• Title/Summary/Keyword: chain-entanglement

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Investigation of entanglement dynamics of flexible polymer chains via comparison of dielectric and viscoelastic properties: a review of recent findings

  • Watanabe, H.
    • Korea-Australia Rheology Journal
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    • v.13 no.4
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    • pp.205-217
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    • 2001
  • This review article summarizes results of recent viscoelastic and dielectric studies for entangled cis-polyisoprene (PI) chains. The PI chains have the so-called type-A dipoles parallel along the chain backbone, and their slow viscoelastic and dielectric relaxation processes reflect the same global chain motion. However, this motion is differently averaged in the viscoelastic and dielectric properties, the former representing the isochronal orientational anisotropy of individual entanglement segments while the latter detecting the orientational correlation of the segments at two separate times (0 and t). On the basis of this difference, the viscoelastic and dielectric data of the entangled PI chains were compared to elucidate detailed features of the chain dynamics. Specifically, the molecular picture of dynamic tube dilation (DTD) incorporated in recent models was tested for linear and star PI chain. The comparison revealed that the DTD picture was valid for linear PI chains but failed for the star PI chains in the dominant part of the terminal relaxation. The failure for the star chains was related to the pre-requisite for the DTD process, rapid equilibration of successive entanglement segments through their constraint release (CR) motion: For the star chains, the dilated tube diameter expected in the terminal regime was considerably large because of a broad distribution of motional modes of the chains, so that the CR-equilibration required for DTD could not occur in time. The terminal relaxation of the star chain appeared to occur through the CR process before the expected DTD process was completed. The situation was different for the linear chain exhibiting narrowly distributed motional modes. The dilated tube expected for the linear chain was rather thin and the required CR-equilibration occurred in time, resulting in the success of the DTD picture. These detailed features of the chain dynamics was revealed only when the viscoelastic and dielectric properties were compared, demonstrating the importance of this comparison.

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The Statistical Mechanics of the Rubber Elasticity which is Affected by the Entanglement Effects (고무탄성에 영향을 미치는 사슬 얽힘 효과에 대한 통계역학적 고찰)

  • Park, Sang-Bo;Lee, Tae-Hong
    • Journal of the Korean Graphic Arts Communication Society
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    • v.21 no.1
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    • pp.45-58
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    • 2003
  • The entanglement effects were described by means of holes through which the network chain must pass. Inhomogeneous entanglement effects were related to the hole distributions on the surface and in the center of spheres in the network chains. It was assumed that holes were subjected to the affiance deformation and the network chains were gaussian distribution. The results of this model calculation was compared with the compression- extension experimental data of PDMS (polydimethyl siloxane) rubber, and then hole's relative position was known to be in the center of two adjacent holes.

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ArcGIS based Analysis of Multiple Accident Areas Caused by Marine Plastic Litter in Republic of Korea

  • Kim, Bo-Ram;Park, Young-Kwon
    • Applied Chemistry for Engineering
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    • v.33 no.4
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    • pp.408-418
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    • 2022
  • Marine accidents involving the entanglement of marine litter have continued to increase, with over 300 to 400 cases per year according to the statistical agency. Entanglement of marine litter may also lead to large-scale marine accidents which cause capsizing and sinking, thereby further causing detrimental casualties and material damages, and thus exceptional attention and care are required. In this study, Incheon, Busan, and Geoje and Tongyeong were found to be the high-frequency locations for accidents, which were selected by considering the ArcGIS analysis about the marine accidents of entanglement of marine litter and the occurrence frequency by the standard. The characteristics of the multiple accident areas involving entanglement of marine litter were the coastal cities where fishing facilities or marine leisure related conditions were activated, with the port which handles much of the traffic of outbound and inbound vessels located nearby. Marine plastic pollution impacts not only the marine ecosystem and food chain, but also the hull and engine of ships, and may further pose threats to the safety of vessels and crews. It is necessary to find a common link between the relevant areas and to strive to remove the root causes of marine accidents by reducing marine litter.

A Study on Existing Rubber Elasticity Theories for Stress-Strain Behavior of Rubber-like Networks

  • Meissner, B.
    • Elastomers and Composites
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    • v.38 no.2
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    • pp.157-166
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    • 2003
  • The Edwards-Vilgis slip-link theory and the Kaliske-Heinrich extended tube theory were tested experimentally using published experimental data on networks of natural and isoprene rubber and on polysiloxane networks. All parameters were adjusted to achieve an optimum fit. The data description obtained with the EV theory is not satisfactory and the parameter values tend to lie outside their reasonably expected range. But for the region of low strains, the Kaliske-Heinrich theory offers a satisfactorily accurate data description which is able to serve for practical purposes. Its crosslink term, however, is based on approximations which lead to a questionable prediction and values determined for the exponent in the entanglement term lie outside the range expected by the KH model. Thus, the title question cannot be given a positive answer. Conclusions published earlier that the trapped entanglements contribute both to the crosslink and constraint (entanglement) term are supported by the present data analysis. Experimental equibiaxial data on hydrocarbon networks do not show any maximum on their stretch ratio dependence, contrary to the predictions of molecular theories. The stretch ratio dependences of relative reduced stresses do not sensitively reflect differences in the chemical nature of the chain backbone (hydrocarbon vs. siloxane) and in the crosslinking method (end-linking vs. random crosslinking).

The Effects of a Chain Extending Agent and Crosslinking Agent on the Toughness of Castor Oil based Polyurethane-Epoxy IPNs (Castor Oil형 폴리우레탄-에폭시 IPNs에서 사슬연장제와 가교제의 영향에 의한 강인성)

  • Kim, Jong-Seok;Yang, Yeong-Seok
    • Applied Chemistry for Engineering
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    • v.10 no.5
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    • pp.639-643
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    • 1999
  • Interpenetrating polymer networks(IPNs) composed of castor oil(CO) polyurethane(PU) and epoxy resin were prepared by the simultaneous polymerization technique. Two types of PU were prepared using 1,4-butanediol(BD) and BD/trimethylolpropane(TMP) as a chain extending agent and crosslinking agent. The PU/epoxy based on BD as a chain extending agent showed more shift in the damping peak than PU/epoxy based on BD/TMP as the PU content was increased. BDPU/epoxy simultaneous interpenetrating polymer networks(SINs) had a better compatibility than BD/TMP-PU/epoxy SINs. For both systems, it was postulated that unique network formation of PU/epoxy SINs as a chain extending agent and crosslinking agent had occurred to a significant extent of phase mixing. The types of chain extender in the PU were found to be an important factor in determining the phase mixing of the IPNs. When the BD/TMP-PU reaction was faster than epoxy network, the extent of phase mixing was retarded by decreasing entanglement of networks. It was found that both PU/epoxy SINs provided enhanced flexural properties and fracture toughness, fracture surfaces of BDPU/epoxy and BD/TMP-PU/epoxy SINs showed the localized shear deformation and generation of stress whitening associated with the cavitation.

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Optimization to Prepare SIS-SBS Modified Asphalt for Waterproof-sheet (SIS-SBS 개질아스팔트 방수시트재 물성 최적화)

  • Lim, Kwang-Hee
    • Korean Chemical Engineering Research
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    • v.55 no.5
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    • pp.690-697
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    • 2017
  • In this study, styrene-isoprene-styrene (SIS)-styrene-butadiene-styrene (SBS) modified asphalt was prepared for waterproof-sheet to measure its properties including softening point, penetration, low temperature flexibility, viscosity and adhesion. Then the properties of SIS-SBS modified asphalt imparted with self-healing were optimized to seek for optimal compositions of SIS and SBS versus asphalt according to response surface methodology (RSM). As the content of SBS or SIS was increased, both properties of softening point and viscosity, measured at high temperature, were increased with a statistical significance. However, the increments of softening point and viscosity per unit content of SBS added, were observed to be greater than those per unit content of SIS added, respectively. It was due to the difference of thermal properties of SBS and SIS at high temperature that the cross-linking degree of SBS was increased by gelation accompanied with the increase of viscosity, while chain-entanglement of SIS was relatively reduced owing to a chain scission of poly(isoprene) blocks causing the decrease of viscosity. To the contrary, SIS-SBS modified asphalt showed a behavior of the least elasticity resulting in both the maximum of penetration and adhesion, measured at room temperature, as well as the lowest low temperature flexibility at the composition of SIS, 4 g and SBS, 8.5 g based on asphalt, 63 g.

Effect of chain structure of polypropylenes on the melt flow behavior

  • Lee, Young-Jun;Sohn, Ho-Sang;Park, Seung-Ho
    • Korea-Australia Rheology Journal
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    • v.12 no.3_4
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    • pp.181-186
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    • 2000
  • Rheological Properties of polypropylenes having different molecular structures (linear polypropylene (PPL) and branched one (PPB)) were studied. Both the extensional flow and oscillatory shear flow properties were checked. Especially, the melt strength of polypropylenes having various shear history were investigated by using in-house-made Rheometer (called SMER). Compared to linear polypropylene, the branched polypropylene shows enhanced melt strength during extensional flow due to the retarded relaxation of molecules. When the slope of melt tension was plotted against take up speed of melt strand, the characteristic peak was observed in case of branched polypropylene, while the linear polypropylene shows only monotonously decreasing pattern. This entanglement was partially disrupted by physical forces such as shear during melt extrusion. However, the melt strength of PPB after multiple extrusion is still higher than PPL, implying the loss of elasticity during multiple extrusion is not so comprehensive. On dynamic experiments, PPB shows typical shear thinning behavior and the tangent delta of PPB is lower than PPL, reflecting high elasticity of PPB.

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Relaxation Phenomena observed for Single Polymer Chains

  • Watanabe, Kenji;Ohno, Naoto;Nakajima, Ken;Nishi, Toshio
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.341-341
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    • 2006
  • Nanofishing enabled us to stretch a single polymer chain with picking it at its two modified termini using atomic force microscope (AFM). Stress-strain curves obtained to date had been the result on slow pulling events and therefore observed phenomena had been interpreted as quasi-static responses. In this study, we extended the capability of nanofishing to the phenomena far from equilibrium state by giving much faster pulling speeds. We could observe a momental increase entanglement and a successive stress relaxation.

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Dynamic Mechanical Behavior of Ultra-High Molecular Weight Polyethylene Irradiated with Gamma Rays

  • Lee, Choon-Soo;Jho, Jae-Young;Park, Kuiwon;Hwang, Tae-Won
    • Macromolecular Research
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    • v.12 no.1
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    • pp.141-143
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    • 2004
  • We have investigated the dynamic mechanical behavior of ultra-high molecular weight polyethylene (UHMWPE) irradiated with varying doses of gamma rays. A relaxation peak in the loss factor curve, which has not been reported previously in the literature, is observed at a temperature above the crystal melting temperature. The peak is unique to UHMWPE and appears to be related to the high degree of entanglement. Because the temperature and intensity of the peak are reduced by irradiation-induced chain scission and crosslinking, respectively, we believe that the peak is associated with disentanglement relaxation. The behavior of the storage modulus in the melt state agrees with the classical theory of rubber elasticity.

The Toughness of Polyurethane and Epoxy Resins IPNs (폴리우레탄-에폭시 IPNs의 강인성)

  • Kim, Jong Seok;Hong, Suk Pyo
    • Applied Chemistry for Engineering
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    • v.9 no.3
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    • pp.445-450
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    • 1998
  • Interpenetrating polymer networks(IPNs) were prepared from castor oil-type polyurethanes(PUs) and epoxy resin. Two types of PU were prepared by using polypropylene ether glycol(PPG) as a chain extending agent and caster oil(CO) as a crosslinking agent. COPU/epoxy simultaneous interpenetrating polymer networks(SINs) based on CO had a better compatibility over the all composition than PPGPU/epoxy SINs based on PPG. The flexural strength of all PPGPU/epoxy SINs was decreased with decreasing entanglement of networks. COPU/epoxy SINs showed the higher fracture toughness and mechanial properties than the PPGPU/epoxy SINs. Fracture surfaces of all of the SINs showed the localized shear deformation and crack deflection rather than generation of stress whitening associated with the cavitation.

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