• Macromolecular Research
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• 제12권2호
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• pp.178-188
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• 2004

We performed molecular dynamics (MD) simulations at 300 K on a series of poly(benzyl ether) (PBE) dendrimers having a different core functionalities. We used the rotational isomeric state Metropolis Monte Carlo (RMMC) method to construct the initial configuration in a periodic boundary cell (PBC) before the MD simulations were undertaken. To elucidate the effects that the structural features have on the chain dimension, the overall internal structure, and the morphology, we monitored the radii of gyration, R$\sub$g/ and the conformational changes during the simulations. The PBE dendrimers in a glassy state adopted less-extended structures when compared with the conformations obtained from the RMMC calculations. We found that R$\sub$g/ of the PBE dendrimer depends on the molecular weight, M, according to the relation, R$\sub$g/∼M$\^$0.22/. The radial distributions of the dendrimers were developed identically in the PBC, irrespective of the core functionality. A gradual decrease in radial density resulted from the fact that the terminal branch ends are distributed all over the molecule, except for the core region.

• Macromolecular Research
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• 제9권3호
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• pp.129-142
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• 2001

To efficiently demonstrate the molecular motion, physical properties, and mechanical properties of polycarbonates, we studied the differences between bisphenol-A polycarbonate(BPA-PC) and tetramethyl bisphenol-A-polycarbonate(TMBPA-PC) using molecular modeling techniques. To investigate the conformations of BPA-PC and TMBPA-PC and the effect of the conformation on mechanical properties, we performed conformational energy calculation, molecular dynamics calculation, and stress-strain curves based on molecular mechanics method. From the result obtained from conformational energy calculations of each segment, the molecular motions of the carbonate and the phenylene group in BPA-PC were seen to be more vigorous and have lower restriction to mobility than those in TMBPA-PC, respectively. In addition, from the results of radial distribution function, velocity autocorrelation function, and power spectrum, BPA-PC appeared to have higher diffusion constant than TMBPA-PC and is easier to have various conformations because of the less severe restrictions in molecular motion. The result of stress-strain calculation for TMBPA-PC seemed to be in accordance with the experimental value of strain-to-failure ∼4%. From these results of conformational energy calculations of segments, molecular dynamics, and mechanical properties, it can be concluded that TMBPA-PC has higher modulus and brittleness than BPA-PC because the former has no efficient relaxation mode against the external deformations.

• Macromolecular Research
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• 제9권4호
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• pp.185-196
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• 2001

The self-assembly of block copolymers can lead to a variety of ordered structures on a nanometer scale. In this article, the self-assembling behaviors of triblock copolymers in the melt and the selective solvent are described with the results obtained from the computer simulations. With the advances of computing power, computer simulations using molecular dynamics and Monte Carlo techniques make it possible to study very complicated phenomena observed in the self-assembly of triblock copolymer. 13king full advantage of the computer simulation based on well-defined model, the effects of various structural and thermodynamic parameters such as the copolymer composition, the block sequence, the pairwise interaction energies, and temperature on the self-assembly are discussed in some detail. Some simulation results are compared with experimental ones End analyzed by comparing them with the theoretical treatment.

• Macromolecular Research
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• 제8권5호
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• pp.224-230
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• 2000

Molecular mechanics technique has been used for finding energy-minimized conformation to understand the mechanism of yielding of glassy polymers in atomistic level. As a model polymer, amor- phous isotactic polypropylene (iPP) was generated by molecular mechanics and molecular dynamics methods. The stress-strain cone was successfully obtained by using molecular mechanics technique. The torsional angle distribution showed no significant change during extension, although the torsional angles of certain bonds in polymer backbone changed more largely than other bonds. No significant change in the van der Waals interaction is observed at yielding point, whereas the torsional angle energy starts to decrease at yield strain.

• Macromolecular Research
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• 제8권3호
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• pp.125-130
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• 2000

Resorcinol formaldehyde resins are synthesized by polycondensation of resorcinol with formal-dehyde and have various structures by the condensation type. The influence of polycondensation type on the stability and structure of the resorcinol formaldehyde resin was studied by molecular mechanics and molecular dynamics. The resins formed by 2,6-polycondensation and 4,6-polycondensationwith head-to-tail orientations have structures of intramolecular hydrogen bonds between 1-hydroxyl groups and between outer hydroxyl groups of the adjacent resorcinols, respectively. The resin formed by 2,6-polycon-densation with head-to-head orientation has a structure that inner hydroxyl groups cluster in the center of the molecule. Energetical stability of the resin is affected by both the intramolecular hydrogen bonds and the steric' hindrance by phenyl group.

• Macromolecular Research
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• 제9권3호
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• pp.164-170
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• 2001

Recently in order to describe the complex rheological behavior of polymer melts with long side branches like low density polyethylene, new constitutive equations called the pom-pom equations have been derived by McLeish and Larson on the basis of the reptation dynamics with simplified branch structure taken into account. In this study mathematical stability analysis under short and high frequency wave disturbances has been performed for the simplified differential version of these constitutive equations. It is proved that they are globally Hadamard stable except for the case of maximum constant backbone stretch (λ = q) with arm withdrawal s$\_$c/ neglected, as long as the orientation tensor remains positive definite or the smooth strain history in the now is previously given. However this model is dissipative unstable, since the steady shear How curves exhibit non-monotonic dependence on shear rate. This type of instability corresponds to the nonlinear instability in simple shear flow under finite amplitude disturbances. Additionally in the flow regime of creep shear flow where the applied constant shear stress exceeds the maximum achievable value in the steady now curves, the constitutive equations will possibly violate the positive definiteness of the orientation tensor and thus become Hadamard unstable.

• Macromolecular Research
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• 제9권3호
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• pp.171-178
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• 2001

We report the diffraction behavior of the functionalized sol-gel film composed of two different silanes. One silane (SGDR1) contains disperse red 1 (DR1) that is composed of an azobenzene unit. The other silane (SGCHC) bears a chalcone derivative that is photocrosslinkable under UV irradiation. Two-beam coupling method was employed for fabricating the diffraction gratings. The dynamics of formation and erasure of the gratings was studied in term of the variation of the diffraction efficiency. The decaying behavior of the polarization efficiency was also observed after turning off the two pump beams. For complete erasure of the diffraction gratings, we irradiated the linearly polarized single beam. During two-beam coupling, we irradiated UV light on the film surface. The effects of the photocrosslink between the double bonds in chalcone units on the value and dynamic properties of diffraction efficiency are mainly studied in this work.

• Macromolecular Research
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• 제15권2호
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• pp.109-113
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• 2007

The surface molecular motion of monodisperse polystyrene (PS) films was examined using scanning vis-coelasticity microscopy (SVM) in conjunction with lateral force microscopy (LFM). The dynamic storage modulus, E', and loss tangent, $tan\delta$, at a PS film surface with number-average molecular weights, $M_n$, smaller than 30 k were found to be smaller and larger than those for the bulk sample, even at room temperature, meaning that the PS surface is in a glass-rubber transition or fully rubbery sate at this temperature when the $M_n$ is small. In order to quantitatively elucidate the dynamics of the molecular motion at the PS surface, SVM and LFM measurements were performed at various temperatures. The glass transition temperature, $T_g$, at the surface was found to be markedly lower than the bulk $T_g$, and this discrepancy between the surface and bulk became larger with decreasing $M_n$. Such an intensive activation of the thermal molecular motion at the PS surfaces can be explained in terms of an excess free volume in the vicinity of the film surface induced by the preferential segregation of the chain end groups.

• 접착 및 계면
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• 제3권1호
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• pp.43-51
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• 2002

Advanced adhesive technologies and demanding applications of adhesive joints can no longer be developed successfully by the traditional "trial and error" approach. Appropriate technical solutions require reference to a reliable basis of well-established scientific knowledge about the elementary mechanisms of adhesion (i.e. the 'fundamental adhesion') as they are responsible for the capability of the compound w transmit mechanical force between the adhesive and the substrate surface (i.e. the 'practical adhesion'). Adhesion mechanisms also influence the formation of polymer structure in the adhesive and the resulting macromolecular dynamics in the interphase that is formed in the adhesive near to the substrate. These manifold molecular factors rule the macroscopic behaviour of an adhesive bond line in terms of mechanical and other physical properties as well as in terms of durability. This paper reviews the level of refinement that understanding of fundamental adhesion has achieved up to now.

• Macromolecular Research
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• 제8권2호
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• pp.59-65
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• 2000

We simulated the conformational changes of polymethacrylates which have side chains with different lengths (methyl and butyl) by molecular dynamics simulation technique. Bulk states of atactic amorphous polymers relaxed at a higher temperature were generated. The chain behaviors of polymethacrylates were investigated upon varying temperatures. Molecular structural information was then obtained by characterizing radial distribution function(RDF), mean square displacement, self diffusion constant, and Connolly surfaces, among others. The estimated self diffusion constants and RDF values of PMMA and PBMA were found to be in good agreement with our expectation in view of the chain flexibility.