Shear-induced Phase Separation Research Articles

The biocompatibility and hemostatic efficacy of silk fibroin nanofibrils fabricated by Shear-Induced phase separation process

The biocompatibility and hemostatic efficacy of silk fibroin nanofibrils fabricated by Shear-Induced phase separation process

A theory for the flow of chemically responsive polymer solutions: Equilibrium and shear-induced phase separation

Chemically responsive polymers are macromolecules that respond to local variations of the chemical composition of the solution by changing their conformation, with notable examples including polyelectrolytes, proteins, and DNA. The polymer conformation changes can occur in response to changes in the pH, the ionic strength, or the concentration of a generic solute that interacts with the polymer. These chemical stimuli can lead to drastic variations of the polymer flexibility and even trigger a transition from a coil to a globule polymer conformation. In many situations, the spatial distribution of the chemical stimuli can be highly inhomogeneous, which can lead to large spatial variations of polymer conformation and of the rheological properties of the mixture. In this paper, we develop a theory for the flow of a mixture of solute and chemically responsive polymers. The approach is valid for generic flows and inhomogeneous distributions of polymers and solutes. To model the polymer conformation changes introduced by the interactions with the solute, we consider the polymers as linear elastic dumbbells whose spring stiffness depends on the solute concentration. We use Onsager’s variational formalism to derive the equations governing the evolution of the variables, which unveils novel couplings between the distribution of dumbbells and that of the solute. Finally, we use a linear stability analysis to show that the governing equations predict an equilibrium phase separation and a distinct shear-induced phase separation whereby a homogeneous distribution of solute and dumbbells spontaneously demix. Similar phase transitions have been observed in previous experiments using stimuli-responsive polymers and may play an important role in living systems.

Denaturation Behavior and Kinetics of Single- and Multi-Component Protein Systems at Extrusion-Like Conditions.

In this study, the influence of defined extrusion-like treatment conditions on the denaturation behavior and kinetics of single- and multi-component protein model systems at a protein concentration of 70% (w/w) was investigated. α-Lactalbumin (αLA) and β-Lactoglobulin (βLG), and whey protein isolate (WPI) were selected as single- and multi-component protein model systems, respectively. To apply defined extrusion-like conditions, treatment temperatures in the range of 60 and 100 °C, shear rates from 0.06 to 50 s⁻1, and treatment times up to 90 s were chosen. While an aggregation onset temperature was determined at approximately 73 °C for WPI systems at a shear rate of 0.06 s⁻1, two significantly different onset temperatures were determined when the shear rate was increased to 25 and 50 s⁻1. These two different onset temperatures could be related to the main fractions present in whey protein (βLG and αLA), suggesting shear-induced phase separation. Application of additional mechanical treatment resulted in an increase in reaction rates for all the investigated systems. Denaturation was found to follow 2.262 and 1.865 order kinetics for αLA and WPI, respectively. The reaction order of WPI might have resulted from a combination of a lower reaction order in the unsheared system (i.e., fractional first order) and higher reaction order for sheared systems, probably due to phase separation, leading to isolated behavior of each fraction at the local level (i.e., fractional second order).

Influence of Thermomechanical Treatment and Ratio of β-Lactoglobulin and α-Lactalbumin on the Denaturation and Aggregation of Highly Concentrated Whey Protein Systems.

The influence of thermomechanical treatment (temperature 60 °C–100 °C and shear rate 0.06 s−1–50 s−1) and mixing ratio of β-lactoglobulin (βLG) and α-lactalbumin (αLA) (5:2 and 1:1) on the denaturation and aggregation of whey protein model systems with a protein concentration of 60% and 70% (w/w) was investigated. An aggregation onset temperature was determined at approx. 80 °C for both systems (5:2 and 1:1 mixing ratio) with a protein concentration of 70% at a shear rate of 0.06 s−1. Increasing the shear rate up to 50 s−1 led to a decrease in the aggregation onset temperature independent of the mixing ratio. By decreasing the protein concentration to 60% in unsheared systems, the aggregation onset temperature decreased compared to that at a protein concentration of 70%. Furthermore, two significantly different onset temperatures were determined when the shear rate was increased to 25 s−1 and 50 s−1, which might result from a shear-induced phase separation. Application of combined thermal and mechanical treatment resulted in overall higher degrees of denaturation independent of the mixing ratio and protein concentration. At the conditions applied, the aggregation of the βLG and αLA mixtures was mainly due to the formation of non-covalent bonds. Although the proportion of disulfide bond aggregation increased with treatment temperature and shear rate, it was higher at a mixing ratio of 5:2 compared to that at 1:1.

Nanorods with Different Surface Properties in Directing the Compatibilization Behavior and the Morphological Transition of Immiscible Polymer Blends in Both Shear and Shear-Free Conditions

To explore the mechanism of how the nanorod surface properties regulate the compatibilization behavior and the morphology transition in demixing polymer blends, we perform dissipative particle dynamics simulations and study the impact of three typical nanorods on the phase separation kinetics and structure as well as their location and arrangement under both shear-free and shear conditions with the variation of nanorod–polymer affinity parameters. Depending on the dispersion and location of nanorods, blends in the quiescent case either undergo full phase separation and generate bulky two-phase morphology, or experience microphase separation and form BμE-like structure, or proceed viscoelastic phase separation and take the kinetically trapped cocontinuous network morphology, whereas shear flow can either accelerate domain coarsening or strongly impact the phase behavior through shear-induced bulk phase separation or shear-induced ordering transition. Particularly, the shear-induced lamellar phase in Janus ...

Organoclay/thermotropic liquid crystalline polymer nanocomposites. Part I: Effects of concentration on morphology, liquid crystallinity and thermal properties

AbstractThermotropic liquid crystalline polymer (TLCP) nanocomposites with different organoclay contents were prepared by a method combining ultrasonication, centrifugation and solution casting methods. The effects of organoclay concentration on morphology, liquid crystallinity and thermal properties of nanocomposites were characterized. Molecular level interactions existed in nanocomposites. With a small amount of organoclay (nominal 3.0 wt %), it was enough to change TLCP properties with enhanced thermal stability though with a small negative effect on liquid crystallinity. When high concentration organoclay was added, thermal stability decreased and liquid crystallinity lost with shearinduced phase separation occurrence.

Miscibility and rheologically determined phase diagram of poly(ethylene oxide)/poly(ε-caprolactone) blends

Poly(ethylene oxide)/poly(e-caprolactone) (PEO/PCL) blends can be widely used in lithium rechargeable battery area or as medical materials, while the miscibility and phase diagram of the blends are still unclear. The present work attempted to establish the blends’ phase diagram using rheometry and investigated the miscibility. The results showed that a miscibility window of upper critical solution temperature character of the blends is revealed. Meanwhile, the abnormal rheological behavior of PEO at temperatures higher than 130 °C has little influence on the phase diagram determination. Different rheological properties of PEO/PCL blends from those of PEO revealed the existence of interactions between PEO and PCL molecular chains. Whereas shear-induced mixing or shear-induced phase separation might occur in phase diagram determination of PEO/PCL blends using rheometry.

Shear-induced phase separation (SIPS) with shear banding in solutions of cationic surfactant and salt

The rheological behavior and microstructure of branched, cationic wormlike micellar (WLM) solutions of 40 mM erucyl bis(hydroxyethyl)methylammonium chloride (EHAC) are studied as a function of added salt (sodium salicylate) concentration, temperature, and shear rate via Rheosmall-angle light scattering (Rheo-SALS). These WLM solutions exhibit shear-enhanced concentration fluctuations leading to shear-induced phase separation (SIPS), manifested as visual turbidity under shear and the appearance of a characteristic “butterfly” scattering pattern in Rheo-SALS experiments. Flow kinematics measurements in a Couette geometry are used to determine the relationship between SIPS and shear banding, i.e., the splitting of the flow into shear bands with different local shear rates. Modeling using the Giesekus constitutive equation aids in discrimination between banding and nonbanding solutions. The combination of Rheo-SALS, dynamic rheology, velocimetry, and constitutive equation modeling allows detailed exploration of the relationship between SIPS, shear banding, fluid microstructure, and the equilibrium phase behavior.

Dynamical coupling between stress and concentration fluctuations in a dynamically asymmetric polymer mixture, investigated by time-resolved small-angle neutron scattering combined with linear mechanical measurements

By time-resolved small-angle neutron scattering (SANS) monitoring of two kinetic phenomena of (i) an early stage of spinodal decomposition and (ii) relaxation of shear-induced phase separation after shear cessation, we quantitatively investigated a growth or relaxation rate R(q) of the concentration fluctuations in a polymer mixture of polystyrene (PS)/poly (vinyl methyl ether) (PVME), where q is the magnitude of scattering vector. R(q) thus determined is largely influenced according to a scheme of dynamical coupling between stress and diffusion. The coupling effect gives rich varieties depending on two crossovers of (i) from viscous to gel-like limits and (ii) from dynamic symmetry to asymmetry, which are tuned by temperature change in the intermediate temperature region between largely different glass transition temperatures, Tg, for each constituent. With respect to q-behaviors of R(q), we observed as follows; (i) in a conventional (dynamically symmetric) viscous limit (T ≥ 110 °C), R(q) shows q2, (ii) in a dynamically asymmetric viscous limit (T = 100–80 °C) R(q) becomes q-independent, (iii) shallow in a dynamically asymmetric gel-limit (T = 80–60 °C), R(q) shows q2 for low q and q-independent for high q, and (iv) deep in a gel-like dynamically asymmetric limit (50–40 °C), R(q) splits into fast and slow modes (showing q2 and q-independent, respectively). In order to explain the rich variety found in R(q), we employed a time-dependent Gintzburg-Landau equation (TDGL) modified to consider the stress and diffusion coupling effect. Two mechanical relaxation times of terminal reptation and Rouse modes were determined by linear viscoelasticity measurements to successfully reproduce the rich variety in R(q) according to the modified TDGL.

Direct Observation of Flow-Concentration Coupling in a Shear-Banding Fluid

We present the first direct evidence of flow-concentration coupling in a shear-banding fluid using the first measurements of scanning narrow-aperture flow ultrasmall-angle neutron scattering. Transmission measurements in the flow-gradient shear plane determine the spatial concentration profile of the material. Shear banding in a model fluid composed of wormlike micelles near an equilibrium isotropic-nematic transition is shown to be concomitant with shear-induced demixing, providing new insight into the nonequilibrium phase behavior of the fluid. The new experimental approach and analysis apply generally to any fluid, and will enable more rigorous testing of theories for shear-banding and shear-induced phase separation.

Organoclay/thermotropic liquid crystalline polymer nanocomposites. Part II: shear-induced phase separation

Experimental studies on a kind of thermotropic liquid crystalline polymer (TLCP) containing 30% p-hydroxybenzoic acid (HBA), 35% hydroquinone (HQ), and 35% sebacic acid (SA) in mole fractions and its nanocomposite (TC3) containing 3.0 wt% organoclay are reported. The structures and dynamics of shear-induced phase separation and the effects of these structures on the macroscopic rheological properties of the nanocomposite are characterized under different shear conditions at 190 °C, which is in the nematic transition region of TLCP. The molecular level interactions between organoclay and TLCP molecules form a percolated-network structure in the composite, causing the composite to display complex viscosity with more than two orders of magnitude greater than that of TLCP in linear regions. However, such a network structure is easily destroyed in steady shear deformation, and it does not recover. Polarized optical microscopy (POM) equipped with a Cambridge shear system and transmission electron microscopy (TEM) confirm a shear-induced phase separation phenomenon during steady shear deformation. Two phases are observed in POM and TEM, with TLCP-rich and organoclay-rich phases. Steady shear at a small shear rate is effective to separate the two phases for characterizations.

Computer simulation study on the shear-induced phase separation in semi-dilute polymer solutions by using Ianniruberto–Marrucci model

In our previous study, a computer simulation scheme based on Doi–Onuki theory is proposed to simulate the dynamics of the shear-induced phase separation in semi-dilute polymer solutions [KOBUNSHI RONBUNSHU 2007, 64, 324]. The scheme employs Ianniruberto–Marrucci model as a constitutive equation to express the viscoelastic behavior of the solution explicitly. The scheme enables us to simulate the time-evolution of stress as well as that of shear-induced structure upon shear-jump. In this study, we focus on the conformation of polymer chains. The dynamics of the polymer chains agrees with those in the “solvent squeeze” model which interprets the shear-induced phase separation phenomena in semi-dilute polymer solutions by Saito et al. [Macromolecules 1999, 32, 4879].

Organoclay/thermotropic liquid crystalline polymer nanocomposites. Part V: morphological and rheological studies

Small amounts of organoclays in different sizes and concentrations were added into thermotropic liquid crystalline polymer (TLCP) by a combination method of ultrasonication, centrifugation, and solution casting (and shear-induced phase separation). Four kinds of organoclay-modified TLCP composites were obtained. TC3 UP was a kind of organoclay which displayed a marked shear-induced phase separation phenomenon at 190 °C and higher temperatures. TC3 UP could be separated into a TLCP-rich part, TC3 white, and an organoclay-rich part, TC3 dark. TC3 white was an organoclay-modified TLCP with fully exfoliated organoclay of a uniform size of 15–25 nm well dispersed in the TLCP. TC3 dark had a typical intercalated model structure with some TLCP molecules confined in organoclay galleries. TC3 FS was an organoclay-modified TLCP with organoclay of comparable size to that of the fully extended TLCP molecule, i.e., 85 nm. The organoclay layers dispersed into the polymeric matrix as a few randomly organized organoclay layers or stacks of layers in the quiescent condition in organoclay-modified TLCPs. The larger organoclay size or higher concentration of organoclay in the composites (such as, TC3 UP and TC3 dark) caused a greater proportion of the layers or stacks be hydro-dynamically impeded in the quiescent state, resulting in the filler–filler interaction becoming important and in fact dominating the long-term viscoelasticity of the composites. Additionally, the ease with which the organoclay structure could be altered by flow was considerably enhanced, primarily because of filler–filler interactions. Organoclay size has primary effect on the liquid crystallinity of TLCP. Small or comparable organoclay size with the fully extended TLCP molecule in TC3 white and TC3 FS has weak or negligible negative influence on the liquid crystallinity of TLCP, while larger organoclay size totally damages the liquid crystallinity of TLCP. The morphologies, liquid crystallinity as well as the linear and non-linear viscoelastic behaviors of organoclay-modified TLCPs have been characterized in detail.

Shear-Induced Phase Separation in Polyelectrolyte/Mixed Micelle Coacervates

A quantitative study of the shear-induced phase separation of a polycation/anionic-nonionic micelle coacervate is presented. Simultaneous rheology and small-angle light scattering (SALS) measurements allow the elucidation of micrometer-scale phase separation under flow in three coacervate solutions. Below 18 degrees C, all three of the coacervate solutions are optically clear Newtonian fluids across the entire shear rate range investigated. Once a critical temperature range and/or shear rate is achieved, phase separation is observed in the small-angle light scattering images and the fluid exhibits shear thinning. Two definitive SALS patterns demonstrate the appearance of circular droplets at low shear rates near the critical temperature and ellipsoidal droplets at higher temperatures and shear rates. The shear-induced droplets range in size from approximately 1 to 4 mum. The ellipsoidal droplets have aspect ratios as high as 4. A conceptual picture in which shear flow extends the polyelectrolyte chains of the clear coacervate liquid phase is proposed. The extended chains create interpolyelectrolyte-micelle interactions and promote expulsion of small ions from the complex, resulting in the formation of micrometer-scale phase-separated droplets.

Shear-induced phase separation and crystallization in semidilute solution of ultrahigh molecular weight polyethylene: Phase diagram in the parameter space of temperature and shear rate

Abstract In the previous papers, we elucidated enhancement of concentration fluctuations, phase separation, and crystallization induced by steady state or step-up shear flow, as observed by shear small-angle light scattering, optical microscopy, and birefringence, for a semidilute solution of ultrahigh molecular weight polyethylene in paraffin as an athermal solvent. However the studies were done only at a given temperature of 124 °C, which is higher than the nominal melting temperature of the quiescent solution Tnm (115–119 °C). It is crucial to extend the studies over a wider temperature range in order to generalize shear-induced phase behavior of the solution. Thus in this work we constructed a kind of phase diagram in the parameter space of temperature (T) and shear rate ( γ ˙ ). The temperature range covered was higher than Tnm, so that the phase diagram is strictly concerned with shear-induced phase behavior (i.e., without shear the solution is homogeneous and in a single-phase state). The diagram identified Regimes I–III in the T– γ ˙ space as will be detailed in the text. In constructing the phase diagram we found the following new points also. (i) The critical shear rate γ ˙ cx which defines the boundary between Regimes I and II was independent of T. (ii) Regime III identified previously through the γ ˙ dependence of the integrated scattered intensity only at a particular temperature T = 124 °C was further separated into two regimes of IIIa and IIIb below and above a critical temperature (147 °C), respectively, through the observation of the γ ˙ dependence as a function of T: In Regime IIIa, the sheared solution developed the optically anisotropic fibrous structures, indicative of the shear-induced crystallization triggered by the shear-induced concentration fluctuations in Regime II; In Regime IIIb, the solution is so stable that it did not show a trend of the shear-induced crystallization even at the highest shear rates accessible in this experiment, but it only showed the shear-induced phase separation. (iii) The critical shear rates γ ˙ c,streak and γ ˙ cz, which define respectively the boundary between Regimes II and IIIa and that between Regimes II and IIIb, are sensitive to temperature.

Shear small-angle light scattering studies of shear-induced concentration fluctuations and steady state viscoelastic properties

We aimed at elucidating the influence of shear-induced structures (shear-enhanced concentration fluctuations and/or shear-induced phase separation), as observed by rheo-optical methods with small-angle light scattering under shear flow (shear-SALS) and shear-microscopy, on viscoelastic properties in semidilute polystyrene (PS) solutions of 6.0 wt % concentration using dioctyl phthalate (DOP) as a Theta solvent and tricresyl phosphate (TCP) as a good solvent. In order to quantify the effects of the shear-induced structures, we conducted a numerical analysis of rheological properties in a homogeneous solution based on the constitutive equation developed by Kaye-Bernstein, Kearsley, and Zapas (K-BKZ). In the low-to-intermediate shear rate gamma region between tau(w) (-1) and tau(e) (-1), where tau(w) and tau(e) are, respectively, terminal relaxation time and the relaxation time for chain stretching, the steady state rheological properties, such as shear stress sigma and the first normal stress difference N(1), for the PS/DOP and PS/TCP solutions are found to be almost same and also well predicted by the K-BKZ equation, in spite of the fact that there is a significant difference in the shear-induced structures as observed by shear-SALS and shear-microscopy. This implies that the contribution of the concentration fluctuations built up by shear flow to the rheological properties seems very small in this gamma region. On the other hand, once gamma exceeds tau(e) (-1), sigma and N(1) for both PS/DOP and PS/TCP start to deviate from the predicted values. Moreover, when gamma further increases and becomes higher than gamma(a,DOP) (sufficiently higher than tau(e) (-1)), above which rheological and scattering anomalies are observed for PS/DOP, sigma and N(1) for PS/DOP and PS/TCP are significantly larger than those predicted by K-BKZ. Particularly, a steep increase of sigma and N(1) for PS/DOP above gamma(a,DOP) is attributed to an excess free energy stored in the system via the deformation of interface of well-defined domains, which are aligned into the stringlike structure developed parallel to the flow axis, and stretching of the chains connecting the domains in the stringlike structures. Thus, we advocate that the effect of shear-induced structures should be well considered on the behavior of sigma and N(1) at the high gamma region above tau(e) (-1) in semidilute polymer solutions.

Mesophase Separation in Polyelectrolyte-Mixed Micelle Coacervates

Mesophase separation has been identified in a polycation/anionic-nonionic mixed micelle system formed by the coacervation of poly(diallyldimethylammoniumchloride)/sodium dodecylsulfate-Triton X-100 in 0.40 M NaCl. The resultant dense, optically clear fluid was studied by turbidity, dynamic light scattering (DLS), and rheology. The presence of two diffusion modes in DLS points to microscopic heterogeneity: coexistence of micelle-rich (dense) domains with micelle-poor (dilute) domains. With an increase in temperature above 20 degrees C, the turbidity rises rapidly along with the intensity of the slow mode. The concomitant decrease in the diffusivity of the slow mode signals an increase in the effective viscosity of the dense domain. With further increase in temperature, dramatic shear thinning is observed, and finally, macroscopic phase separation can be identified by centrifugation. At a temperature near that for quiescent phase separation, we observe shear-induced phase separation. We propose a mechanism to explain the connection between temperature- and shear-induced mesophase separation.

Rheooscillations of a Bottlebrush Polymer Solution Due to Shear-Induced Phase Transitions between a Shear Molten State and a Line Hexatic Phase

Time-resolved small-angle X-ray scattering (SAXS) experiments were carried out on concentrated solutions of bottlebrush polymers exposed to an external shear flow. We followed the rheological response of the sample online. If the experiment is performed in the strain-controlled mode, the rheological response of the bottlebrush polymer solution to the rotational shear shows oscillations with changes in viscosity of almost 2 orders of magnitude. The SAXS data reveal that this oscillatory response is due to a reentrant phase transition between a shear molten phase and a line hexatic phase. It is not due to shear-induced phase separation leading to shear band formation. The in-situ rheological SAXS measurements allow a detailed description of the structural changes occurring in the sample during structural buildup and breakdown.

Shear flow behavior of a dynamically symmetric polymeric bicontinuous microemulsion

We have investigated the shear flow behavior of a dynamically symmetric polymeric bicontinuous microemulsion using rheology and in situ small angle x-ray scattering. The microemulsion consists of a ternary blend of poly (ethylene-alt-propylene) (PEP), poly (butylene oxide) (PBO), and a PEP-PBO diblock copolymer. Steady shear experiments reveal an unusual shear thickening behavior at the onset of the non-Newtonian regime, which is consistent with the strain hardening and frequency thickening (at large strains) under oscillatory shear. Scattering experiments indicate development of anisotropy in the bicontinuous structure within the thickening regime. Subsequent shear thinning is observed at intermediate shear rates. Shear-induced bulk phase separation is detected at very high rates. This work complements previous studies on a dynamically extremely asymmetric bicontinuous microemulsion, and thereby establishes the universal rheological properties of polymeric microemulsions. Possible underlying molecular me...

Temperature-Dependent Phase Behavior of Polyelectrolyte−Mixed Micelle Systems

The effect of temperature on the phase behavior of a polycation-anionic/nonionic mixed micelle system, poly(dimethyldiallylammonium chloride)-sodium dodecylsulfate/Triton X-100, was studied over a wide range of surfactant compositions, ionic strengths, and polycation molecular weights using turbidimetry and dynamic light scattering. Soluble complexes become biphasic upon heating through either liquid-liquid (coacervation) or liquid-solid (precipitation) separation. The biphasic boundary comprises two regions: a coacervate domain exhibiting a lower critical solution temperature and a second superimposed domain in which either solids or very dense and viscous fluids are formed upon heating. The position of the first region is symmetrically centered around conditions corresponding to charge neutralization of complexes and their aggregates at incipient phase separation. The second region, observed at high micelle charge, corresponds to the collapse of polycation onto micelle surfaces and expulsion of counterions and can produce either dense coacervate or precipitate. The two regions exhibit different dependences on ionic strength, polyelectrolyte molecular weight, and concentration, from which inferences about the mechanisms of phase separation may be drawn. Preliminary observations of the dense liquid phases isolated after coacervation disclose a number of interesting optical and rheological properties, possibly arising from shear-induced phase separation.