Gerrit Brinke

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Papers by Gerrit Brinke

Macromol. Rapid Commun. 4/2011

Macromolecular Rapid Communications, 2011

For the first time a bicontinuous structure, with the supramolecular blocks forming the core of t... more For the first time a bicontinuous structure, with the supramolecular blocks forming the core of the core-shell gyroid morphology, has been realized in block copolymer-based hydrogen-bonded side-chain supramolecules. By dissolving the side chains well-ordered nanoporous films were obtained. Further information can be found in the article by G. G. du Sart, I. Vukovic, Z. Vukovic, E. Polushkin, P. Hiekkataipale, J. Ruokolainen, K. Loos,* and G. ten Brinke* on page 366. Back Cover: The image shows walnutlike microparticles with supramolecular liquid-crystalline ordering fabricated by combining a simple self-organized precipitation method with hydrogen-bonding interactions. Their morphologies can be easily controlled with the feed ratio between an azopyridyl polymer and sebacic acid. Further details can be found in the article by H. Liu, T. Kobayashi, and H. Yu* on page 378.

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Lower critical solution temperature behavior of ethylene propylene copolymers in multicomponent solvents

Journal of Applied Polymer Science, 1986

The lower critical solution temperature (LCST) locus for ethylene-propylene copolymers has been d... more The lower critical solution temperature (LCST) locus for ethylene-propylene copolymers has been determined as a function of pressure in a variety of single and multicomponent solvents. The lower critical end-point temperature (LCEP), which is the intersection of the LCST locus with the vapor-pressure curve, was found to be predictable from the solvent density as previously established for single-component solvents by Charlet and Delmas.1 Dissolving a low-molecular hydrocarbon gas such as propylene in an alkane has a dramatic effect on lowering the LCEP, and can reduce phase-separation temperatures to levels at which this technique becomes attractive as a practical method for polymer recovery from diluents such as those used in solution polymerizations. Temperatures considerably above the LCEP are needed to minimize the residual polymer concentration in the solvent in the two-liquid-phase region. The solvent critical temperature must be approached for essentially complete elimination of the polymer from the solvent phase. The LCST locus was found to be a linear function of pressure for all of the systems investigated, and the slope of the line, d(LCST)/dP, could be well correlated as a function of solvent density and critical temperature. From the relationship between the LCEP and solvent density and the correlation for d(LCST)/dP, the location of the LCST locus can be readily predicted from a knowledge of solvent properties.

Ordered structures of molecular bottlebrushes

Trends in Polymer Science, 1997

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Mathematical modeling of the effects of annealing on enthalpy relaxations of polymer interfaces

Macromolecules, 1990

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Miscibility of poly(vinyl chloride) and poly(vinyl acetate)

Macromolecules, 1991

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Compositional and Orientational Ordering in Rod−Coil Diblock Copolymer Melts

Macromolecules, 2002

Compositional and orientational ordering in rod-coil diblock copolymer melts Reenders, M.; ten Br... more

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Orientation and shape of flexible polymers in a slit

The Journal of Chemical Physics, 1990

The shape and orientation of a polymer in a good solvent confined between two parallel plates is ... more The shape and orientation of a polymer in a good solvent confined between two parallel plates is investigated by Monte Carlo simulations of self-avoiding random walks on a simple cubic lattice. Decreasing the width of the slit, the coil starts, due to its anisotropic shape, to orient long before its shape changes. Only after the longest principal axis is aligned considerably parallel to the plates, the coil is squeezed. Using a scaled distance between the plates, a corresponding state behavior as a function of chain length is found. The results are in good agreement with predictions based on an analytical rigid ellipsoid model with principal axes’ lengths set equal to the span lengths along the principal axes of inertia of the self-avoiding random walk.

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Chain elongation suppression of cyclic block copolymers in lamellar microphase-separated bulk

The Journal of Chemical Physics, 2004

Chain elongation suppression of cyclic block copolymers in microphase-separated bulk was determin... more Chain elongation suppression of cyclic block copolymers in microphase-separated bulk was determined quantitatively. Solvent-cast and annealed films are confirmed to show alternating lamellar structure and their microdomain spacing D increases with increasing total molecular weight M according to the relationship D∝M0.59, which agrees quite consistently with the theoretically predicted power law, i.e., D∝M3/5. This result is in contrast to the well-established issue for linear block copolymers, where the relationship D∝M2/3 has been confirmed to hold both experimentally and theoretically. This means that chain elongation of each component block is suppressed considerably, owing to their looped conformation in strongly segregated bulk.

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Poly(para-dioxanone) and poly(L-lactic acid) blends: thermal, mechanical, and morphological properties

Journal of Applied Polymer Science, 2003

Blends of two semicrystalline polymers, poly(l-lactic acid) (PLLA) and poly-p-dioxanone (PPD) hav... more Blends of two semicrystalline polymers, poly(l-lactic acid) (PLLA) and poly-p-dioxanone (PPD) have been prepared by solvent casting in different compositions. Thermal, morphological, and mechanical properties of the blends were studied using modulated differential scanning calorimetry, wide-angle X-ray diffractometry, scanning elec- tron microscopy (SEM), polarizing light microscopy (PLM), and tensile tests. Thermal analysis showed two glass transi- tion temperatures nearly constant

Determination of the Flory-Huggins interaction parameter of polystyrene?polybutadiene blends by thermal analysis

Journal of Applied Polymer Science, 1997

Blends of polystyrene (PS) and polybutadiene (PBD) were investigated by differential scanning cal... more Blends of polystyrene (PS) and polybutadiene (PBD) were investigated by differential scanning calorimetry. From the phase composition diagram of the blends, it appears that PBD dissolves more in the PS-rich phase than does PS in the PBD-rich phase. This result is consistent with the behavior of the specific heat increment at the glass transition temperature of PBD in the PS-PBD blends. From the measured glass transition temperature and apparent weight fractions of PS and PBD dissolved in each phase, values of the Flory-Huggins polymer-polymer interaction parameter (x 12) were determined to be 0.0040-0.0102 depending on the composition and molecular weights of the PS and the PBD. No significant difference in x 12 was observed among the blending methods. The composition-dependent value of the Flory-Huggins polymer-polymer interaction parameter was found to be similar to the value of x 12. The polymer-polymer interaction parameter appears to depend on the degree of polymerization of the polymers as well as on the apparent volume fraction of the polymers dissolved in each phase.

$Figure 2 Phase composition diagram of PS 116,000-— PBD 270,000 blends from (A, ©) solution casting and (A, @) freeze-drying: (A, A) weight fraction of PS in the PS-rich phase; (O, @) weight fraction of PS in the PBD-rich phase. In the present study, this behavior is explained quantitatively” in Figures 1—4 in which are pre-$

$Figure 1 Phase composition diagram of PS 237,700-— PBD 270,000 blends from (A, ©) solution casting and (A, @) freeze-drying: (A, A) weight fraction of PS in the PS-rich phase; (O, @) weight fraction of PS in the PBD-rich phase.$

$Table II Apparent Weight Fraction (W) and Apparent Volume Fraction (@) of PS and PBD Components in the PS-rich Phase and the PBD-rich Phase and the Polymer—Polymer Interaction Parameter of PS 237,000—PBD 270,000 Mill Blends * Blend composition given as overall weight fraction PS in the PS—PBD blend. » Data from Kim and Burns.’ Subscript 1 denotes PS component. 7;,’s are in K. ° Single prime denotes PS-rich phase; double prime denotes PBD-rich phase. wi} is calculated from eq. (2). 4 All gy’s are calculated from eqs. (6) and (7). © All y,.’s are calculated from ea. (5).$

$* Blend composition given as overall weight fraction PS in the PS—PBD blend. All apparent weight fractions are calculatec from eq. (4). » All y’s are calculated from eq. (5). ° All gio’s are calculated from eqs. (6) and (7). Table IV Comparison of the Polymer-Polymer Interaction Parameter, yi. and £12, for the Different Molecular Weights of PS and PBD in PS-PBD Solution-cast Blends$

$Figure 3 Phase composition diagram of PS 237,700-— PBD 128,000 blends from (A, ©) solution casting and (A, @) freeze-drying: (A, A) weight fraction of PS in the PS-rich phase; (O, @) weight fraction of PS in the PBD-rich phase.$

$Figure 4 Phase composition diagram of PS 116,000-— PBD 128,000 blends from (A, ©) solution casting and (A, @) freeze-drying: (A, A) weight fraction of PS in the PS-rich phase; (O, @) weight fraction of PS in the PBD-rich phase. sented phase composition diagrams of solution- cast and freeze-dried PS 237,700—PBD 270,000, PS 116,000—PBD 270,000, PS 237,700—PBD 128,000, and PS 116,000—PBD 128,000 blends, respectively. From Figures 1—4, we can see that the amount of PS dissolved in the PBD-rich phase (W 17) is less than the amount of PBD dissolved in$

$Figure 5 Model calculation of polymer—polymer in- teraction parameter (g12) with degree of polymerization (m;) and apparent volume fraction (¢;).”$

$Table V Comparison of the Polymer-Polymer Interaction Parameter, 12 and 212, for the Differe Molecular Weights of PS and PBD in PS-PBD Freeze-dried Blends * Blend composition given as overall weight fraction PS in the PS—PBD blend. All apparent weight fractions are calculated from eq. (4). » All yw’s are calculated from eq. (5). © All gi’s are calculated from eqs. (6) and (7).$

$Table VI Interaction Parameters for PS 233,000-—PBD 270,000-Toluene* * Data from Narasimhan et al.® ’ Blend composition given as overall weight fraction PS in the PS—PBD blend.$

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Spectra of Liouville operators

Communications in Mathematical Physics, 1976

Ordered Arrays of Ferroelectric Nanoparticles by Pulsed Laser Deposition on PS-b-P4VP(PDP) Supramolecule-Based Templates

Chemistry of Materials, 2009

Thin films of comb-shaped supramolecules have been used to create arrays of spatially separated o... more Thin films of comb-shaped supramolecules have been used to create arrays of spatially separated ordered nanorods with a polystyrene core and a poly(4-vinyl pyridine) corona. Room temperature pulsed laser deposition of a uniform layer of lead titanate on top of these nanorod arrays and subsequent heating to 565°C, far above the degradation temperature of the block copolymer nanorods, resulted in ordered arrays of ferroelectric lead titanate nanoparticles, due to the evaporation of the polymer rods and the SrTiO 3 substrate-nucleated crystallization of the lead titanate. The spacing in between the ordered cylinders of the template and the nonselective nature of the coating procedure sets the method apart from conventional block copolymer templating techniques involving parallel cylindrical structures. Given the nonselective nature of the coating method, this template procedure is applicable for a large variety of inorganics.

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Fluctuations in the concentration profiles of correlated random copolymer melts

Correlated random copolymers are multiblock copolymers with a rather large polydispersity in the ... more Correlated random copolymers are multiblock copolymers with a rather large polydispersity in the block lengths: the variation in the block length is of the same order of magnitude as the average block length. The phase behavior of a melt of correlated random copolymers is qualitatively different from the phase behavior of regular monodisperse multiblock copolymers. It was already known that the system undergoes a disorder-order transition to a microphase separated state having a crystal symmetry, where the period decreases sharply with decreasing temperature. The fluctuation corrections to the phase diagram are, however, considerable. Near the order-disorder transition the profiles of the ordered phases are strongly fluctuating, giving the profiles an irregular appearance. Even if the blocks in the molecules are long, there is a large increase in the region of stability of the disordered phase. Below the mean-field spinodal this phase is strongly fluctuating as well, giving it the appearance of a microphase separated structure.

Confined chains with specific interactions, bridges, loops and osmosis

Journal de Physique II

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1.1 Design Principles of Polymer-Based Hydrogen-Bonded Supramolecules.. 118

Towards Monodomains of Self-Organized Comb-Shaped Polymeric Supramolecules

MRS Proceedings, 2003

We have previously shown that hierarchical self-organization is achieved upon physically bonding ... more We have previously shown that hierarchical self-organization is achieved upon physically bonding amphiphilic molecules to diblock copolymers. Here we discuss the effect of imposed shear flow to achieve overall alignment of the locally self-organized structures. We will first present shear aligned polystyrene-block-poly(4-vinyl pyridine) diblock copolymers (PS-b-P4VP), where pentadecyl phenol (PDP) has been hydrogen bonded to the pyridines. Depending on the selected molecular weights, eg. hexagonal arrangement of PS cylinders in the lamellar matrix of P4VP(PDP) can be obtained with high overall order of both structures. This is a template to obtain discrete PS nanorods, which have P4VP corona once the PDP molecules have been cleaved off by a solvent treatment. Selecting a relatively high molecular weight PS block and a short P4VP block leads to mesoporous materials with emptied cylinders with P4VP brushes at the walls. The glassy state of the PS matrix prevents the pores from collaps...

Self-assembling in block copolymer systems

Topological effects in ring polymer solutions

Aps March Meeting Abstracts, Mar 1, 1998

A comparison between the morphology of semicrystalline polymer blends of poly(ε-caprolactone)/poly(vinyl methyl ether) and poly(ε-caprolactone)/(styrene-acrylonitrile)

Polymer, 1994

The morphology of polymer blends of poly(e-caprolactone) (PCL) and poly(vinyl methyl ether) (PVME... more The morphology of polymer blends of poly(e-caprolactone) (PCL) and poly(vinyl methyl ether) (PVME) is compared with that of PCL and a random copolymer of styrene and acrylonitrile (SAN). The main objective is to determine the influence of the glass transition temperature of the amorphous component (TB,,) on the morphology of the semicrystalline polymer blends. These blends represent the two extreme cases corresponding to Tc < Ts,a and Tc > Tg.,, where Tc is the crystallization temperature. The morphology of these blends, with PVME and SAN representing the amorphous components, have been studied by small angle X-ray scattering. For both blends the long period increases with the addition of amorphous polymer, which is a strong indication for an interlamellar morphology. D.s.c. experiments, including enthalpy relaxation, are used to investigate the crystallinity and the interphases. The overall amount of crystallinity in both blends decreases with increasing content of amorphous polymer. However, the fraction of PCL that crystallizes decreases in PCL/SAN and increases slightly in PCL/PVME. Apparently, the addition of the low T~,, PVME improves the crystallization of PCL in accordance with a simple Gamblers Ruin Model type argument. The high Tg,a of SAN means this does not occur in PCL/SAN blends. Conventional d.s.c. experiments show an interphase of pure amorphous PCL in PCL/SAN blends and enthalpy relaxation experiments demonstrate its presence in PCL/PVME blends as well.

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Micro and Macrophase Separation in Mixtures of Annealed Comb Copolymers and Oligomers

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Gerrit Brinke

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