Converting the nanodomains of a diblock-copolymer thin film from spheres to cylinders with an external electric field

We investigate the ability of an applied electric field to convert the morphology of a diblock-copolymer thin film from a monolayer of spherical domains embedded in the matrix to cylindrical domains that penetrate through the matrix. As expected, the applied field increases the relative stability of cylindrical domains, while simultaneously reducing the energy barrier that impedes the transition to cylinders. The effectiveness of the field is enhanced by a large dielectric contrast between the two block-copolymer components, particularly when the low-dielectric contrast component forms the matrix. Furthermore, the energy barrier is minimized by selecting sphere-forming diblock copolymers that are as compositionally symmetric as possible. Our calculations, which are the most quantitatively reliable to date, are performed using a numerically precise spectral algorithm based on self-consistent-field theory supplemented with an exact treatment for linear dielectric materials.

Electric field alignment in thin films of cylinder-forming diblock copolymer

We investigate thin films of cylinder-forming diblock copolymer confined between electrically charged parallel plates, using self-consistent-field theory ( SCFT) combined with an exact treatment for linear dielectric materials. Our study focuses on the competition between the surface interactions, which tend to orient cylinder domains parallel to the plates, and the electric field, which favors a perpendicular orientation. The effect of the electric field on the relative stability of the competing morphologies is demonstrated with equilibrium phase diagrams, calculated with the aid of a weak-field approximation. As hoped, modest electric fields are shown to have a significant stabilizing effect on perpendicular cylinders, particularly for thicker films. Our improved SCFT-based treatment removes most of the approximations implemented by previous approaches, thereby managing to resolve outstanding qualitative inconsistencies among different approximation schemes.

Undulation instability in block-copolymer lamellae subjected to a perpendicular electric field

We examine the stability of lamellar stacks in the presence of an electric field, E-0, applied normal to the lamellae. Calculations are performed with self-consistent field theory (SCFT) supplemented by an exact treatment of the electrostatic energy for linear dielectric materials. The calculations identify a critical electric field, E-0*, beyond which the lamellar stack becomes unstable with respect to undulations. This E-0* rapidly decreases towards zero as the number of lamellae in the stack diverges. Our quantitative predictions for E-0* are consistent with previous experimental measurements by Xu and co-workers.

Laboratory kinetic studies of the reactions of Cl atoms with species of biogenic origin: δ3-Carene, isoprene, methacrolein and methyl vinyl ketone

The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10-10, (2.1 ± 0.5) × 10-10, (3.2 ± 0.5) × 10-10, and (4.9 ± 0.5) × 10-10 cm3 molecule-1 s-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and δ3-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.

Temperature-responsive properties and drug solubilization capacity of amphiphilic copolymers based on N-vinylpyrrolidone and vinyl propyl ether

A series of amphiphilic copolymers were synthesized by free-radical copolymerization of N-vinylpyrrolidone (NVP) with vinyl propyl ether (VPE), and the structure of the copolymers was characterized by elemental analysis and gel permeation chromatography. The reactivity of VPE in copolymerization was found to be significantly lower than the reactivity of NVP, which resulted in a decrease of copolymers’ yields and molecular weights with higher content of VPE in the feed mixture. An investigation of the behavior of the copolymers in aqueous solutions at different temperatures by dynamic light scattering revealed the presence of lower critical solution temperature, which depending on the content of VPE ranged within 23−38 °C. Aqueous solutions of these copolymers were studied by fluorescent spectroscopy with pyrene as a polarity probe to reveal the formation of hydrophobic domains. The copolymers were found to be useful for enhancing the solubility of riboflavin in water.

Coriolis perturbations in the infrared spectrum of ethylene

Rotational structure has been resolved and analyzed in two of the infrared‐active perpendicular bands of C2H4 vapor: the Type b fundamental band, ν10, at 826 cm—1, and the Type c fundamental band, ν7, at 949 cm—1. Many of the individual PP and RR branch lines have been observed. The analysis has been confined to values of the quantum number K≥3, for which energy levels ethylene shows no detectable deviations from a symmetric‐top rotational structure. The analysis reveals a Coriolis interaction between ν7 and ν10, and between ν4 and ν10, and values of the Coriolis constants ζ7,10z and ζ4,10y are obtained; these are related to normal coordinate calculations for the appropriate symmetry species, and force constants are derived to fit the observed zeta constants. The band center of ν10 has been revised from the original figure of 810 cm—1 to the new value, 826 cm—1, and the inactive frequency ν4 is estimated to lie at 1023±3 cm—1, in good agreement with the previous estimate of 1027 cm—1. The change in the value of ν10 leads to a suggested change in the value of the Raman‐active fundamental ν6 from 1236 to 1222 cm—1. New combination bands have been observed at 2174 cm—1, assigned as ν3+ν10; and at 2252 cm—1, assigned as ν4+ν6; also rotational structure has been resolved and analyzed in the ν6+ν10 band at 2048 cm—1. The new data obtained for the C2H4 molecule are summarized in Table XII, with all of the other data presently available on the vibrational and rotational constants.

Vibrational intensities VI: ethylene and its deutero-isotopes

Absolute intensity measurements have been made on the fundamental vibrations of ethylene and four of its deuteroisotopes. The bands were pressure broadened with nitrogen at 50 atmos, and the intensities were determined by the method of Wilson and Wells except that the observed optical density was integrated against logv rather than v. Normal coordinates have been calculated, and the intensities have been interpreted in terms of quantities (∂p/∂Si) giving the change in dipole moment with respect to each internal symmetry coordinate. Data from the different isotopic species have been used to eliminate ambiguities in the interpretation. Effective bond moments are calculated for each symmetry coordinate.

Monte Carlo phase diagram for diblock copolymer melts

The phase diagram for diblock copolymer melts is evaluated from lattice-based Monte Carlo simulations using parallel tempering, improving upon earlier simulations that used sequential temperature scans. This new approach locates the order-disorder transition (ODT) far more accurately by the occurrence of a sharp spike in the heat capacity. The present study also performs a more thorough investigation of finite-size effects, which reveals that the gyroid (G) morphology spontaneously forms in place of the perforated-lamellar (PL) phase identified in the earlier study. Nevertheless, there still remains a small region where the PL phase appears to be stable. Interestingly, the lamellar (L) phase next to this region exhibits a small population of transient perforations, which may explain previous scattering experiments suggesting a modulated-lamellar (ML) phase.

Architectural effect on the surface tension of an ABA triblock copolymer melt

The excess surface energy of lamellae formed by an ABA triblock copolymer melt oriented parallel to a neutral surface is evaluated using self-consistent field theory (SCFT). Consistent with experiments and previous SCFT calculations, we find a preference for the A-rich domains at the surface, which can only be attributed to the architectural asymmetry between the A and B blocks. The behavior was previously attributed to a loss of bridging configurations that occurs when the B-domain resides at the surface. Here we demonstrate that it is actually the presence of chain ends that reduces the excess surface energy of an A-rich domain relative that of a B-rich domain.

Lateral phase separation in grafted diblock copolymer films

Tethered films of polystyrene-block-poly(methyl methacrylate) copolymers of varying composition and molecular weight were investigated using atomic force microscopy and the observed structures compared with theoretical predictions. Although the experimental results were in qualitative agreement with the theory, there was significant quantitative variation. This was attributed to the presence of solvent in the films prior to and during annealing, a hypothesis supported by new preliminary calculations reported here. Solvent exchange experiments (where a good solvent for both polymer blocks was gradually replaced by a selective solvent), were also performed on the films. This procedure generated textured films in which the structure was defined by miscibility of the polymer blocks with the second solvent.

Rates of production of acetate, propionate, and butyrate in the rumen of lactating dairy cows given normal and low-roughage diets

Five lactating dairy cows with a permanent cannula in the rumen were given ( kg DM/d) a normal diet (7.8 concentrates, 5.1 hay) or a low-roughage (LR) diet (11.5 concentrates, 1.2 hay) in two meals daily in a two-period crossover design. Milk fat (g/kg) was severely reduced on diet LR. To measure rates of production of individual volatile fatty acids (VFA) in the rumen, 0.5 mCi 1-C-14-acetic acid, 2-C-14-propionic acid, or 1-C-14-n-butyric acid were infused into the rumen for 22 h at intervals of 2 to 6 d; rumen samples were taken over the last 12 h. To measure rumen volume, we infused Cr-EDTA into the rumen continuously, and polyethylene glycol was injected 2 h before the morning feed. Results were very variable, so volumes measured by rumen emptying were used instead. Net production of propionic acid more than doubled on LR, but acetate and butyrate production was only numerically lower. Net production rates pooled across both diets were significantly related to concentrations for each VFA. Molar proportions of net production were only slightly higher than molar proportions of concentrations for acetate and propionate but were lower for butyrate. The net energy value (MJ/d) of production of the three VFA increased from 89.5 on normal to 109.1 on LR, equivalent to 55 and 64% of digestible energy, respectively. Fully interchanging, three-pool models of VFA C fluxes are presented. It is concluded that net production rates of VFA can be measured in non-steady states without the need to measure rumen volumes.