Rheological analysis of core-stabilized Pluronic F127 by semi-interpenetrating network (sIPN) in aqueous solution

Li, Xiaolei,Park, Eun-kyoung,Hyun, Kyu,Oktavia, Listiana,Kwak, Minseok Society of Rheology 2018 Journal of rheology Vol.62 No.1

<P>A poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (Pluronic F127) micelle system was stabilized using an ultraviolet-induced semi-interpenetrating network (sIPN). The sIPN structure within the micelle cores was found to stabilize the micelles against low temperatures, but affected the resulting material properties. In this study, the rheological properties of Pluronic F127 with sIPN (F127-sIPN) and without sIPN (F127) were compared. The presence of the sIPN structure increased the gelation temperature (T-gel) at the same concentration, and unlike F127, F127-sIPN exhibited strong heating rate dependent and thermodynamically irreversible behaviors. Hard gels containing various concentrations of F127-sIPN and F127 were investigated at 40 degrees C. At concentrations above 18 wt. %, both F127-sIPN and F127 exhibited similar linear viscoelastic properties due to the tight, ordered core-shell micelles packing, but the two systems exhibited different behaviors below 18 wt. % concentration. To investigate this difference, hard gels with 16 wt. % F127-sIPN and F127 were selected, and two types of nonlinear rheological tests were conducted, i.e., large amplitude oscillatory shear (LAOS) and strain-rate frequency superposition (SRFS) tests. The cage modulus of F127-sIPN obtained from LAOS testing showed it maintained its elastic contribution over the large deformation region meaning that a loose core network still existed. The relaxation time spectrum of F127-sIPN obtained by SRFS testing indicated it had two relaxation modes (fast and slow) whereas that for F127 had only a fast mode. The slow relaxation mode of F127-sIPN is associated with crosslinking of the sIPN. Since these behaviors were not observed in linear rheological tests, it was concluded that nonlinear rheological tests provide more structural information about hard gels. (C) 2017 The Society of Rheology.</P>

Rheological characteristics of non-spherical graphite suspensions

Mustafa, Hiromoto Usui,Ishizuki, Masanari,Shinge, Ibuki,Suzuki, Hiroshi The Korean Society of Rheology 2003 Korea-Australia rheology journal Vol.15 No.1

Since the microstructure of functional thin films depends on the dispersion characteristics of dense slurry, it is important to control the agglomerative nature of slurries under processing. The present authors have been discussing the model prediction of agglomerative nature and local rate of agglomeration in dense suspensions. The experiments have been peformed under shear flow using the nearly spherical and oblate type graphite particles. In this study, the experiment has been conducted using water and glycerol as dispersion media. Stress control type rheometer was used to measure the slurry rheology. Local agglomeration of graphite particles has been predicted by using Usui's model. The experimental results show that both the shape and slurry processing method affect on the local dispersion condition. The agglomeration formed by oblate type graphite particles seems to be more difficult to break up than that of spherical particles.

Droplet deformability and emulsion rheology: steady and dynamic behavior

Saiki Yasushi,Prestidge Clive A. The Korean Society of Rheology 2005 Korea-Australia rheology journal Vol.17 No.4

The static and dynamic rheological behavior of concentrated sodium dodecylsulfate (SDS) stabilized, deformability controllable polydimethylsiloxane (PDMS) emulsions is reported and comparisons made with silica (hard sphere) suspensions. Steady-mode measurements indicate 'hard' (viscoelastic) droplets behave as hard spheres, while 'soft' (viscous) droplets induce structural flexibility of the emulsion against shear. Dynamic-mode measurements reveal that viscoelasticity of droplets provides the great magnitude of elasticity for the 'hard' emulsion, while formation of planar films between droplets is the origin of the elasticity of 'soft' emulsions. Combination of steady and dynamic rheological behavior has enabled depiction of droplet structure evolution in relation to the shear stress applied, especially by taking advantage of the normal force that reflects the transient deformation of droplets.

Finite element analysis of planar 4:1 contraction flow with the tensor-logarithmic formulation of differential constitutive equations

Kwon Youngdon The Korean Society of Rheology 2004 Korea-Australia rheology journal Vol.16 No.4

High Deborah or Weissenberg number problems in viscoelastic flow modeling have been known formidably difficult even in the inertialess limit. There exists almost no result that shows satisfactory accuracy and proper mesh convergence at the same time. However recently, quite a breakthrough seems to have been made in this field of computational rheology. So called matrix-logarithm (here we name it tensor-logarithm) formulation of the viscoelastic constitutive equations originally written in terms of the conformation tensor has been suggested by Fattal and Kupferman (2004) and its finite element implementation has been first presented by Hulsen (2004). Both the works have reported almost unbounded convergence limit in solving two benchmark problems. This new formulation incorporates proper polynomial interpolations of the log­arithm for the variables that exhibit steep exponential dependence near stagnation points, and it also strictly preserves the positive definiteness of the conformation tensor. In this study, we present an alternative pro­cedure for deriving the tensor-logarithmic representation of the differential constitutive equations and pro­vide a numerical example with the Leonov model in 4:1 planar contraction flows. Dramatic improvement of the computational algorithm with stable convergence has been demonstrated and it seems that there exists appropriate mesh convergence even though this conclusion requires further study. It is thought that this new formalism will work only for a few differential constitutive equations proven globally stable. Thus the math­ematical stability criteria perhaps play an important role on the choice and development of the suitable con­stitutive equations. In this respect, the Leonov viscoelastic model is quite feasible and becomes more essential since it has been proven globally stable and it offers the simplest form in the tensor-logarithmic formulation.

From rheometry to rheology

Sridhar, T. The Korean Society of Rheology 2000 Korea-Australia rheology journal Vol.12 No.1

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.

Direct numerical simulations of viscoelastic turbulent channel flows at high drag reduction

Housiadas Kostas D.,Beris Antony N. The Korean Society of Rheology 2005 Korea-Australia rheology journal Vol.17 No.3

In this work we show the results of our most recent Direct Numerical Simulations (DNS) of turbulent viscoelastic channel flow using spectral spatial approximations and a stabilizing artificial diffusion in the viscoelastic constitutive model. The Finite-Elasticity Non-Linear Elastic Dumbbell model with the Peterlin approximation (FENE-P) is used to represent the effect of polymer molecules in solution, The corresponding rheological parameters are chosen so that to get closer to the conditions corresponding to maximum drag reduction: A high extensibility parameter (60) and a moderate solvent viscosity ratio (0.8) are used with two different friction Weissenberg numbers (50 and 100). We then first find that the corresponding achieved drag reduction, in the range of friction Reynolds numbers used in this work (180-590), is insensitive to the Reynolds number (in accordance to previous work). The obtained drag reduction is at the level of $49\%\;and\;63\%$, for the friction Weissenberg numbers 50 and 100, respectively. The largest value is substantially higher than any of our previous simulations, performed at more moderate levels of viscoelasticity (i.e. higher viscosity ratio and smaller extensibility parameter values). Therefore, the maximum extensional viscosity exhibited by the modeled system and the friction Weissenberg number can still be considered as the dominant factors determining the levels of drag reduction. These can reach high values, even for of dilute polymer solution (the system modeled by the FENE-P model), provided the flow viscoelasticity is high, corresponding to a high polymer molecular weight (which translates to a high extensibility parameter) and a high friction Weissenberg number. Based on that and the changes observed in the turbulent structure and in the most prevalent statistics, as presented in this work, we can still rationalize for an increasing extensional resistance-based drag reduction mechanism as the most prevalent mechanism for drag reduction, the same one evidenced in our previous work: As the polymer elasticity increases, so does the resistance offered to extensional deformation. That, in turn, changes the structure of the most energy-containing turbulent eddies (they become wider, more well correlated, and weaker in intensity) so that they become less efficient in transferring momentum, thus leading to drag reduction. Such a continuum, rheology-based, mechanism has first been proposed in the early 70s independently by Metzner and Lamley and is to be contrasted against any molecularly based explanations.

Rheological properties of chitosan solutions

Hwang, Jae-Kwan,Shin, Hae-Hun The Korean Society of Rheology 2000 Korea-Australia rheology journal Vol.12 No.3

Rheological properties of chitosan solutions were investigated as a function of polymer concentration. The viscosity curves for chitosan solutions consisted of two distinct viscosity regions, the Newtonian zero-shear viscosity (η$_{0}$) region and the shear rate dependent apparent viscosity (η$_{app}$) region. The shear rate dependence of viscosity was more clearly observed at higher chitosan concentrations. The critical coil overlap parameter (C*〔η〕) was determined to be approximately 3.2 from a plot of zero-shear specific viscosity η$_{sp,0}$ vs coil overlap parameter (C〔η〕), which was lower than C〔η〕4.0 reported for other random coil polysaccharides. It was also found that the slope of η$_{sp,0}$ vs C〔η〕 was 3.9 at concentrated C〔η〕>C*〔η〕domain, while 1.2 at dilute C〔η〕<C*〔η〕domain. The steady viscosity (η) of chitosan solution displayed a good superposition at η/η$_{0}$ ${\gamma}$/${\gamma}$$_{0.8}$ relation.ion.n.n.

Rheology of alumina suspensions stabilized with Tiron

Gulicovski, J.J.,Cerovic, Lj.S.,Milonjic, S.K. The Korean Society of Rheology 2008 Korea-Australia rheology journal Vol.20 No.2

Pressure filtration technique was used to obtain defect-free microstructure of green cast ceramic bodies. Stable alumina suspensions of desired rheology (<5 Pa s at $1\;s^{-1}$) containing 60-80 mass. % solid loading were prepared in the alkaline region (at $pH{\approx}9$) with an optimum amount of 0.5 dmb % of Tiron added. Acidic region (at $pH{\approx}4$) enabled the preparation of 60 mass. % suspensions with addition of 1.5 dmb % of Tiron. The best quality slip was processed from an 80 mass.% suspension with 63% of theoretical density. The homogeneity of particle packing and the absence of defects in microstructure were proven by narrow pore size distribution (ranging from 32 to 64 nm, with up to 85% abundance), confirming advantages of the wet consolidation route.

Rheological properties and thermal degradation behaviors of sonochemically treated polycarbonate/polysiloxanes blends

Choi, Mi-Kyung,Kim, Yu-Bin,Kim, Ji-Hye,Kim, Hyung-Su The Korean Society of Rheology 2008 Korea-Australia rheology journal Vol.20 No.4

Two polysiloxanes having different chemical structures were blended with polycarbonate (PC) under ultrasonic irradiation in solution. The polysiloxanes used were poly(methylphenyl siloxane) and vinyl-terminated poly(dimethyl siloxane). It was of primary interest to investigate the effect of polysiloxane structure on the rheological properties of PC/polysiloxane blends. It was found that a small amount (1.5 phr) of polysiloxanes greatly altered the melt viscosities and elasticity of PC. In particular, incorporation of poly(methylphenylsiloxane) led to a notable increase in elasticity with greater shear sensitivity of PC. The observed rheological behaviors of PC/polysiloxane blends were partly explained in conjunction with the tendencies found in ultrasonic degradation of polysiloxanes. Thermal stability and morphology in sonicated blends of PC/polysiloxane blends were also discussed.

Rheological anomalies of the poly(ethylene 2, 6-naphthalate) and poly(ethylene terephthalate) blends depending on the compositions

Lee, Hyang-Mok,Suh, Duck-Jong,Kil, Seung-Bum,Park, O-Ok,Yoon, Kwan-Han The Korean Society of Rheology 1999 Korea-Australia rheology journal Vol.11 No.3

The effects of the transreactions on the rheological properties have been found in the poly(ethylene 2, 6-naphthalate) (PEN) and poly (ethylene terephthalate) (PET) blends. The rheological properties were very much dependent on the blend compositions, which, in turn, were related to extent of the reactions. In particular, a blend with 50/50 wt% composition exhibits an unusual and remarkable decrease in complex viscosity and it may be related to the randomness of the copolymer structure through transreactions. It has been identified by investigating the extent of transreactions and block length of the copolymer from the (ethylene 2, 6-naphthalate) (EN) and (ethylene terephthalate) (ET) units from $^1{H}$ n.m.r. spectra.