Theory of polymer brushes grafted to finite surfaces

In this work, a model based in strong‐stretching theory for polymer brushes grafted to finite planar surfaces is developed and solved numerically for two geometries: stripe‐like and disk‐like surfaces. There is a single parameter, , which represents the ratio between the equilibrium brush height and the grafting surface size, that controls the behavior of the system. When is large, the system behaves as if the polymer were grafted to a single line or point and the brush adopts a cylindrical or spherical shape. In the opposite extreme when it is small, the brush behaves as semi‐infinite and can be described as a planar undeformed brush region and an edge region, and the line tension approaches a limiting value. In the intermediate case, a brush with non‐uniform height and chain tilting is observed, with a shape and line tension depending on the value of . Relative stability of disk‐shaped, stripe‐shaped, and infinite lamellar micelles is analyzed based in this model. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 663–672     

Size of a polymer chain in an environment of quenched chains

We perform high‐coordination three‐dimensional (3D) lattice simulations of a single chain of N monomers embedded in matrices of quenched chains, at different concentrations ρ, using pruned‐enriched Rosenbluth sampling. The partition function is well‐described by the expression, , where is a universal constant, and is the concentration dependent lattice connectivity constant. For sufficiently long chains, , we find that the radius of gyration R varies nonmonotonically with ρ; R decreases gradually from its unperturbed dimensions R₀ until , after which it increases relatively rapidly due to repulsion between monomers. Motivated by the similarity in the shape of the curves, and results on Gaussian chains, we successfully superpose all the simulation data onto a single master curve. Finally, we test the relationship , suggested by a Flory‐type scaling model, where ρ_c is the critical percolation threshold, and is a universal constant. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1611–1619     

Nonmonotonic swelling of agarose‐carbopol hybrid hydrogel: Experimental and theoretical analysis

A hybrid gel is synthesized by physical mixing of agarose and carbopol and an interpenetrating network of Agarose‐Carbopol (AC) hybrid gel is observed by atomic force microscopy. This hybrid gel exhibits pH‐responsiveness and mechanical stability as well as tunable swelling. These hydrogels depict a nonmonotonic swelling behavior as a function of pH. In particular, the equilibrium degree of swelling increases with pH of bath solution until its maximum value around pH = , followed by a decrease at higher pH values. The degree of swelling is increased by the concentration of carbopol when the concentration of agarose is low [ ], or decreased by the concentration of agarose when is high [ ]. A physics‐based model is also adapted to characterize the swelling‐shrinking behavior of different compositions of AC gels. This swelling‐shrinking behavior of AC hydrogels will have potential applications in smart hydrogel‐based devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 444–454     

Rationalizing the self‐assembly of poly‐(3‐hexylthiophene) using solubility and solvatochromic parameters

The assembly of poly(3‐hextylthiophene) (P3HT) in solvent mixtures is studied using solubility and solvatochromic parameters. Correlations between the excitonic coupling of P3HT assemblies and the Kamlet–Taft (α, β, π*) and solvent scales reveal that lower excitonic coupling values are observed in binary mixtures characterized by low β values (0 < β ≤ 0.25) and low polarity (0.1 ≤ ≤ 0.3). Hansen solubility theory is revisited by evaluating the directionality of the solubility distance, R_a. Relationships between the excitonic coupling and the Δδ_h and Δδ_p vector components indicate that the polarity of the solvent (Δδ_p) and the specific solvent‐solvent interactions reflected by the Δδ_h component direct the formation of well‐ordered P3HT aggregates. The complementary results of the solubility and solvatochromic parameter analyses are in agreement with one another. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 841–850     

Unusual dynamics of ring probes in linear matrices

We perform Monte Carlo simulations of ring and linear polymers in linear matrices, and investigate the diffusivity of the probes. As the matrix chain length N_m is increased from 10 to 300 monomers, the diffusivity D_l of a linear probe (N_l = 300) decreases monotonically, while that of a ring probe D_r varies non‐monotonically, with a peak around . We perform additional simulations with a single probe molecule ( ) in a linear matrix ( ). The non‐monotonicity in D_r persists even after ring–ring interactions are eliminated. Topology dependent differences in the short‐time dynamics of the probes are observed; unlike linear probes, mean‐squared displacements of ring probes depend on N_m. Primitive path analysis suggests that the difference in dynamics originates from differences in entanglement structure. For linear probes, the degree of entanglement is independent of N_m. For ring probes, we observe two regimes: when N_m is small, the number of threadings decreases as N_m increases, eventually transitioning to a plateau. In the small N_m regime, the change in the degree of entanglement offsets the change in the mobility of the matrix chains, leading to a non‐monotonic variation in D_r. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 169–177     

Structure of sodium carboxymethyl cellulose aqueous solutions: A SANS and rheology study

We report a small angle neutron scattering (SANS) and rheology study of cellulose derivative polyelectrolyte sodium carboxymethyl cellulose with a degree of substitution of 1.2. Using SANS, we establish that this polymer is molecularly dissolved in water with a locally stiff conformation with a stretching parameter . We determine the cross sectional radius of the chain ( 3.4 Å) and the scaling of the correlation length with concentration (ξ = 296 c^?1∕2Å for c in g/L) is found to remain unchanged from the semidilute to concentrated crossover as identified by rheology. Viscosity measurements are found to be in qualitative agreement with scaling theory predictions for flexible polyelectrolytes exhibiting semidilute unentangled and entangled regimes, followed by what appears to be a crossover to neutral polymer concentration dependence of viscosity at high concentrations. Yet those higher concentrations, in the concentrated regime defined by rheology, still exhibit a peak in the scattering function that indicates a correlation length that continues to scale as . © 2014 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 492–501     

Triplet harvesting in poly(9‐vinylcarbazole) and poly(9‐(2,3‐epoxypropyl)carbazole) doped with CdSe/ZnS quantum dots encapsulated with 16‐(N‐carbazolyl) hexadecanoic acid ligands

Semiconductor quantum dots (QDs) can be used as alternative for transition metal complexes to harvest the nonemissive triplet excitons in organic light‐emitting diodes (OLEDs). In search for a QD‐based OLED material generating blue emission, poly(9‐vinylcarbazole) (PVK) and poly(9‐(2,3‐epoxypropyl) carbazole) (PEPK) are chosen as host for blue‐emitting CdSe/ZnS core/shell QDs. The QDs are encapsulated with 16‐(N‐carbazolyl) hexadecanoic acid (C16), a ligand terminated by a carbazole moiety. As alternative for PVK, PEPK, where the lower molecular weight and less extensive excimer formation could promise a better film formation and more extensive exciton hopping, is explored. The efficiencies of singlet ( ) and triplet ( ) energy transfer to the C16 capped QDs are estimated by combining stationary photoluminescence spectra and fluorescence decays of pristine polymer films with those of polymer films doped with the QDs. At a loading of 30 wt % of the QDs, increases from 12 ± 1% in PVK to 41 ± 2% in PEPK while increases from 37 ± 22% in PVK to 72 ± 48% in PEPK. The investigation of the film morphology by atomic force microscopy confirms that the main factor limiting the triplet transfer efficiency in the PVK matrix is the clustering of the C16 capped QDs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 539–551     

Influence of the crystallization on the molecular mobility and ionic DC conductivity behaviors of relaxor ferroelectric P(VDF‐TrFE‐CTFE) terpolymers

The dynamics of semicrystalline poly(vinylidene fluoride‐trifluoroethylene‐chlorotrifluoroethylene) (P(VDF‐TrFE‐CTFE)) terpolymers were fully investigated as a function of temperature and frequency, by means of broadband dielectric spectroscopy. Four types of relaxation regimes were observed over the full dielectric spectroscopy, namely (second) relaxation in the sub‐glass state, (segmental dynamics) in the rubbery state, the Curie transition and space charge carrier motion at high temperatures. Constrained segmental dynamics were observed in the terpolymer containing the highest crystalline fraction for which a narrow relaxation time distribution was found. These results indicate a decreasing average size of the cooperative rearranging region over the crystalline fraction. A decrease of the strength index values also implied a more fragile behavior for terpolymers with a higher degree of crystallinity. An exceptional increase in dielectric strength was found as the crystallinity increased. This behavior could be explained by an enhanced interphase (constrained amorphous phase). The Curie transition showed an accelerating relaxation rate for a more fragile terpolymer. Moreover, a motion of the space charge carrier ions was observed in the higher temperature range. Finally, there was evidence that the segmental dynamics in the amorphous phase was responsible for the motion of the space charge carrier ions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1645–1657     

Extension rate of the straight jet in electrospinning of poly(N‐isopropyl acrylamide) solutions in dimethylformamide: Influences of flow rate and applied voltage

In the electrospinning process, the measurement of extension rate of the straight jet is not an easy task. In this study, the diameter profile of the tapering straight jet is determined with a laser light‐scattering technique. Afterwards, the jet extension rate () is derived and used to compare with the solution‐intrinsic rates, for example, the terminal relaxation rate and the Rouse relaxation rate. The extension rate of the straight jet depends on position: it is highest near the cone apex (region I) and decays to a constant value in the major jet (region II) until approaching the jet end (region III), at which the extension rate abruptly drops to nearly zero, that is, _I >_II ≫_III ∼ 0. The jet diameter in region III is independent of solution concentration and applied voltage, but is scaled to the flow rate with an exponent of ∼0.37. The derived exponent is consistent with a simple prediction based on the counterbalance between the stretching electric force and the compressive force induced by the air drag force. Provided that air friction becomes overwhelming at the straight jet end, the long electrified jet is likely to buckle, thereby triggering the instability of jet whipping. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 319–329     

Crystallinity of poly(3‐hexylthiophene) in thin films determined by fast scanning calorimetry

Using fast scanning calorimetry, we determined the crystallinity of thin films of poly(3‐hexylthiophene) crystallized from the melt from measurements of the specific melting enthalpy. A broad range of film thicknesses from 10 µm down to 26 nm was covered. The sample mass was determined from measurements of the specific heat capacity in the molten state allowing a quantitative analysis of the heat flow data. Films with a thickness 400 nm slowly cooled from the melt showed the same crystallinity as bulk samples measured with conventional DSC. Below 350 nm the melting enthalpy decreased strongly. We assign this strongly reduced crystallinity to the restricted crystallization kinetics originating from hindered spherulitic growth under thin film confinement. A higher crystallinity could be partially regained by extended isothermal crystallization at elevated temperatures. Much faster cooling, with rates above about 100 Ks^?1 led to a partial suppression of crystallization even for thick films. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1791–1801     

Controlling aggregate formation in conjugated polymers by spin‐coating below the critical temperature of the disorder–order transition

Aggregates – that is short‐ranged ordered moieties in the solid‐state of π‐conjugated polymers – play an important role in the photophysics and performance of various optoelectronic devices. We have previously shown that many polymers change from a disordered to a more ordered conformation when cooling a solution below a characteristic critical temperature . Using in situ time‐resolved absorption spectroscopy on the prototypical semiconducting polymers P3HT, PFO, PCPDTBT, and PCE11 (PffBT4T‐2OD), we show that spin‐coating at a temperature below can enhance the formation of aggregates with strong intra‐chain coupling. An analysis of their time‐resolved spectra indicates that the formation of nuclei in the initial stages of film formation for substrates held below seems responsible for this. We observe that the growth rate of the aggregates is thermally activated with an energy of 310 meV, which is much more than that of the solvent viscosity (100 meV). From this we conclude that the rate controlling step is the planarization of a chain that is associated with its attachment to a nucleation center. The success of our approach for the rather dynamic deposition method of spin‐coating holds promise for other solution‐based deposition methods. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 532–542     

Enthalpy of fusion of poly(3‐hexylthiophene) by differential scanning calorimetry

The enthalpy of fusion for a perfect, infinite poly(3‐hexylthiophene) (P3HT) crystal () must be known to evaluate the absolute crystallinity of P3HT. This value, however, is still ambiguous as different values have been reported using various experimental techniques. Here, we extrapolate the enthalpy of fusion for extended chain crystals of oligomeric P3HT to infinite molecular weight and obtain a value of 42.9 ± 2 J/g employing differential scanning calorimetry with a correction based on grazing incidence small angle X‐ray scattering data. Also, we define the onset of chain folding within P3HT crystallites at a chain length of 5 Kuhn segments. Knowledge of allows calculation of P3HT percent crystallinity in thin films for applications such as organic field effect transistors and solar cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1469–1475     

Variation of the strain rate during CSM nanoindentation of glassy polymers and its implication on indentation size effect

The indentation strain rate is currently assumed to remain unvaried during continuous stiffness measurement (CSM) nanoindentation where is imposed to remain constant. To probe the validity of this assumption for the nanoindentation of glassy polymers, a series of experiments have been performed at different set values on poly(methyl methacrylate) and polycarbonate using CSM technique. It is firstly shown that the actual value changes drastically at shallow indentation depths and it takes a considerable depth, which is material independent, for this parameter to attain a stabilized value. Furthermore, the strain rate is measured directly as the descent rate of the indenter divided by its instantaneous depth ( ), and indirectly via considering the variations of the load and hardness during the test. Both of these approaches reveal that the strain rate is considerably larger at shallow depths, and the depth beyond which it becomes constant is material and ratio dependent. Finally, by considering the relationship between the hardness and strain rate, it is observed that although the strain rate variation alters the hardness, its contribution is not able to justify the observed indentation size effect; hence, other contributing factors for this phenomenon are discussed for their possible effects. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2179–2187     

Simulating local mobility and mechanical properties of thermostable polyimides with different dianhydride fragments

The dynamic and mechanical properties of the three thermoplastic polyimides—crystallizable polyimide BPDA‐P3 and amorphous polyimides ODPA‐P3 and aBPDA‐P3—have been simulated using the atomistic molecular dynamics technique. The three simulated polyimides differ in the chemical structure of their corresponding dianhydride fragments. Analyzing the local orientational mobility of different phenylene rings, it has been established that the increase of the glass‐transition temperature (T_g) in the ordered set is caused by the slowing down of the phthalimide rings relaxation in the corresponding dianhydride fragments. It has been observed that rather poor mechanical characteristics upon aBPDA‐P3 stretching in the strain‐hardening regime are also due to the low orientational mobility of the phthalimide rings. The correlation between the dynamic fragility and the polyimides strain‐hardening moduli has been observed; the increase of the dynamic fragility leads to the increase of the strain‐hardening modulus. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 375–382     

Effect of chain structure on the glass transition temperature and viscoelastic property of cis‐1,4‐polybutadiene via molecular simulation

In this work, by adopting the united atom model of cis‐1,4‐poly(butadiene) (PB), we systemically investigate the effect of the chain structure on the glass transition temperature (T_g) and the viscoelastic property of PB system. First, we analyze the atom translational mobility, bond reorientation dynamics, torsional dynamics, conformational transition rate, and dynamic heterogeneity of the PB chains with different chain structures in detail by determining the corresponding T_g. In addition, our results clearly indicate that with the decrease of the amount of the free end atoms of PB via the end‐linking method, the mobility of the PB chains quickly decreases. As a result, the T_g of the PB chains gradually increases. Depending on the chain structure and the calculation method, the T_g of the PB chains varies from 154 to 240 K. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below T_g. The calculated activation energy varies from 7.37 to 16.37 KJ/mol for different chain structures above T_g, which can be compared with those for other polymers. In addition, through the end‐linking approach the strong interaction between the PB chains improves the storage modulus G′ and the loss modulus . Meanwhile, the immobility of the free end atoms effectively reduces the friction loss of the chains under the shear field, which is reflected by the low loss factor . In summary, this work can further help to understand the effect of the chain structure on the dynamic properties of the PB chains. Meanwhile, it provides an effective approach to reduce the energy loss during the dynamic periodic deformation, which can cut the fuel consumption via the end‐linking method. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1005–1016     

Morphological and mechanical behavior of montmorillonite grafted block copolymer brushes

Here we report the phase behavior of a family of montmorillonite (MMT) block copolymer brushes (MBBs), a novel class of polymer nanocomposites. MBBs are comprised of discrete MMT platelets encapsulated with block copolymer brushes. These MBBs were synthesized via surface-initiated atom transfer radical polymerization using halogenated alkylammonium surfactants to localize initiation sites on the clay surfaces. Two styreninc MBB systems—poly(styrene-b-n-butyl acrylate) and poly(styrene-b-t-butyl acrylate)—were prepared varying the composition and total 80–250 kDa. MBB materials were compared with their non-clay bulk block copolymer counterparts via electron microscopy and a host of mechanical tests in both the solid and melt states. Notably, MBBs have similar melt-state rheological properties compared to neat block copolymers and are thus amenable to current processing techniques. MBBs were found to self-assemble into single grain morphologies across incredibly large areas (>3 μm) which resulted in extremely well-ordered, defect-free lamellar structures with applications in microelectronics. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 353–361     

Femtosecond laser fabrication of high‐Q whispering gallery mode microresonators via two‐photon polymerization

Whispering gallery mode microresonators have been triggering considerable advances in science due to their ability to confine light within small dielectric volumes, which makes them suitable for a wide range of applications. Lithographic approaches have been the dominant technique for fabricating microresonators; however, they restrict the choice of materials due to their multistep processing nature. As an alternative, they report the direct laser fabrication of acrylic based hollow microcylinder resonators, via two‐photon polymerization, with good structural integrity and sidewall roughness of 1.5 nm, which make them promising candidates for photonic applications in the near‐infrared. Such polymeric microresonators exhibit finesse close to 10³ and a quality factor of 1 10⁵, a performance achieved without any additional processing step, which would restrict the choices of materials to be incorporated into the polymeric resonator. This advantage thereby broadens the widespread use of the polymeric microresonators, making them an excellent platform for lasing and nonlinear optics studies in the near‐infrared. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 569–574     

Improved description of the orbital relaxation effect by practical use of the self‐energy

The self‐energy shift in the orbital relaxation (OR) term of the polarization propagator complete through the second‐order is presented. In combination with the optimal damping parameter in the OR term, the modified propagator produces the excitation energy of the coupled‐cluster with singles and doubles (CCSD) accuracy. The self‐energy shift requires the floating‐point operation of , where N refers to the magnitude of the molecular size. Because the second‐order polarization propagator requires the floating‐point operation of , the additional computational effort to construct the self‐energy is negligibly small. Numerical results are shown for several molecules including glycine, 2,3,5,6‐tetrafluorobenzene, and naphthalene, and promising agreements with those of CCSD are confirmed within less than 0.2 eV. The basis set dependence is also tested for the water molecule using aug‐cc‐pV NZ (N = D–7), where this newly developed approach mimics the behavior of the CCSD values. The self‐energy shifting for the second‐order response matrix in combination with the use of a dumping parameter is efficiently implemented for calculations of medium‐sized molecular systems, including glycine and naphthalene. The developed approach provides CCSD‐like accuracy at a more affordable computational expense. © 2014 Wiley Periodicals, Inc.     

Modulation of ionization and structural properties of weak polyelectrolytes due to 1D, 2D,and 3D confinement

What is the impact of reducing the space available to molecules onto their properties is a fundamental question for capillary systems, molecular biology and transport, protein and material sciences. Possibly influenced by space restriction, ionization degree has rarely been studied for confined polyelectrolytes; Monte Carlo titrations and coarse‐grained models are thus used to investigate structural and ionization changes induced on a single polyelectrolyte chain by confinement into slit (1D), cylindrical (2D), or spherical (3D) cavities. Four polyelectrolyte models differing in chain stiffness and the possible formation of charged hydrogen bonds (c? H? bonds) are studied. Low pH effective ionization constants (pK_a ) of confined chains are lower than for the free species if c? H? bonds can be formed. This is especially evident for 3D‐confined stiff chains, a finding rationalized by the impact of global compression onto chain conformations. If no c? H? bonds are allowed, chain ionization is largely unaffected by 1D or 2D confinement, while it is depressed by 3D. Chain confinement Helmholtz energy (ΔA _conf) was computed as a function of both pH and confining width (W) to gauge the impact of ionization‐induced stiffening onto ΔA _conf versus W behavior, the partition coefficient governing absorption, and the average number of c? H? bond formed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1088–1102     

Miscibility maps for polymer blends: Effects of temperature,pressure, and molecular weight

We study a Gibbs free energy model for describing the thermodynamics of compressible polymer blends in the case of nonpolar polymers. This model is a mean field model equivalent to the cell model of Prigogine et al. and close also to the model by Flory‐Orvoll and Vrij. The model is expressed as a function of the interaction energies between monomer pairs (a, b, and c), the degrees of polymerization (X_A and X_B), a close packing parameter ρ₀, the temperature, and the pressure. We derive an analytical expression regarding blend miscibility. All the already observed phase behaviors are recovered: the occurrence of two kinds of upper critical solution transition (UCST): case‐I and case‐II UCST for which the pressure has a destabilizing or stabilizing effect, respectively, and lower critical solution transition; cases where the pressure have a non‐monotonous effect on the UCST temperature; cases where the spinodal lines close up under high pressures; and the so‐called hour‐glass transition. The model allows for making explicit the effect of the different physical parameters on phase behavior. We calculate complete miscibility maps regarding the occurrence of the various possible kinds of transitions in the 2D space b/a and X_A, for different values of , applied pressure P, and chain length ratios. This approach may come as a complement to already existing, more quantitative and elaborated approaches. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 419–443