• Korea-Australia Rheology Journal
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• v.11 no.4
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• pp.305-311
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• 1999

The shear behavior of polymers obtained by means of devices such as capillary and cone-and-plate rheo-meters is commonly used to assess their processing performance and as a characterization tool. However, the number of instances when two polymers have the same shear properties but perform differently during certain types of processing operations (e.g. film blowing and sheet extrusion) indicate that shear properties alone may not be sufficient to characterize polymeric fluids. We begin by defining the kinematics of shear-free or extensional flow and the associated material functions. The extensional and shear behavior of three different types of polyethylene (PE) are then compared to illustrate the points that one cannot ascertain the extensional properties of polymer melts from their shear properties and, furthermore, there may not be a simple relation between properties obtained from one type of extensional flow and those of another type. The kinematics of most processing flows are extensional rather than shear in nature, and , hence, the performance of polymers during processes such as fiber spinning, film casting, film blowing, thermoforming, blow molding, and even extrusion is more readily accounted for through extensional viscosity measurements. Methods for carrying out extensional flow measurements are then reviewed including approximate methods. To illustrate the sensitivity of extensional viscosity measurements to subtle changes in the molecular architecture of PEs, results are presented for samples with a narrow molecular weight distribution but with varying numbers of long chain branches. Finally, constitutive equations which allow one to separate shear and extensional flow behavior are discussed as any attempts to simulate the subtle processing differences between two polymers will require constitutive equations of this nature.

• Journal of the Korean Society of Visualization
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• v.19 no.1
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• pp.81-87
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• 2021

Extensional flow of viscoelastic fluids is widely utilized in various industrial processes such as electrospinning, 3D printing and plastic injection molding. Extensional rheological properties, such as apparent viscosity and relaxation time, play an important role in the design and evaluation of the viscoelastic fluid-involved processes. In this work, we propose a lab-built capillary breakup extensional rheometer (CaBER) based on flow image processing to investigate the capillary breakup of polyethylene oxide (PEO) solution and its extensional rheological properties. We found that the apparent extensional viscosity and extensional relaxation time of the PEO solution are independent of the strike time. The proposed CaBER is expected to be applied to characterization of the extensional rheological properties of viscoelastic fluids at low cost with high precision.

• Macromolecular Research
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• v.10 no.3
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• pp.135-139
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• 2002

Blends of the linear bisphenol-A polycarbonate (L-PC) and randomly branched bisphenol-A polycarbonate (Br-PC), prepared by co-rotating twin screw extrusion, were investigated using differential scanning calorimetry (DSC), sag resistance time tester, extensional rheometry, and advanced rheometric expansion system (ARES). From the DSC results, the glass transition temperature (T$_{g}$) of the L-PC/Br-PC blend was increased with the increase of Br-PC in the blend, and the blend showed a single T$_{g}$, which suggests a miscible blend. The sag resistance time of the L-PC/Br-PC blend was increased with the increase of Br-PC in the blends. From the results of rheological measurements of the L-PC/Br-PC blends, the extensional viscosity and the complex viscosity of the blends were found to increase with the increase of Br-PC in the blends. The increase of extensional viscosity and complex viscosity was related with the increase of sag resistance time with the Br-PC in the L-PC/Br-PC blends.nds.

• Korea-Australia Rheology Journal
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• v.20 no.3
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• pp.109-116
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• 2008

The effect of intermolecular aggregation induced by hydrophobic and electrostatic interactions on shear and elongational flow properties of aqueous acrylic thickener solutions is discussed. Complex shear modulus is determined at frequencies up to $10^4$ rad/s employing oscillatory squeeze flow. Extensional flow behavior is characterized using Capillary Break-up Extensional Rheometry. Aqueous solutions of poly(acrylic acid)(PAA)/poly(vinylpyrrolidone-co-vinylimidazole) (PVP-VI) mixtures exhibit unusual rheological properties described here for the first time. Zero-shear viscosity of the mixtures increases with decreasing pH and can exceed that of the pure polymers in solution by more than two orders of magnitude. This is attributed to the formation of complexes induced by electrostatic interactions in the pH range, where both polymers are oppositely charged. PAA/PVP-VI mixtures are compared to the commercial thickener Sterocoll FD (BASF SE), which is a statistical co-polymer including (meth) acrylic acid and ethylacrylate (EA) forming aggregates in solution due to "sticky" contacts among hydrophobic EA-sequences. PAA/PVP-VI complexes are less compact and more deformable than the hydrophobic Sterocoll FD aggregates. Solutions of PAA/PVP-VI exhibit a higher zero-shear viscosity even at lower molecular weight of the aggregates, but are strongly shear-thinning in contrast to the weakly shear-thinning solutions of Sterocoll FD. The higher ratio of characteristic relaxation times in shear and elongation determined for PAA/PVP-VI compared to Sterocoll FD solutions reflects, that the charge-induced complexes provide a much stronger resistance to extensional flow than the aggregates formed by hydrophobic interactions. This is most likely due to a break-up of the latter in extensional flow, while there is no evidence for a break-up of complexes for PAA/PVP-VI mixtures. These flexible aggregates are more suitable for the stabilization of thin filaments in extensional flows.

• Korea-Australia Rheology Journal
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• v.19 no.1
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• pp.1-5
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• 2007

By combining ultrasonic energy which is essential for the chain scission of polymer molecules and a multifunctional agent (MFA) having double bonds at its ends, we were able to modify the molecular structure of polycarbonate (PC) from linear to a branched structure during melt processing. The three double bonds in chain ends of MFA were expected to act as sites for trapping macroradicals of PC during the course of ultrasound-assisted mixing process. The transformation of molecular structure of PC was confirmed by the measurements of rheological properties of the modified PC. After the ultrasonic irradiation of PC together with MFA, increase in complex viscosities and shear-thinning behavior were observed. The Cole-Cole plot and measurement of extensional viscosities revealed the characteristic features of branched structure with well-defined extensional behavior which is comparable to that of a commercial branched PC.

• Korea-Australia Rheology Journal
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• v.12 no.1
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• pp.39-53
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• 2000

Using a variety of examples from the recent literature on extensional flow of polymer solutions, this paper shows that simple constitutive equations are unable to capture the diversity of chain conformations in such flows. Such diversity is a feature of extensional flows and arises because deformation leads to significant chain extension. Substantial local extension appears even at low strains and the behaviour of these stretched out portions influences the dynamics of the chain and makes a dominant contribution to the stress. Both the distribution function and the chain conformation appear to follow different paths during stretching and relaxation. As a result the second moment of the distribution function does not contain enough information to correctly predict the dynamics. Resolution of this deficiency in simple constitutive models is one of the challenges for rheology.

• Korea-Australia Rheology Journal
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• v.13 no.1
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• pp.29-35
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• 2001

The development of filament stretching extensional rheometers over the past decade has enabled the systematic measurement of the transient extensional stress growth in dilute and semi-dilute polymer solutions. The strain-hardening in the extensional viscosity of dilute solutions overwhelms the perturbative effects of capillarity, inertia & gravity and the kinematics of the extensional deformation become increasingly homogeneous at large strains. This permits the development of a robust open-loop control algorithm for rapidly realizing a deformation with constant stretch history that is desired for extensional rheometry. For entangled fluids such as concentrated solutions and melts the situation is less well defined since the material functions are governed by the molecular weight between entanglements, and the fluids therefore show much less pronounced strain-hardening in transient elongation. We use experiments with semi-dilute/entangled and concentrated/entangled monodisperse polystyrene solutions coupled with time-dependent numerical computations using nonlinear viscoelastic constitutive equations such as the Giesekus model in order to show that an open-loop control strategy is still viable for such fluids. Multiple iterations using a successive substitution may be necessary, however, in order to obtain the true transient extensional viscosity material function. At large strains and high extension rates the extension of fluid filaments in both dilute and concentrated polymer solutions is limited by the onset of purely elastic instabilities which result in necking or peeling of the elongating column. The mode of instability is demonstrated to be a sensitive function of the magnitude of the strain-hardening in the fluid sample. In entangled solutions of linear polymers the observed transition from necking instability to peeling instability observed at high strain rates (of order of the reciprocal of the Rouse time for the fluid) is directly connected to the cross-over from a reptative mechanism of tube orientation to one of chain extension.

• Macromolecular Research
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• v.14 no.3
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• pp.318-323
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• 2006

We investigated the rheological behaviors and orientation of three different types of layered silicate composite systems under external flow: microcomposite, intercalated and exfoliated nanocomposites. Rheological measurements under shear and uniaxial extensional flows, two-dimensional, small-angle X-ray scattering and transmission electron microscopy were conducted to investigate the properties, as well as nano- and micro-structural changes, of polymer/layered silicate nanocomposites. The preferred orientation of the silicate layers to the flow direction was observed under uniaxial extensional flow for both intercalated and exfoliated systems, while the strain hardening behavior was observed only in the exfoliated systems. The degree of compatibility between the polymer matrix and clay determined the microstructure of polymer/clay composites, strain hardening behavior and spatial orientation of the clays under extensional flow.

• 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.

• The Korean Journal of Rheology
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• v.9 no.3
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• pp.111-117
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• 1997

대표적인 신장유동의 하나인 방사공정을 통해 액정고분자를 포함한 블렌드 섬유의 신장유동의 특성과 형구학적 성질간의 관계를 고찰하였다. 신장유동에 의해 분산상인 액정 고분자는 미세섬유구조를 바뀌었고 압출온도가 높을수록 더욱 발달된 미세섬유구조를 가졌 다. 이러한 분산상의 미세구조 변화에 대한 설명은 블렌드의 신장유동특성을 나타내는 신장 점도비로서 가능하였다. 즉, 압출온도가 높을수록 방사사선에서 신장변형률속도가 z지고 신 장점도비가 작아지므로 분산상의 신장변형이 더 많이 되었다고 판단된다. 방사이전의블렌드 내의 분산상은 압출온도를달리하여도 모두 구형으로 존재함을 발견하였고 이사실로부터 분 산상의 미세섬유구조는 방사사선에서의 신장변형에 의해 주로 이루어졌음을 확인하였다.