G. ten Brinke

G. ten Brinke
University of Groningen | RUG · Zernike Institute for Advanced Materials (ZIAM)

About

300
Publications
38,447
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13,843
Citations
Citations since 2016
12 Research Items
2855 Citations
20162017201820192020202120220100200300400500600
20162017201820192020202120220100200300400500600
20162017201820192020202120220100200300400500600
20162017201820192020202120220100200300400500600

Publications

Publications (300)
Article
Full-text available
Involving supramolecular chemistry in self-assembling block copolymer systems enables design of macromolecular architectures that are challenging to obtain through conventional all-covalent routes. In this work we present supramolecular double-comb triblock terpolymers in which both outer blocks are able to interact with a surfactant via hydrogen b...
Article
Full-text available
Involving supramolecular chemistry in self-assembling block copolymer systems enables design of complex macromolecular architectures that, in turn, could lead to complex phase behavior. It is an elegant route, as complicated and sensitive synthesis techniques can be avoided. Highly grafted double-comb diblock copolymers based on symmetric double hy...
Article
The combination of asymmetric P4VP-b-PAPI diblock copolymers (i.e. fP4VP ≠ fPAPI) and 3-NDP surfactants in hydrogen-bonded [poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine)](3-nonadecylphenol)x (P4PA(3-NDP)x) supramolecular double-comb diblock copolymers could potentially result in rather interesting morphologies. However, plasticization of t...
Article
The formation of ordered morphologies in thin films of symmetric diblock copolymer melts is considered theoretically. Somewhat surprisingly, under proper boundary conditions the presence of a lamellar chemical pattern on the substrate, being sufficiently pronounced and with the right period, is found to induce the formation of diamond-like morpholo...
Article
Full-text available
The formation of unusual multilayered parallel lamellae-in-lamellae in symmetric supramolecular double-comb diblock copolymers is presented. While keeping the concentration of surfactant fixed, the number of internal layers was found to increase with molecular weight M up to 34 for the largest block copolymer. The number of internal structures n wa...
Article
Full-text available
The formation of unusual multilayered parallel lamellae-in-lamellae in symmetric supramolecular doublecomb diblock copolymers is presented. While keeping the concentration of surfactant fixed, the number of internal layers was found to increase with molecular weight M up to 34 for the largest block copolymer. The number of internal structures n was...
Article
Block copolymers are known to spontaneously form ordered structures at the nano-to mesoscale. Although the number of different morphologies is rather limited in diblock copolymer systems, their phase behavior becomes increasingly more complex with each additional building block. Synthesis of such all-covalent materials is, however, a very challengi...
Article
To provide a faster calculation of the block copolymer phase diagrams a simplified version of the self-consistent field theory (SCFT) is proposed. Multi-component block copolymers with interactions between repeated units described by the χ-parameters satisfying the Hildebrand conditions are studied. This case is shown to correspond to a degeneratio...
Article
Linear poly(4-tert-butoxystyrene)-b-poly(4-vinylpyridine) (PtBOS-b-P4VP) diblock copolymers are synthesized using reversible addition–fragmentation chain transfer polymerization. The self-assembly of four different PtBOS-b-P4VP diblock copolymers is studied using small-angle X-ray scattering and transmission electron microscopy and a number of inte...
Article
The self-assembly of the hydrogen-bonded complexes between poly(p-hydroxystyrene) (PpHS) and 4-alkylpyridine amphiphiles is studied using infrared spectroscopy, differential scanning calorimetry, polarized optical microscopy, transmission electron microscopy and small- and wide-angle X-ray scattering. Interesting differences are observed with the w...
Article
A new promising class of ordered block copolymer morphologies in thin films we call diamond-like morphologies (DLM) is theoretically described in detail. This class comprises the cubic morphologies possessing diamond symmetry Fd3¯m as well as its tetragonal and orthorhombic generalizations. The characteristic property of the DLM is that the corresp...
Article
Controlled radical polymerization of 4-vinylpyridine (4VP) and N-acryloylpiperidine (API) by the RAFT process allowed preparation of well-defined double hydrogen bond accepting P4VP-b-PAPI diblock copolymers. The miscibility of this new monomer pair was studied via a random copolymer blend approach and resulted in a Flory–Huggins interaction parame...
Article
The unique mechanical performance of nacre, the pearly internal layer of shells, is highly dependent on its complex morphology. Inspired by the structure of nacre, the fabrication of well-ordered layered inorganic-organic nanohybrids is presented herein. This biomimetic approach includes the use of a block copolymer template, consisting of hydropho...
Article
The self-assembly of P4VP(3-PDP)1.0 and P4VP(4-NDP)1.0 supramolecular comb-shaped copolymers has previously been shown to have very interesting thermal properties, since besides crystallization of 3-PDP/4-NDP’s alkyl tails, an additional order-disorder transition (ODT) was observed as well. In order to get a better insight into the processes involv...
Article
Poly(vinylidene fluoride) (PVDF) has reached the second largest production volume of fluoropolymers in recent years, and its popularity can be ascribed to high thermal stability and chemical inertness combined with its ferroelectric behavior. Copolymerization of vinylidene fluoride with other monomers leads to a wide variety of products with modifi...
Article
A double-comb diblock copolymer was constructed experimentally using a double supramolecular approach. Addition of 3-nonadecylphenol (3-NDP) amphiphiles to a symmetric, double hydrogen bond accepting poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) (P4VP-b-PAPI) diblock copolymer resulted in microphase separation on both the block copolymer a...
Article
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Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered archit...
Article
Double-crystalline poly(L-lactide)-block-poly(vinylidene fluoride)-block-poly(L-lactide) (PLLA-b-PVDF-b-PLLA) triblock copolymers were successfully synthesized through ring opening polymerization of L-lactide and benzoyl peroxide initiated polymerization of vinylidene fluoride, followed by copper(I)-catalyzed azide-alkyne coupling of the functional...
Data
Electro-hydrodynamic equations describing the behavior of a charged polymer jet are analyzed by analytical methods and scaling approach. A FENE-P constitutive equation is employed to describe the viscoelastic properties of a conducting polymer liquid. Effects of the electric field, the flow rate, and the material parameters on the jet dynamics are...
Article
Full-text available
Ordered planar morphologies in A-b-(B-b-A)2-b-C and (B-b-A)2-b-C terpolymer melts are studied within the framework of the self-consistent field theory for volume fractions of components A, B, and C in the ratio 1:1:2 and the Flory-Huggins interaction parameters satisfying χAB = 2χAC. The stable phases turn out to be the disordered, hexagonal, paral...
Article
The phase behavior of block copolymer based supramolecular complexes polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and amphiphilic pentadecylphenol (PDP) molecules resembles the phase behavior of conventional block copolymers. Several PS-b-P4VP(PDP) complexes are found to self-assemble into gyroid nanostructures. Typically, the grains are ran...
Article
Full-text available
The aim of this study was to obtain enhanced textural properties of macroporous crosslinked copolymer poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) by synthesizing nanocomposites with acid-modified bentonite. Nanocomposites were obtained by introducing various amounts of acid-modified bentonite (BA) into the reaction system. All sam...
Article
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3D nanostructured inorganic materials appear as promising candidates for various practical applications. Here we focus on metal nanofoams, a class of 3D nanomaterials uniquely combining the properties of metals and nanoporous materials, and review the recent developments in their preparation methods. Common approaches, such as dealloying, sol–gel s...
Article
Full-text available
PVDF-based block copolymers have been employed as precursors for the construction of PVDF/PMAA/Ni nanocomposites. New poly(tert-butyl methacrylate)-block-poly(vinylidene fluoride)-block-poly(tert-butyl methacrylate) (PtBMA-b-PVDF-b-PtBMA) triblock copolymers were synthesized via atom transfer radical polymerization (ATRP) of tBMA from chlorine-term...
Article
Hierarchical self-assembly of supramolecular double-comb diblock copolymer complexes, based on a diblock copolymer in which both blocks can participate in the hydrogen bonding with short amphiphiles, is discussed. A symmetric poly(4-vinylpyridine)-b-poly-(N,N-dimethylacrylamide) (P4VP-b-PDMA) diblock copolymer was synthesized via reversible additio...
Article
Supramolecular complexes of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers and small molecules such as pentadecylphenol (PDP) have been studied extensively in recent years. In the present study, PS-b-P4VP(PDP) complexes with a minority P4VP(PDP) block are morphologically characterized focusing on the region between the lamel...
Article
Full-text available
The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical p...
Article
Full-text available
The surface of single-walled carbon nanotubes (SWCNTs) was functionalized with azide-terminated poly(vinylidene fluoride) (PVDF). Functionalization was confirmed by dispersibility, Raman spectroscopy, and thermogravimetric analyses. Raman spectra show disordering of the SWCNTs, thus, strongly suggesting that PVDF was covalently attached to SWCNTs....
Article
The double gyroid network morphology has been the focus of extensive research efforts as one of the most appealing block copolymer structures for practical applications. We performed an extensive study of the phase behavior of the supramolecular complex PS-b-P4VP(PDP)x to develop a systematic route to its double gyroid morphology. The morphological...
Article
Full-text available
A-b-(B-b-A)n-b-B multiblock copolymers composed of short middle diblock units (B-b-A)n and two long A- and B-outer blocks were successfully prepared. The multiblock copolymers consist of polystyrene (S) and poly(p-hydroxystyrene) (pHS) and were prepared through sequential anionic polymerization of styrene and 4-tert-butoxystyrene, followed by hydro...
Article
Full-text available
We revisit the idea of the existence of the ordered block copolymer phase possessing diamond symmetry Fdm (space group No. 227), which was first put forward within the framework of the strong segregation approach. For this purpose we study the order–disorder and order–order transitions in molten two-scale multiblock copolymersAmN/2(BN/2AN/2)nBmN/2v...
Article
This is a brief overview on the phase behavior of polymer blends and block copolymers. The self-assembly of flexible diblock copolymers is well understood now, although the recent finding of a new stable phase (Fddd (O70)) suggests that surprises are still possible. The attention has gradually shifted to more complex systems, such as triblock and m...
Article
Full-text available
A proper quantification of the specific surface area of nanoporous materials is necessary for a better understanding of the properties that are affected by the high surface-area-to-volume ratio of nanoporous metals, nanoporous polymers and nanoporous ceramics. In this paper we derive an analytical expression that relates the specific surface area o...
Article
A theoretical study on the effect of polydispersity of two-length-scale binary multiblock copolymers on the shape of the structure factor is presented. A bifurcation diagram is constructed showing the partition of the parameter space into domains differing in the way in which the homogeneous melt loses thermodynamic stability. When the polydispersi...
Article
Full-text available
The phase behavior of (A-comb-C)-b-(B-comb-C) diblock copolymer melts is investigated using the strong segregation theory approach. Three different regimes are distinguished. In regime 1 both disordered comb blocks are microphase separated from each other, in regime 2 the side chains C are microphase separated from the disordered A-b-B diblock back...
Article
Metal nanofoams with a porosity above 50% v/v have recently attracted great interest in materials science due to their interesting properties. We demonstrate a new straightforward route to prepare such nanofoams using diblock copolymer-based PS-block-P4VP(PDP) supramolecules that self-assemble into a bicontinuous gyroid morphology, consisting of PS...
Article
Full-text available
The self-assembly in diblock copolymer-based supramolecules, obtained by hydrogen bonding short side chains to one of the blocks, as well as in two-length-scale linear terpolymers results in hierarchical structure formation. The orientation of the different domains, e.g. layers in the case of a lamellar-in-lamellar structure, is determined by the m...
Article
DNA block copolymer doing it all: A potentially scalable self-assembly method for single-walled carbon nanotubes (SWNTs) involves the use of amphiphilic DNA block copolymers. One such hybrid is able to cover the entire area of solution-based SWNT technologies, from selective dispersion to nondestructive functionalization to high-yield device fabric...
Article
Front Cover: 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 articl...
Article
Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene- block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP)complexes. After structure formation, PD...
Article
The effect of annealing on the structure and the helix orientation in Langmuir-Blodgett (LB) monolayers of diblock copolymers (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) with unidirectional helix orientation deposited on hydr...
Article
The azimuthal helix orientation of the rigid-rod amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) in Langmuir-Blodgett (LB) monolayers was investigated using polarized transmission Fourier transf...
Article
Full-text available
The effect of chain length on the helix orientation of α-helical diblock copolypeptides in Langmuir and Langmuir–Blodgett monolayers is reported for the first time. Amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(α-L-glutamic acid) (PLGA) and poly(γ-methyl-L-glutamate-ran-γ-stearyl-L-glutamate) with 30 mol% of stearyl substituents (PML...
Article
The surface potentials and effective dipole moments of alpha-helical amphiphilic diblock copolypeptides during monolayer compression at the air-water interface are reported. Amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol % of ste...
Article
Different types of lamellar-within-lamellar structure formations in A-b-(B-b-A)(n)-b-C terpolymer melts, with a volume fraction of components A, B, and C in the ratio of 1:1:2, are analyzed in the strong segregation limit using a simple theoretical approach. We consider the lamellar, parallel lamellar-within-lamellar, and perpendicular lamellar-wit...
Article
Four different poly(tert-butoxystyrene)-b-polystyrene-b-poly(4-vinylpyridine) (PtBOS-b-PS-b-P4VP) linear triblock copolymers, with the P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and tert-butoxystyrene and between tert-butoxy...
Article
The synthesis of amphiphilic diblock copolypeptides consisting of poly(α-L-glutamic acid) (PLGA) and poly(γ-methyl-L-glutamate-ran-γ-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) and their monolayer behavior at the air–water interface have been studied. PLGA-b-PMLGSLG was synthesized via a diblock copolymer precursor consisti...
Article
We report here the first results of order-disorder transition (ODT) in a self-assembled comb-like polymer-amphiphile supramolecular system as identified from the change in positron lifetime parameters. We have used poly(4-vinyl pyridine) hydrogen bonded with 3-pentadecyl phenol, which upon heating showed a stepwise reduction in o-Ps intensity at th...
Article
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 temperat...
Article
Full-text available
We present a statistical mechanical approach for predicting the self-assembled morphologies of amphiphilic diblock copolymers in the melt. We introduce two conformationally asymmetric linear copolymer models with a local structural asymmetry, one of a ‘‘comb-tail’’ type and another that we call ‘‘continuous jackknife model.’’ The copolymers consist...
Article
Polypyrrole has been chemically synthesized on thin film nanostructures obtained from comb-shaped supramolecules of polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) hydrogen bonded with pentadecylphenol (PDP). PDP was washed from thin films of cylindrical and lamellar self-assembled comb-copolymer systems, which resulted in removal of the upper...
Article
Full-text available
Using the self-consistent-field theory numerical procedure we find that the period D of the lamellar-in-lamellar morphology formed in symmetric multiblock copolymer melts A(mN/2)(B(N/2)A(N/2))(n)B(mN/2) at intermediate segregations changes nonmonotonically with an increase in the relative tail length m. Therewith D reveals, as a function of the Flo...
Article
Full-text available
Due to their ability to microphase separate into well ordered structures with periodicities on the nanometre scale, block copolymers have received widespread attention as building blocks for the fabrication of nanomaterials. In particular, thin films of block copolymers promise new technological breakthroughs in e.g. computer memory applications. T...
Article
Random copolymers of styrene and 4-vinylpyridine P(S1-x-co-4VPx) were synthesized to study the effect of the random copolymer “repulsion” on the self-assembly in hydrogen-bonded complexes with pentadecylphenol (one PDP molecule per 4VP group). The major trends observed as a function of the fraction of styrene monomers 1 - x in the random copolymer...
Article
Four different poly(fer/-butoxystyrene)-b-polystyrene-b-poly(4- vinylpyridine) (P/BOS-b-PS-b-P4VP) linear triblock copolymers, with a P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and fer/-butoxystyrene and between fer/-butoxys...
Article
Full-text available
A simple theoretical analysis of the lamellar-in-lamellar self-assembled state of ternary C–b–(B–b–A)m–b–B–b–C multiblock copolymer melts in the strong segregation limit is presented using the Alexander–de Gennes approximation. For a given value of m, the influence of the chain length of the various blocks and the value of the Flory–Huggins χAB and...
Article
The terrace formation behavior of chloroform vapor annealed thin films of asymmetric, low molecular weight comb-shaped supramolecules consisting of a short polystyrene (PS) block and a long supramolecular block of poly(4-vinylpyridine) (P4VP) hydrogen bonded with pentadecylphenol (PDP) on silicon oxide (SiO2) was examined with atomic force microsco...
Article
Full-text available
A theoretical description of the lamellar-in-lamellar self-assembly of binary A-b-(B-b-A)(m)-b-B-b-A multiblock copolymers in the strong segregation limit is presented. The essential difference between this binary multiblock system and the previously considered C-b-(B-b-A)(m)-b-B-b-C ternary multiblock copolymer system is discussed. Considering the...
Article
Conformational properties of amphiphilic stiff-chain macromolecules in concentrated solutions in poor solvent have been studied via computer modeling. We have found that the conformational state of macromolecules in such systems depends on the macromolecular stiffness and on the way the solution has been prepared. Thus, if the concentration of glob...
Article
Using atom transfer radical polymerization (ATRP), poly(tert-butyl methacrylate-b-styrene-b-4-vinylpyridine) or PtBMA-b-PS-b-P4VP linear triblock copolymers were synthesized. Different homopolymer and diblock copolymer macroinitiators were used for different block copolymerizations. For a selected triblock copolymer the self-assembly was studied wi...
Article
Full-text available
The coil-globule transition in rigid-chain amphiphilic macromolecules was studied by means of computer simulation, and the phase diagrams for such molecules in the solvent quality-persistence length coordinates were constructed. It was shown that the type of phase diagram depends to a substantial extent on the degree of polymerization of a macromol...