The influence of shear on the dewatering of high consistency nanofibrillated cellulose furnishes

This paper demonstrates a way to utilize the rheological properties of high consistency microfibrillated and nanofibrillated cellulose (MFC and NFC) based furnishes for improved dewatering. This is relevant to a new manufacturing platform that is being developed to form composite webs from suitable mixtures of MFC or NFC, traditional pulp fibres and pigments. The studied furnishes were evaluated in the consistencies range of 5–15 % with an MCR 300 rheometer and an immobilization cell. This setup enables us to characterize the rheology of the samples before and during the dewatering process. Classical rheological methods are used to characterise MFC and NFC furnishes. Yield stress as an indicator of the flocculated network strength was found to increase with the consistencies, following the increase in elastic moduli, which indicated a gel-like strongly flocculated matrix. The shear thinning properties of furnishes are observed to follow the Oswald’s rheological model on a wide range of shear rates. It was found that when the MFC and NFC furnishes were dewatered under vacuum conditions, the final solids content was increased with application of shear. This behaviour is more pronounced for furnishes which contained the more swollen NFC (higher WRV, i.e. higher zeta potential). This effect is further exemplified by the change of the complex and dynamic viscosities during the dewatering. The shear rate, the fibre content, and the furnish consistencies were also found to influence the dewatering rate.     

Titrimetric methods for the determination of surface and total charge of functionalized nanofibrillated/microfibrillated cellulose (NFC/MFC)

Total and surface charge of three different carboxymethylated nanofibrillated/microfibrillated cellulose (NFC/MFC) samples were investigated by using titrimetric methods (conductometric and polyelectrolyte (PE) titrations). Conductometric titration was found to be suitable method for the NFC total charge measurements when the back titration with HCl was applied. Surface charge measurements of NFC/MFC were conducted by using both indirect and direct PE titrations. The direct PE titration was found to be a more suitable method for the surface charge determination of NFC/MFC whereas the indirect PE titration produced too high surface charge values. This is presumably due to kinetically locked polyelectrolyte conformations on the NFC/MFC surfaces or entrapment of residual polymer after adsorption onto the NFC/MFC gel network. Finally, NFC was propargyl-functionalized and the changes in surface and total charge were successfully monitored and compared to those of propargyl-functionalized pulp. A good correlation between the titrimetric methods and elemental analysis was observed.     

The role of chain structure in the rheological behavior of vinyl acetate-vinyl alcohol copolymers

A comparative study of the viscoelastic properties of melts of vinyl acetate-vinyl alcohol copolymers with equimolar compositions characterized by different statistical distributions of chain units has been performed. It has been shown that the principle of temperature-frequency superposition is obeyed by copolymers close to a random copolymer, but is violated by copolymers with the block distribution of units. Unlike amorphous random copolymers, a multiblock copolymer is characterized by weak crystallinity, the absence of the relaxation flow state, and a more pronounced tendency to form interchain hydrogen bonds both between two hydroxyl groups and between hydroxyl and ester groups.     

The rheological and crystallization behavior of polyoxymethylene

In the polymer melt processing, the solidification has a huge importance on the properties of the resulting part. For a semi-crystalline resin, this phenomenon involves a complex interplay between crystallization and the material rheology. In this work, an investigation is carried out on the influence of thermal conditions on crystallization kinetics and rheology of two commercial polyoxymethylene (POM) copolymers. In particular, isothermal crystallization experiments using differential scanning calorimetry (DSC) and rotational rheometry to measure the dynamic viscosity are performed. The evolution of the relative crystallinity and Normalized Rheological Function (NRF) are correlated by a recent technique which allows simultaneous analysis of several measurements, even if they are not carried out at same temperatures. On this basis, a relationship between the crystallinity and the hardening, i.e. the sharp increase in the viscosity, is obtained.     

Novel aqueous spongy foams made of three-dimensionally dispersed wood-fiber: entrapment and stabilization with NFC/MFC within capillary foams

This article describes the preparation of novel aqueous spongy foams that are composed of three-dimensionally distributed wood-fiber networks stabilized with nanofibrillate cellulose (NFC) and/or microfibrillated cellulose (MFC). The free standing aqueous spongy foams were prepared with the entrapment of NFC and/or MFC—stabilized air-in-water (A/W) capillary foams using “gel trapping technique”. The stability of spongy foams could be controlled by manipulating the volume fraction of NFC and/or MFC and a secondary liquid immiscible with the continuous phase of the NFC and/or MFC suspension. Possible morphology and mechanical distribution of NFC and/or MFC within spongy foams were verified with optical microscope, SEM, and functional load-bearing method. Owing to three-dimensionally dispersed wood-fiber structure, ultra-lightweight (0.01–0.06 g/cm³), high porosity (>90%), and microporous (10–80 μm), the NFC and/or MFC reinforced spongy foams, improved compressional strength-vertical direction obviously, from 0.0 to more than 13.78 kPa.     

On the swelling behavior of linear end-grafted polystyrene in methanol/toluene mixtures

Neutron reflectivity measurements have been performed with polystyrene (PS) brushes of different graft densities ranging from =0.020 to =0.051 in contact with toluene/methanol mixtures of different composition. The brushes were prepared by a grafting-from procedure resulting in linear chains of average molecular weight _n=300,000 g mol^–1. The recorded reflectivity curves could be analyzed to a first approximation by assuming a flat scattering length density profile within the brush normal to the surface with a moderate Gaussian smearing of the interface brush/solvent. With increasing toluene content a substantial thickness increase was found with the swollen brush at 70 vol.% being 3.7 times thicker than the dry collapsed film. At low toluene contents the preferential incorporation of this good solvent for the PS brush exceeds a factor 3.5 relative to the molar ratio of the bulk solvent mixture with methanol.

Evaluation of rheological properties and swelling behaviour of sonicated scleroglucan samples

Scleroglucan is a natural polysaccharide that has been proposed for various applications. However there is no investigation on its property variations when the molecular weight of this polymer is reduced. Scleroglucan was sonicated at two different polymer concentrations for different periods of time and the effect of sonication was investigated with respect to molecular weight variations and rheological properties. Molar mass, estimated by viscometric measurements, was drastically reduced already after a sonication for a few min. Sonicated samples were used for the preparation of gels in the presence of borate ions. The effect of borax on the new samples was investigated by recording the mechanical spectra and the flow curves. A comparison with the system prepared with the dialysed polymer was also carried out. The anisotropic elongation, observed with tablets of scleroglucan and borax, was remarkably reduced when the sonicated samples were used for the preparation of the gels.     

The rheological behavior of ethylene vinyl acetate copolymer/rectorite nanocomposites during the melt extrusion process

To optimize the preparation process for ethylene vinyl acetate (EVA)/rectorite nanocomposites during the melt extrusion, the effect of rectorite on the rheological property of molten polymer has been explored in this paper. The dispersion of rectorite in EVA was probed by X‐ray diffraction, and the rheological behaviors of EVA copolymer and EVA/rectorite nanocomposites during the extrusion process were investigated by means of HAAKE minilab. The positron results reveal that introducing the rectorite in EVA matrix increases the interfaces in composites. And the rheological results indicate that the viscosity of EVA and EVA/rectorite nanocomposites in the molten state was influenced by the processing temperature, processing time and shearing rate. For all the samples, the viscosity increases with increasing the shear rate, and decreases with increasing extrusion temperature. Moreover, compared with the pure EVA, the EVA/rectorite nanocomposite presents a lower viscosity at the same processing condition. Copyright © 2016 John Wiley & Sons, Ltd.     

Unusual swelling behavior of films of polyvinyl- and polyvinylidene/fluorides in various solvents

The swelling of PVF and PVDF films in various solvents was investigated. It was found that in the swollen state both polymers show little tendency to retain the solvent that leaks out under a mild pressure and evaporates quickly when the specimen is exposed to air. The equilibrium swelling ratios were measured in numerous solvents. From the results it is concluded that the solubility parameters are δ_PVDF = 12.0–12.3, δ_PVF = 12.0–12.1. The unusual swelling behavior is explained by strong polymer–polymer interactions via dipoles which tend to replace polymer–solvent interactions once the sample is withdrawn from the solvent.     

Microstructure and swelling behavior of ion-exchange resin

The microstructure and swelling kinetics of ion-exchange resins having sulfonic acid groups were investigated by small-angle neutron scattering (SANS) and swelling experiments as functions of the crosslinking density (CD), pH, and the salt concentration (C_salt). The swelling kinetics was analyzed on the basis of the Tanaka-Fillmore swelling equation for the cooperative diffusion of polymer gels. The swelling behavior was very sensitive to CD, but not to pH and C_salt. The SANS intensity functions, I(q), were independent of CD and well described with a power law function, I(q) ∼ q^−D, where q and D are the magnitude of the scattering vector and the mass-fractal dimension, respectively. D was estimated to be ∼2, indicating that the resin consisted of a rather coarsely interconnected domains irrespective of CD at swelling equilibrium. It was found that CD is the most important parameter determining the swelling power of ion-exchange resin. However, no remarkable variations were found in the microstructure in the order of tens to hundreds of angstrom. © 1996 John Wiley & Sons, Inc.     

The model of the rheological behavior of gelatinized starch at low concentrations

The optical density at the wavelength from 300 to 800 nm and the rheological behavior of gelatinized starch at its concentration from 3 to 30 g/L and the medium pH from 2 to 11 were investigated. The volume concentration of the swelling associates of macromolecules or their globules increases when pH of gelatinized starch rises. An influence of the volume concentration of gelatinized starch on the dependence of the shear stress on shear rate was studied. The dynamic viscosity is proportional to the volume concentration at the gelatinized starch concentration lower than 25% and proportional to the logarithm of the volume concentration at the starch concentration greater than 25%. Proposed mathematical model takes into account an influence of the volume concentration of swelling starch globules and the concentration of glucoside links of macromolecules between the globules of macromolecules or their associates on the dynamic viscosity of gelatinized starch. This model allows to describe the experimental data obtained.     

Selective swelling induced pore generation of amphiphilic block copolymers: The role of swelling agents

Swelling of block copolymers by selective solvents has emerged as an extremely simple and efficient process to produce nanoporous materials with well‐controlled porosities. However, the role of the swelling agents in this pore‐making process remains to be elucidated. Here we investigate the evolution of morphology, thickness, and surface chemistry of thin films of polystyrene‐block‐poly (2‐vinyl pyridine) (PS‐b‐P2VP) soaked in a series of alcohols with changing carbon atoms and hydroxyl groups in their molecules. It is found that, in addition to a strong affinity to the dispersed P2VP microdomains, the swelling agents should also have a moderate swelling effect to PS to allow appropriate plastic deformation of the PS matrix. Monohydric alcohols with longer aliphatic chains exhibit stronger ability to induce the pore formation and a remarkable increase in film thickness is associated with the pore formation. High‐carbon alcohols including n‐propanol, n‐butanol, and n‐hexanol produce cylindrical micelles upon prolonged exposure for their strong affinity toward the PS matrix. In contrast, methanol and polyhydric alcohols including glycol and glycerol show very limited effect to swell the copolymer films as their affinity to the PS matrix is low; however, they also evidently induce the surface segregation of P2VP blocks. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 926–933     

Osmotic swelling behavior of globules of W/O/W emulsion liquid membranes

The osmotic swelling behavior of water-in-oil-in-water (W/O/W) type emulsion liquid membranes (ELMs) was investigated. Using an optical microscope equipped with a camera, the changes in the size of the W/O/W globules were monitored over a long period of time (up to about 4 h). The osmotic pressure gradient between the internal and external aqueous phases was induced by creating a concentration difference of d-glucose between the two aqueous phases. The results indicate that the swelling ratio, defined as the ratio of globule diameter at time t to globule diameter at t=0, decreases with the increase in ϕ_W/O(0) (initial volume fraction of internal aqueous phase droplets). The swelling ratio generally increases with the increase in the concentration of surfactant present in the membrane (oil) phase. The permeation coefficient of water also increases with the increase in the surfactant concentration. With the increase in ϕ_W/O(0) up to about 0.42, the permeation coefficient decreases only slightly. However, with further increase in ϕ_W/O(0), a sharp reduction in the permeation coefficient occurs. The mechanism of water transfer in ELMs of the present work is reasoned to be the diffusion of hydrated surfactants.     

Synthesis and swelling behavior of pH-responsive polybase brushes

We synthesize polybase brushes and investigate their swelling behavior. Poly(2-(dimethylamino)ethyl methacrylate)) (PDMAEMA) brushes are prepared by the "grafting from" method using surface-initiated Atom Transfer Radical Polymerization to obtain dense brushes with relatively monodisperse chains (PDI = 1.35). In situ quaternization reaction can be performed to obtain poly(2-(trimethylamino)ethyl methacrylate)) (PTMAEMA) brushes. We determine the swollen thickness of the brushes using ellipsometry and neutron reflectivity techniques. Brushes are submitted to different solvent conditions to be investigated as neutral brushes and weak and strong polyelectrolyte brushes. The swelling of the brushes is systematically compared to scaling models. It should be pointed out that the scaling analysis of different types of brushes (neutral polymer and weak and strong polyelectrolyte brushes) is performed with identical samples. The scaling behavior of the PDMAEMA brush in methanol and the PTMAEMA brush in water is in good agreement with the predicted scaling laws for a neutral polymer brush in a good solvent and a polyelectrolyte brush in the osmotic regime. The salt-induced contraction of the quaternized brush is observed for high salt concentration, in agreement with the predicted transition between the regimes of the osmotic brush and the salted brush. From the crossover concentration, we calculate the effective charge ratio of the brush following the Manning counterion condensation. We also use PDMAEMA brushes as pH-responsive polybase brushes. The swelling behavior of the polybase brush is intermediate with respect to the behavior of the neutral polymer brush in a good solvent and the behavior of the quenched polyelectrolyte brush, as expected. The effective charge ratio of the PDMAEMA brush is determined as a function of pH using the scaling law of the polyelectrolyte brush in the osmotic regime.     

Phase and rheological behavior of the polymerizable surfactant CTAVB and water

The phase and rheological behaviors of the polymerizable surfactant, cetyltrimethylammonium benzoate (CTAVB), and water as a function of surfactant concentration and temperature are investigated here. The critical micelle concentration (cmc) and the (cmc(2)), as well as the Krafft temperature (T(K)), are reported. A large highly viscous micellar solution region and hexagonal- and lamellar-phase regions were identified. The micellar solutions exhibit shear thickening in the dilute regime, below the overlapping or entanglement concentration. At higher concentrations, wormlike micelles form and the solutions show strong viscoelasticity and Maxwell behavior in the linear regime and shear banding flow in the nonlinear regime. The linear viscoelastic regime is analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation and scission of the micelles. The steady and unsteady responses in the nonlinear regime are compared with the predictions of the Bautista-Manero-Puig (BMP) model. Model predictions follow the experimental data closely.     

Correlation of chemical structure and swelling behavior in N-alkylacrylamide hydrogels

The thermoshrinking properties have been studied for the series of N-alkyl-acrylamide hydrogels (alkyl = methyl, ethyl, isopropyl, and n-propyl), which were prepared by free-radical copolymerization of the alkylacrylamide, sodium acrylate, and N,N′-methylenebis(acrylamide) (BIS) in aqueous solution. The reaction mixtures were prepared using the same nominal compositions in an effort to study the effect of the chemical structure of the alkyl substituent on the gel swelling behavior as a function of temperature. The alkyl group was found to have a pronounced effect on the features of gel swelling. Generally, larger alkyl chains produced dramatic decreases in gel transition temperature. In addition, a change in the nature of the swelling behavior from continuous to discontinuous was noted upon changing the alkyl group from ethyl to the two propyl derivatives. Discontinuous transitions were accompanied by hysteresis. The transition temperatures of the isomeric propyl derivatives were found to differ by 12°C, with n-propyl exhibiting the lower value. Additionally, a quantitative correlation was found between the gel transition temperatures and the water/octanol partition coefficients for appropriately chosen small molecule model compounds. The transition temperatures of other gels in the series, including the cyclopropyl derivative and the n-propyl/isopropyl copolymer gels (NIPA/NNPA), also fit this correlation. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2095–2102, 1998     

The equilibrium fraction of bridging chains and the swelling behavior of ABA triblock copolymer mesophases

The physical cross-linked network due to B blocks bridging different A domains of a microphase separated melt formed by an ABA copolymer in the strong-segregation limit is examined. The system is considered to consist of swollen elements of the same size, each containing an A domain and a B layer anchored to the A domain as loops or bridges. A lattice model and a generator-matrix method are employed to calculate the equilibrium fraction of the bridging B chains of the ABA mesophase and the equilibrium swelling concentration of the B layer in a selective solvent for the planar, cylindrical and spherical A domain structures. The effects of chain length and of two-dimensional surface density of the AB joints are discussed. The equilibrium fraction of the bridging chains as a function of chain stiffness and the equilibrium swelling concentration as a function of the fraction of bridging chains and of the interaction parameter are calculated. In addition, the segment density distributions of both loop and bridging chains for both the pure ABA and the swollen ABA mesophases are provided.     

Influence of polymer reprocessing cycles on the microstructure and rheological behavior of polypropylene/mineral oil oleogels

The overall objective of this work was to study the effect of reprocessing cycles of isotactic polypropylene (PP) on the rheological behavior and microstructure of gel-like dispersions in mineral oil. PP was subjected to 10 reprocessing cycles and oleogel samples were further prepared by using the mixing rheometry technique and characterized from a rheological point of view and polarized light optical microscopy (PLOM). Recycled polymer samples were also characterized by means of rheological measurements, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) to evaluate the property changes induced by reprocessing. The values of different linear viscoelastic functions (elastic modulus and complex viscosity) of recycled PP decrease with the number of reprocessing cycles, which influences oleogel rheological response. An empirical exponential correlation between the storage modulus (G′) of PP samples and the plateau modulus ($G_N^o$) of oleogels has been proposed to predict the rheological behavior of oleogels. Results were explained considering the scission of PP chains induced by the thermomechanical reprocessing treatment applied.