Rheological Behavior of Dope Solutions of Poly(acrylonitrile‐co‐itaconic acid) in N,N‐dimethylformamide: Effect of Polymer Molar Mass

The rheological behavior of dope solutions of poly(acrylonitrile‐co‐itaconic acid) or poly(AN‐co‐IA) is important from the point of view of deriving the spinning conditions for good quality special acrylic fibers. The viscosity of the resin dope is dictated by the polymer concentration, molar mass, temperature and shear force. The dynamic shear rheology of concentrated poly(AN‐co‐IA) polymer dope solutions in N, N‐dimethylformamide, in the molar mass (M¯_v) range of 1×10⁵ to 1×10⁶ g/mol, was investigated in the shear rate (γ′) range of 1×10¹ to 5×10⁴ min^?1. An empirical relation between η and M¯_v was found to exist at constant shear rate. The dope viscosity was dependent on the molar mass and the shear rate at a given temperature (T) and concentration. The polymer molar mass index of dope viscosity (m) was calculated as functions of concentration (c), shear rate and temperature. The m values increased with shear rate and temperature. A master equation relating m, with shear rate and temperature was derived for a given dope concentration. At higher shear rates, m tends to the value of 3.4, which is close to the molar mass index of viscosity reported for molten thermoplastics. m increased significantly with shear rate and nominally with temperature, while an increase in concentration decreased it. The onset of shear thinning of the dope shifted to a lower shear rate regime with an increase in polymer concentration and the molar mass. For a given value of molar mass, the increase in viscosity of the dope solution with polymer concentration was dependent on the shear rate.     

Miscibility and morphology of poly(ethylhexylacrylate)/liquid crystal blends prepared under different conditions

A comparative study of the phase diagrams and morphology of blends of poly(2‐ethylhexylacrylate) and low molecular weight liquid crystals (LCs) prepared under different conditions is presented. Two LCs are used; one is the 4‐cyano‐4′‐n‐pentyl‐biphenyl and the other is the eutectic mixture of cyanoparaphenylenes known as E7. Two series of blends are prepared under different conditions. The first series is obtained by the polymerization induced phase separation (PIPS) process under UV‐curing starting from a monomeric mixture, while the second series is prepared by a combination of the solvent induced phase separation and the thermally induced phase separation process starting from a mixture containing a commercial polymer with known molecular weight. Using gel permeation chromatography, it is found that the polymer molecular weight of the UV‐cured systems decreases with the concentration of LC in the precursor mixture. The experimentally obtained phase diagrams of these two series of systems show a miscibility shift at the composition where the molar mass of the polymer in the PIPS/UV blend exceeds that of the commercial polymer. Data are rationalized in terms of the Flory‐Huggins theory of isotropic mixing and the Maier‐Saupe theory of nematic order. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 18–27, 2007     

Novel propylmethacrylate-monofunctionalized polyhedral oligomeric silsesquioxanes homopolymers prepared via radical bulk free polymerization

Novel propylmethacrylate-monofunctionalized polyhedral oligomeric silsesquioxanes (POSS-PMA) homopolymers were obtained, in good yield, by free bulk radical polymerizations of the low melting macromer heptaisobutylpentacyclooctasiloxan-1-(yl)propylmethacrylate [(PMA)(i-Bu)₇T₈], 1, by using different initiator/macromer molar ratios. Their characterization was accomplished by TG, DTG and DSC analyses, Gel permeation chromatography (GPC) and MALDI-TOF mass spectrometry. The results indicate that both macromolecular as well as the thermal properties of the new materials are dependent on the initiator/macromer molar ratio used in the polymerization process. By increasing the amount of initiator, polymers with lowest molecular masses, highest molecular weight distributions (MWD) and lowest thermal stability were obtained. High value of MWD was found for all the samples. The different thermal behavior observed for the sample prepared by using the highest amount of initiator is explained by the formation of polymer branched chain, induced by chain transfer to polymer processes. MALDI-TOF mass spectra resulted diagnostic of the homopolymers compositions displaying a series of peaks corresponding to oligomeric structures present in the polymeric samples. The thermal polymerization of 1 performed without employing catalyst was also investigated. Only low yields (4%) of short oligomers (from dimer to pentamer), bearing degraded POSS cages, were isolated.     

Effects of molar mass, concentration and thermodynamic conditions on polymer-induced flow drag reduction

Drag reduction in Taylor flow of polystyrene solutions is investigated using a commercial rheometer equipped with a standard double-gap sample holder with axial symmetry. The dependence of drag reduction on various factors, including polymer molar mass, polymer concentration, and thermodynamic conditions is studied. Drag reduction induced by polystyrene in toluene is found to increase with increasing polymer concentration in the dilute concentration regime. It is also seen that molecules with high molar mass of the polymer promote drag reduction. In terms of hydrodynamic volume fraction normalisation, it is found that most of the drag reduction effect occurs at volume fractions below 0.2. It is observed that drag reduction is favoured by good thermodynamic conditions of the polymer-solvent system. Both the flow induced extension of the polymer chains and the hydrodynamic volume fraction occupied by the polymer molecules seem to play an important role for the drag reduction effect.     

Dynamic mechanical properties of cyclohexane-based glass-forming liquid crystals and a linear side chain polymer analogue

A nematic and a cholesteric liquid crystal, both derived from trans-1,3,5-cyclohexanetri-carboxylic acid, and a linear side chain polymer analogue were characterized in terms of storage (G') and loss (G') moduli as functions of frequency and temperature. It was found that all three model compounds show a shear shinning flow behaviour with zero shear viscosities of the low molar mass systems significantly less than that of the polymer system at the same reduced temperature, T/T^g. With shift factors prescribed by the WLF equation, both the G' and G' data of all three compounds are adequately represented by master curves. Furthermore, within the framework of the stretched exponential model, the relaxation behaviours of the low molar mass systems are well described by a single Maxwell element, whereas the polymer system shows a relatively broad distribution of relaxation times. The observed viscoelastic properties suggest a relative ease of material processing of the low molar mass systems compared to the polymer analogue due to a lower zero shear viscosity and a single relaxation time characterizing the dynamics of response to a mechanical or thermal stimulus.     

振荡剪切流场下PS/PVME/SiO2复合物的相行为

利用光学显微镜-剪切台联用系统研究了振荡剪切流场下聚苯乙烯（PS）/聚甲基乙烯基醚（PVME）/二氧化硅（SiO₂）纳米粒子复合物的热力学稳定性. 结果表明,小振幅振荡剪切可导致PS/PVME共混物出现类似在稳态流场下的剪切诱导相容及剪切诱导相分离现象. 共混体系存在临界振荡频率ω_c,当振荡频率低于ω_c时,发生剪切诱导相分离（SID）行为,反之发生剪切诱导相容（SIM）行为. SiO₂纳米粒子的加入使复合体系的相容性提高. 存在一个临界SiO₂纳米粒子含量φ_c,当SiO₂纳米粒子含量高于φ_c时,复合体系中不存在临界振荡频率ω_c,低振荡频率下的剪切诱导相分离得到抑制. 此外,复合体系的上述行为与升温速率和共混物组成密切相关.     

Small angle neutron scattering study of polyelectrolyte conformation incorporated into hybrid threadlike micelles under strong shear flows

A small angle neutron scattering study revealed that polyelectrolytes, sodium salts of partially sulfonated polystyrenes with narrow distributed molar masses of Mn = 27 x 10(3) and 340 x 10(3), which were incorporated into hybrid threadlike micelles formed with cetyltrimethylammonium bromide in aqueous (deuterium oxide) solutions at a quiescent state, behaved as rigid rods with lengths of 16 and 200 nm and the same radius of 2.3 approximately 2.4 nm, respectively. Under strong shear flows at shear rates much higher than the reciprocal of the mechanical relaxation time for the solution, the formed hybrid threadlike micelles were highly orientated to the shear flow axis owing to the generation of a shear induced liquid crystalline phase. The polyelectrolytes incorporated into the highly orientated micelle also maintained essentially the same conformation as those in the randomly orientated micelles in a quiescent state even at high shear rates.     

Amphiphilic dendronized homopolymers

A series of second generation of amphiphilic dendronized homopolymers are efficiently synthesized, and their thermoresponsiveness in aqueous solutions and secondary structures in methanol solutions are described. These polymers are constructed in each repeat unit with various generations of hydrophobic 4-aminoproline and hydrophilic oligoethylene glycol (OEG)-based dendrons, and their over-all hydrophilicity is tuned by varying these dendron generations. Polymers with or without the first generation of proline dendron show good water solubility at room temperature, but exhibit typical thermoresponsive behaviors at elevated temperatures as characterized by turbidity measurements using UV-vis spectroscopy, while the polymer with the secondary generation of proline dendron is not soluble in water. All polymers show ordered secondary structures as evidenced by the optical rotation and circular dichroism experiments. Finally, assembly of these amphiphilic homopolymers into porous films via breath figure (BF) technique is described, and polymer structures are found to show significant influence on the morphology of porous film.     

Solution properties of thermothickening copolymers bearing hydrocarbon end‐capped oxyethylene units

Novel thermothickening copolymers composed of acrylamide and a macromer bearing hydrocarbon end‐capped oxyethylene units were synthesized. Influences of polymer concentration, salt content, shear rate, and temperature on the solution behavior were investigated. The polymer solution exhibited shear‐thickening behavior at low‐to‐moderate shear rates (<50 s^?1), and the shear‐thickening behavior was dependent on polymer concentration, NaCl content, and temperature. With the increase of salinity, apparent viscosity of polymer solution increased dramatically (especially at low shear rates). At higher NaCl content (>20 wt %), polymer solutions became physical gel, and the apparent viscosity increased by several orders of magnitude. The polymer solutions exhibited excellent thermothickening behavior, even at the low concentration of 0.15 wt %. The results of rheological measurements showed that the storage and loss modulus were successfully fitted to a single Maxwell element at low temperature (<60 °C). © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1799–1808, 2010     

Rheology and interdiffusion in miscible blends of a low molar mass liquid crystal and bisphenol A–polycarbonate

The melt rheology of blends of a low molar mass liquid crystal (LC) blended with bisphenol A–polycarbonate (PC), and the self‐diffusion of the polycarbonate in the blends are reported. Results of small angle light scattering indicate that the LC is miscible in the mixture for weight fraction of LC less than 6%. The rheological properties of the blended sample within the miscible regime of the blends vary significantly with LC content. Although at low shear rates, the viscosity is similar to that of the pure polycarbonate, at high shear rates the curves show three regions of behavior, as has been described previously for pure LCs. The diffusion coefficient was obtained from interdiffusion studies using nuclear reaction analysis of bilayer films. An addition of only 1 wt % LC to the polycarbonate significantly increased the diffusion coefficient, but at higher concentration the converse was found. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2187–2195, 2007     

Rheological Behavior and Non-enzymatic Degradation of a Sulfated Galactan from Halymenia durvillei (Halymeniales, Rhodophyta)

The rheological behavior of a sulfated galactan extracted from Halymenia durvillei, a red seaweed collected in the coastal waters of a small island of Madagascar (Nosy-be in Indian Ocean), was investigated in dilute and semi-dilute solutions. In dilute solution with NaCl at 0.3?M, the polysaccharide adopted a coil conformation whereas, at higher concentrations, the polymer had the behavior of shear-thinning fluid, typical of polymer with high molar mass or semi-rigid conformation. Degradations of this lambda carrageenan-like, using radical depolymerization, and high-pressure homogenization led to several samples of various and controlled molar masses. The measure of their intrinsic viscosities permitted the determination of the relationship of Mark?CHouwink?CSakurada.     

Effects of Sodium Salicylate on the Microstructure of an Aqueous Micellar Solution and Its Rheological Responses

In this article, we consider the effects of sodium salicylate on the microstructure evolution and rheological responses of an aqueous cetyltrimethylammonium bromide (CTAB) solution. The experimental runs covered CTAB solutions ranging from dilute to semidilute, which were far above its critical micelle concentration. Sodium salicylate (NaSal) was used as a structure-forming agent with the molar ratio of NaSal to CTAB ranging from 0.1 to 10.0. The experimental results showed that the rheological responses of the surfactant solution were influenced strongly by both the CTAB concentration and the molar ratio. At low molar ratios, below 0.3, the surfactant solutions behaved like a Newtonian fluid. However, as the molar ratio increased, the deviation from Newtonian behavior became pronounced. Specifically, for 0.05 M CTAB solutions with molar ratios ranging from 1.0 to 5.0, an apparent yield stress developed at low shear rates and a stress plateau was displayed at intermediate shear rates. When the shear rate exceeded a certain threshold value, the shear stress increased, again passing over the plateau value. In addition, viscoelastic response and relaxation behavior were observed. The relaxation behavior after the cessation of flow was strongly dependent on the molar ratio, which was also confirmed by rheo-optical observations. The optical anisotropy measured by rheo-optical methods was closely related to flow-induced stretching and alignment of the wormy micelles and was consistent with the rheological responses. Copyright 2000 Academic Press.     

Continuum theory of polymer crystallization

We present a kinetic model of crystal growth of polymers of finite molecular weight. Experiments help to classify polymer crystallization broadly into two kinetic regimes. One is observed in melts or in high molar mass polymer solutions and is dominated by nucleation control with G approximately exp(1/TDeltaT), where G is the growth rate and DeltaT is the supercooling. The other is observed in low molar mass solutions (as well as for small molecules) and is diffusion controlled with G approximately DeltaT, for small DeltaT. Our model unifies these two regimes in a single formalism. The model accounts for the accumulation of polymer chains near the growth front and invokes an entropic barrier theory to recover both limits of nucleation and diffusion control. The basic theory applies to both melts and solutions, and we numerically calculate the growth details of a single crystal in a dilute solution. The effects of molecular weight and concentration are also determined considering conventional polymer dynamics. Our theory shows that entropic considerations, in addition to the traditional energetic arguments, can capture general trends of a vast range of phenomenology. Unifying ideas on crystallization from small molecules and from flexible polymer chains emerge from our theory.     

Microstructures by solvent drop evaporation on polymer surfaces: dependence on molar mass

When a solvent drop evaporates from a polymer surface, it leaves behind a characteristic structure, typically a crater. We deposited toluene drops with a microsyringe onto planar polystyrene (PS) surfaces and analyzed the surface topography after drying. For low molar mass PS (Mw = 20.9-24.3 kDa) dotlike protrusions with a ridge at the periphery formed on the polymer surface. With increasing molar mass the central region decreased in height. At Mw = 29.6-643 kDa a craterlike structure with a depression in the center and a ridge was observed. At even higher molar mass, irregular structures without rotational symmetry occurred. We explain the observed dependence on the molar mass with a different degree of entanglement, leading to different dissolution rates and different diffusion constants.     

Liquid–liquid phase separation in aqueous solutions of poly(ethylene glycol) methacrylate homopolymers

Here, the liquid–liquid phase separation (LLPS) in aqueous solutions containing poly(ethylene glycol) (PEG) methacrylate homopolymers is reported for the first time. In this study, the thermoresponse of concentrated solutions of DEGMA₆₀ (two ethylene glycol, EG, groups) TEGMA₇₁ (three EG groups), OEGMA300_x (4.5 in average EG groups) of varying molar masses (MM), and OEGMA500₂₈ (nine in average EG groups) is discussed. Interestingly, the temperature of LLPS (T_LLPS) is controlled by the length of the PEG side chain, the MM of the OEGMA300_x and the polymer concentration. More specifically, the transition temperature decreases with: (i) Decrease in the length of the PEG side chain, (ii) increase in MM of the OEGMA300_x, and increase in concentration. In addition, LLPS is also observed in mixtures of OEGMA300_x with Pluronic® F127. In conclusion, these systems present a thermally induced LLPS, with the transition temperature being finely tuned to room temperature when DEGMA is used. These systems find potential use in numerous applications, varying from purification to “water-in-water” emulsions.     

Influence of Molar Mass and Concentration on the Thermogelation of Methylcelluloses

In this study, thermogelation of methylcelluloses is investigated in relation to the molar mass and concentration in aqueous medium. A large hysteresis between heating and cooling ramps was observed whatever the conditions. The heating process in particular was studied to analyze the two steps of gelation using rheometry. At low temperature, in the sol state, viscosity depends on the concentration and molar mass. Over 30°C a gel-like behavior was observed including two steps (the second step is a strong gel with phase separation) having storage moduli that are nearly independent of polymer molar mass but are directly related to polymer concentration.     

Lubrication, adsorption, and rheology of aqueous polysaccharide solutions

Aqueous lubrication is currently at the forefront of tribological research due to the desire to learn and potentially mimic how nature lubricates biotribological contacts. We focus here on understanding the lubrication properties of naturally occurring polysaccharides in aqueous solution using a combination of tribology, adsorption, and rheology. The polysaccharides include pectin, xanthan gum, gellan, and locus bean gum that are all widely used in food and nonfood applications. They form rheologically complex fluids in aqueous solution that are both shear thinning and elastic, and their normal stress differences at high shear rates are found to be characteristic of semiflexible/rigid molecules. Lubrication is studied using a ball-on-disk tribometer with hydrophobic elastomer surfaces, mimicking biotribological contacts, and the friction coefficient is measured as a function of speed across the boundary, mixed, and hydrodynamic lubrication regimes. The hydrodynamic regime, where the friction coefficient increases with increasing lubricant entrainment speed, is found to depend on the viscosity of the polysaccharide solutions at shear rates of around 10(4) s(-1). The boundary regime, which occurs at the lowest entrainment speeds, depends on the adsorption of polymer to the substrate. In this regime, the friction coefficient for a rough substrate (400 nm rms roughness) is dependent on the dry mass of polymer adsorbed to the surface (obtained from surface plasmon resonance), while for a smooth substrate (10 nm rms roughness) the friction coefficient is strongly dependent on the hydrated wet mass of adsorbed polymer (obtained from quartz crystal microbalance, QCM-D). The mixed regime is dependent on both the adsorbed film properties and lubricant's viscosity at high shear rates. In addition, the entrainment speed where the friction coefficient is a minimum, which corresponds to the transition between the hydrodynamic and mixed regime, correlates linearly with the ratio of the wet mass and viscosity at ～10(4) s(-1) for the smooth surface. These findings are independent of the different polysaccharides used in the study and their different viscoelastic flow properties.     

Short wavelength light reflecting films from side‐chain liquid crystal homopolymers with chiral spacers

A series of acrylate monomers with alkoxy tails of varying lengths are synthesised and polymerised. The butoxy analogue had a stable enantiotropic cholesteric liquid crystalline phase which formed a grandjean texture when prepared as a thin film between glass slides. The polymer was mixed with a low molar mass nematic liquid crystal in various proportions and the pitch of the chiral nematic phases were determined using a cano‐wedge cell technique. The polymer prepared from (S)‐2‐(4‐butoxyphenyl‐4′‐benzoyloxy)‐1‐methyl ethyl acrylate had a pitch length of 113 nm which indicates that the polymer film could be employed in optical devices requiring selective reflection of light with short wavelengths in the region of 170 nm. Copyright © 2001 John Wiley & Sons, Ltd.     

Competitive adsorption of nonionic surfactant and nonionic polymer on silica

Competitive adsorption of the nonionic polymer poly(ethylene oxide) (PEO) and the nonionic surfactant of the type poly(ethylene oxide) alkyl ether from aqueous solutions on a silica surface is examined. From one-component solutions, both species readily adsorb onto silica and, in the bulk of mixed (two-component) solutions, polymer-surfactant complexes are not observed. Because both species bind by the same mechanism to silica, subtle differences in layer structure, or other species-specific parameters, determine whether one or both of the species will adsorb. It was found that various surfactants can displace PEO up to a certain critical molecular weight. Surfactants with a high aggregation number, in bulk and on the surface, can displace PEO with a higher molar mass than surfactants with a low aggregation number. As the molar mass of the polymer increases, the time a surfactant needs to completely displace the polymer increases. We can explain both the existence of the critical molar mass and the decrease in adsorption kinetics with a shift in the critical surface association concentration (CSAC).     

Phase and structural transformations in melts, solutions, and blends of crystallizing polymers under deformation

Experimental results concerning the effect of shear deformation on phase and structural transitions in melts, solutions, and blends of crystallizing polymers are generalized and analyzed. The mechanism responsible for the influence of deformation on the melting (crystallization) temperature, on the structure of the polymers, and on the position of liquidus curves of their solutions and blends depending on the shear rate, molecular mass, and concentration of components is considered.