Phase equilibria of quasi-binary systems consisting of multicomponent polymers 1 and 2. IV: Poly(ethylene oxide)/poly(propylene oxide) systems

To confirm the reliability of the theory of phase equibria of multicomponent polymer 1/multicomponent polymer 2 systems (i.e. quasi-binary systems) and the method of computer experiment based on this theory (Brit. Polym. J., 23 (1990)285; 23 (1990)299; Polym. Int., 29 (1992)219), could point curves (CPC), two-phase volume ratios ( R ) and critical solution points (CSP) have been determined experimentally for the quasi-binary mixtures of poly(ethylene oxide) (M¯_w = 647, M¯_w/M¯_n = 1.15; M¯_w and M¯_n, the weight-average and numberaverage molecular weights, respectively) and poly(propylene oxide) (M¯_w = 2028, M¯_w/M¯_n = 1.08; and M_w = 2987, M_w/M_n = 1.13). The hydroxyl end groups of both polymers were methoxylated in advance by the Cooper & Booth method (Polymer, 18 (1977)164). The thermodynamic interaction parameter between both polymers, χ₁₂, and the concentration dependence parameters for the above quasi-binary systems were determined by the method proposed in a previous paper (Brit. Polym. J., 23 (1990)299). CPC, R and CSP values calculated on the basis of the theory are in good agreement with the values determined experimentally.     

Optical data storage by novel photoelectrochromic polymer

A novel elastic polymer containing 4,4′-bipyridinium salts with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as part of the main chain was synthesized. The cast film showed persistent and reversible colour changes due to photoinduced electron transfer upon excitation of an ion-pair charge-transfer band (_ex >365 nm) in vacuo. The lifetime of the coloured state markedly depended on temperature. The optically written data were stored without decay below 0°C and were erased thermally at elevated temperatures. The colour changes were reversibly repeatable for many times.     

Surface tailoring of an ethylene propylene diene elastomeric terpolymer via plasma‐polymerized coating of tetramethyldisiloxane

In the research presented here, we explore the use of a low‐energy plasma to deposit thin silicone polymer films using tetramethyldisiloxane (TMDSO) (H(CH₃)₂? Si? O? Si? (CH₃)₂H) on the surface of an ethylene propylene diene elastomeric terpolymer (EPDM) in order to enhance the surface hydrophobicity, lower the surface energy and improve the degradation/wear characteristics. The processing conditions were varied over a wide range of treatment times and discharge powers to control the physical characteristics, thickness, morphology and chemical structure of the plasma polymer films. Scanning electron microscopy (SEM) shows that pore‐free homogeneous plasma polymer thin films of granular microstructure composed of small grains are formed and that the morphology of the granular structure depends on the plasma processing conditions, such as plasma power and time of deposition. The thicknesses of the coatings were determined using SEM, which confirmed that the thicknesses of the deposited plasma‐polymer films could be precisely controlled by the plasma parameters. The kinetics of plasma‐polymer film deposition were also evaluated. Contact angle measurements of different solvent droplets on the coatings were used to calculate the surface energies of the coatings. These coatings appeared to be hydrophobic and had low surface energies. X‐ray photoelectron spectroscopy (XPS) and photoacoustic Fourier‐transform infrared (PA‐FT‐IR) spectroscopy were used to investigate the detailed chemical structures of the deposited films. The optimum plasma processing conditions to achieve the desired thin plasma polymer coatings are discussed in the light of the chemistry that takes place at the interfaces. Copyright © 2004 Society of Chemical Industry     

Cover Picture: Toward Large‐Scale Alignment of Electrohydrodynamic Patterning of Thin Polymer Films (Adv. Funct. Mater. 15/2006)

By integrating lithography and self‐assembly via electrohydrodynamic instabilities, Russel and co‐workers are able to guide initially flat polymer films to evolve into periodic arrays of pillars over regions much greater in extent than their natural domain sizes, as detailed on p. 1992. Novel structures that involve a combination of linear ridges and pillars are also produced, mainly as as result of the dynamic merging among preformed pillars. To pattern thin polymer films via electrohydrodynamic instabilities, we design and utilize two different kinds of mask patterns to guide pillars into alignment over regions much greater in extent than their natural domain sizes. First, narrow protruding ridges that intersect to form regular patterns on the mask trigger the growth of pillars beneath. Later, square and triangular packings of pillars develop in the regions enclosed by those ridges, preserving the registry from one domain to the next over a much larger area than within individual domains in unpatterned portions of the mask. Second, small square protrusions that are prealigned into a large regular array on the mask guide the formation of square packings of pillars in domains that conform to the mask, forming a large array of pillars. Novel structures involving a combination of linear ridges and pillars are also produced mainly due to the dynamic merging among preformed pillars. Finally, we find vertex symmetry of the mask pattern is necessary for generating and preserving ordered patterns on the polymer film.     

Phase equilibrium in solutions of star-shaped macromolecules: an improved Okada-Numasawa model

The two-region Okada-Numasawa model for solutions of star-shaped polymers has been improved by means of a change in the integration order and introduction of a concentration-dependent and molar-mass-dependent Flory-Huggins interaction parameter (the second and third approximations of the Flory-Huggins theory). To overcome calculation difficulties, a special algorithm for computing coexistence curves of polymeric systems with an UCST has been used. The agreement between the experimental and calculated coexistence curves for the star-shaped polystyrene (PS)-cyclohexane system has been improved: the difference between T_cs is ∼0.33 K against ∼12 K as given by the original model.     

Sol-gel preparation of a di-ureasil electrolyte doped with lithium perchlorate

Solid polymer electrolytes (SPEs) synthesized by the sol-gel process and designated as di-ureasils have been prepared through the incorporation of lithium perchlorate, LiClO₄, into the d-U(2000) organic-inorganic hybrid network. Electrolytes with lithium salt compositions of n (where n indicates the number of oxyethylene units per Li⁺ ion) between ∞ and 0.5 were characterized by conductivity measurements, cyclic voltammetry at a gold microelectrode, thermal analysis and Fourier transform Raman (FT-Raman) spectroscopy. The conductivity results obtained suggest that this system offers a quite significant improvement over previously characterized analogues doped with lithium triflate [S.C. Nunes, V. de Zea Bermudez, D. Ostrovskii, M.M. Silva, S. Barros, M.J. Smith, R.A. Sá Ferreira, L.D. Carlos, J. Rocha, E. Morales, J. Electrochem. Soc. 152 (2) (2005), A429]. “Free” perchlorate ions, detected in all the samples examined, are identified as the main charge carriers in the sample that yields the highest room temperature conductivity (n = 20). In the di-ureasils with n ≤ 10 ionic association is favoured and the ionic conductivity drops.     

Cover Picture: Light‐Emitting Organic Solar Cells Based on a 3D Conjugated System with Internal Charge Transfer (Adv. Mater. 22/2006)

The cover image illustrates the dual photovoltaic and electroluminescence function of a single‐layer device based on a thienylenevinylene–triphenylamine with internal charge transfer (ICT), as reported by Cravino, Roncali, and co‐workers on p. 3033. The material forms an organic glass with isotropic electronic properties while ICT leads simultaneously to an extension of the photoresponse to the red and to an increase of the open circuit voltage. The use of an additional layer of C₆₀ further improves the photovoltaic. Images of the sun and moon courtesy NASA/JPL–Caltech.     

Effects of multiple weak interactions on the binding of phenolic compounds by polymeric adsorbents

To investigate the effects of multiple weak interactions on the binding of phenolic compounds by polymeric adsorbents, macroporous polystyrene (PS) resin and PS‐based adsorbents with different hydrogen‐bond acceptor atoms (PS CH₂( OCH₂CH₂)_n OCH₃, n = 0, 1, 2, and 3, denoted as PS‐EG₀, PS‐EG₁, PS‐EG₂, and PS‐EG₃) were prepared. The phenol adsorption strength order on these adsorbents was PS/PS‐EG₀ < PS‐EG₁ < PS‐EG₂ < PS‐EG₃, indicating that the adsorption on PS and PS‐EG₀ was driven by hydrophobic and π–π interactions, and the adsorption on PS‐EG₁, PS‐EG₂, and PS‐EG₃ was driven by a hydrogen bond in addition to hydrophobic and π–π interactions. PS‐EG₂ may adsorb a second phenol molecule on each binding site and PS‐EG₃ may adsorb second and third ones. The adsorption strength of resorcinol increased in the order of PS, PS‐EG₁, and PS‐EG₂, indicating that the adsorption was driven by 0, 1, and 2 hydrogen bonds in addition to hydrophobic and π–π interactions. Similarly, the adsorption of phloroglucinol on PS, PS‐EG₁, PS‐EG₂, and PS‐EG₃ was driven by 0, 1, 2, and 3 hydrogen bonds in addition to hydrophobic and π–π interactions because the adsorption strength increased in this order. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4652–4658, 2006     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

Morphology development in polyethylene/polystyrene blends: the influence of processing conditions and interfacial modification

The influence of processing conditions and interfacial modification on the morphology evolution and the composition range within which fully co‐continuous high density polyethylene/polystyrene blend structures can exist during blending in a single screw extruder was studied. Blends ranging from pure A to pure B component, with and without compatibilizer, were prepared under two different shear rates. It was found that high shear rates displaced the breakdown–coalescence balance of the dispersed nodules to the side of coalescence, narrowing the percolation domain and the critical composition for full co‐continuity decreased with increasing shear rates. The addition of a tri‐block compatibilizer induced the percolation threshold of the polystyrene phase to begin at lower percentages of polyethylene but the phase inversion point did not change. The experimental results are discussed in the light of various theoretical models. Copyright © 2005 Society of Chemical Industry