γ transition of poly- (vinylidene fluoride) in the miscible blends

The simultaneous DSC-FTIR was used for the observation of crystallization and melting of poly(vinylidene fluoride) (PVDF) and its blends with poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The isothermal crystallization was carried out under the condition of both α-form and γ-form crystallized competitively. The crystal growth rate of α -form and γ -form were evaluated from the absorbance changes at 795 cm^-1 (α -form, CH₂ rocking) and 810 cm^-1 (γ -form, CH₂ rocking) obtained by the DSC-FTIR. The crystal growth rate of γ -form decreased at the same crystallization temperature in the order of PVDF/syn-PMMA, PVDF/PEMA and PVDF/at-PMMA, which was corresponding to the order of interaction parameter. The mechanism of α -g transition of PVDF in the miscible blends with at-PMMA, syn-PMMA and PEMA was evaluated from the relationship between the decrease of α -form and the increase of γ -form. The critical crystallization temperature, at which the transformation from α -form to γ -form proceeded only in the solid state, shifted to higher temperature side in the order of interaction parameter. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ternary blends of poly(ethylene oxide) and acrylate-based copolymers: Crystallinity, miscibility, interactions and proton conductivity

In the present work, blends of poly(ethylene oxide) (PEO), poly(acrylonitrile-co-methyl acrylate) (PANMA) and poly(4-vinylphenol-co-2-hydroxyethyl methacrylate) (PVPh-HEM) were studied by DSC, FTIR and electrochemical impedance spectroscopy (EIS). PEO/PANMA blends were found to be immiscible, while PEO/PVPh-HEM blends are miscible and PVPh-HEM/PANMA exhibits partial miscibility behaviour. The ternary PEO/PANMA/PVPh-HEM blends exhibited miscible compositions for PVPh-HEM and PEO-rich systems. The miscibility observed is a direct consequence of the hydrogen bond interactions among the polymer chains, in which the phenol groups in PVPh-HEM interact with both PEO and PANMA chains. The proton conductivity of a selected membrane based on the ternary blend containing 60% PEO and doped with H₃PO₄ aqueous solution reached 8 × 10⁻³ Ω⁻¹ cm⁻¹ at room temperature and 3 × 10⁻² Ω⁻¹ cm⁻¹ at 80 °C.     

To Study the Effect of Nanoparticle TiO2 on Sodium (Na+) – Ion Conducting Solid Polymer Electrolyte System: [80PEO:20NaPF6]

To study the effect of nanofiller particle TiO₂ on sodium (Na⁺) – ion conducting solid polymer electrolyte (SPE) film: [80PEO:20NaPF₆] and nanocomposite polymer electrolyte (NCPE): [80PEO:20NaPF₆] + xTiO₂, where x = 1–9 wt. (%) have been prepared. SPE film composition: [80PEO:20NaPF₆] selects as Ist-phase host and nano-sized (<100 nm) filler materials TiO₂ as IInd-phase dispersoid. Both SPE and NCPE films have been prepared by the hot-press technique. Filler particle-dependent conductivity study reveals the NCPE system: [80PEO:20NaPF₆] + 8TiO₂ as the highest conducting composition with σ_rt − 3.53 × 10⁻⁶ S cm⁻¹, which is approximately one order of magnitude higher than the SPE optimum conducting composition (OCC) (σ_rt) ≈ 7.78 × 10⁻⁷ S cm⁻¹. Ion transport properties for both SPE and NCPE system have been evaluated in terms of ionic conductivity (σ) and total ionic (t_ion)/cationic (t₊) transference numbers using combined AC/DC techniques in order to evaluate its usefulness in all-solid-state battery applications. Structural/thermal properties have been characterized using X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques. A cyclic voltammetry (CV) study has been performed in SPE and NCPE OCC film to evaluate the electrochemical performance for battery application.     

Study of the reactions of OH with HCl,HBr, and HI between 298 K and 460 K

The reactions between OH radicals and hydrogen halides (HCl, HBr, HI) have been studied between 298 and 460 K by using a discharge flow-electron paramagnetic resonance technique. The rate constants were found to be k_HCl(298 K) = (7.9 ± 1.3) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ with a weak positive temperature dependence, k_HBr (298-460 K) = (1.04 ± 0.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, and k_HI(298 K) = (3.0 ± 0.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, respectively. The homogeneous nature of these reactions has been experimentally tested.     

An enhanced poly(vinylidene fluoride) matrix separator with TEOS for good performance lithium-ion batteries

The low crystallinity poly(vinylidene fluoride)/tetraethyl orthosilicate silane (PVDF/TEOS) composite separator with a finger-like pore structure for lithium-ion battery has been successfully prepared by non-solvent-induced phase separation (NIPS) technique. The PVDF/TEOS composite separator shows the excellent wettability and electrolyte retention properties compared with Celgard 2320 separator. AC impedance spectroscopy results indicate that the novel PVDF/TEOS composite separator has ion conductivity of 1.22 mS cm⁻¹ at 25 °C, higher than that of Celgard 2320 separator (0.88 mS cm⁻¹). The lithium-ion transference number of PVDF composite separator added 0.7% TEOS was 0.481, better than that of Celgard 2400 (0.332). What is more, the lithium-ion batteries assembled with PVDF/TEOS composite separator show good cycling performance and rate capability.

     

Dithienobenzothiadiazole‐Based Conjugated Polymer: Processing Solvent‐Relied Interchain Aggregation and Device Performances in Field‐Effect Transistors and Polymer Solar Cells

DTfBT‐Th₃, a new conjugated polymer based on dithienobenzothiadiazole and terthiophene, possesses a bandgap of ≈1.86 eV and a HOMO level of −5.27 eV. Due to strong interchain aggregation, DTfBT‐Th₃ can not be well dissolved in chloro­benzene (CB) and o‐dichlorobenzene (DCB) at room temperature (RT), but the polymer can be processed from hot CB and DCB solutions of ≈100 °C. In CB, with a lower solvation ability, a certain polymer chain aggregation can be preserved, even in hot solution. DTfBT‐Th₃ displays a field‐effect hole mobility of 0.55 cm² V⁻¹ s⁻¹ when fabricated from hot CB solution, which is higher than that of the device processed from hot DCB (0.16 cm² V⁻¹ s⁻¹). In DTfBT‐Th₃‐based polymer solar cells, a good power conversion efficiency from 5.37% to 6.67% can be achieved with 150−300 nm thick active layers casted from hot CB solution, while the highest efficiency for hot DCB‐processed solar cells is only 5.07%. The results demonstrate that using a solvent with a lower solvation ability, as a “wet control” process, is beneficial to preserve strong interchain aggregation of a conjugated polymer during solution processing, showing great potential to improve its performances in optoelectronic devices.

     

Experimental determination of the rate constants of the reactions of HO2 + DO2 and DO2 + DO2

The rate constants of the reactions of DO₂ + HO₂ (R1) and DO₂ + DO₂ (R2) have been determined by the simultaneous, selective, and quantitative measurement of HO₂ and DO₂ by continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near infrared, coupled to a radical generation by laser photolysis. HO₂ was generated by photolyzing Cl₂ in the presence of CH₃OH and O₂. Low concentrations of DO₂ were generated simultaneously by adding low concentrations of D₂O to the reaction mixture, leading through isotopic exchange on tubing and reactor walls to formation of low concentrations of CH₃OD and thus formation of DO₂. Excess DO₂ was generated by photolyzing Cl₂ in the presence of CD₃OD and O₂, small concentrations of HO₂ were always generated simultaneously by isotopic exchange between CD₃OD and residual H₂O. The rate constant k₁ at 295 K was found to be pressure independent in the range 25–200 Torr helium, but increased with increasing D₂O concentration k₁ = (1.67 ± 0.03) × 10⁻¹² × (1 + (8.2 ± 1.6) × 10⁻¹⁸ cm³ × [D₂O] cm⁻³) cm³ s⁻¹. The rate constant for the DO₂ self-reaction k₂ has been measured under excess DO₂ concentration, and the DO₂ concentration has been determined by fitting the HO₂ decays, now governed by their reaction with DO₂, to the rate constant k₁. A rate constant with insignificant pressure dependence was found: k₂ = (4.1 ± 0.6) × 10⁻¹³ (1 + (2 ± 2) × 10⁻²⁰ cm³ × [He] cm⁻³) cm³ s⁻¹ as well as an increase of k₂ with increasing D₂O concentration was observed: k₂ = (4.14 ± 0.02) × 10⁻¹³ × (1 + (6.5 ± 1.3) × 10⁻¹⁸ cm³ × [D₂O] cm⁻³) cm³ s⁻¹. The result for k₂ is in excellent agreement with literature values, whereas this is the first determination of k₁.     

Characterization and evaluation of commercial poly (vinylidene fluoride)‐g‐sulfonatedPolystyrene as proton exchange membrane

The possibility of developing low‐cost commercial grafted and sulfonated Poly(vinylidene fluoride) (PVDF‐g‐PSSA) membranes as proton exchange membranes for fuel cell applications have been investigated. PVDF‐g‐PSSA membranes were systematically prepared and examined with the focus of understanding how the polymer microstructure (degree of grafting and sulfonation, ion‐exchange capacity, etc) affects their methanol permeability, water uptake, and proton conductivity. Fourier transform infrared spectroscopy was used to characterize the changes of the membrane's microstructure after grafting and sulfonation. The results showed that the PVDF‐g‐PSSA membranes exhibited good thermal stability and lower methanol permeability. The proton conductivity of PVDF‐g‐PSSA membranes was also measured by the electrochemical impedance spectroscopy method. It was found that the proton conductivity of PVDF‐g‐PSSA membranes depends on the degree of sulfonation. All the sulfonated membranes show high proton conductivity at 92°C, in the range of 27 to 235 mScm⁻¹, which is much higher than that of Nafion212 (102 mScm⁻¹ at 80°C). The results indicated that the PVDF‐g‐PSSA membranes are particularly promising membranes to be used as polymer electrolyte membranes due to their excellent stability, low methanol permeability, and high proton conductivity.