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  • Articles  (29)
  • Rheology
  • Springer  (29)
  • American Geophysical Union
  • American Physical Society
  • Annual Reviews
  • Nature Publishing Group
  • 1995-1999  (27)
  • 1980-1984  (2)
  • 1970-1974
  • 1935-1939
  • 1
    Electronic Resource
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    Springer
    Rheologica acta 34 (1995), S. 137-146 
    ISSN: 1435-1528
    Keywords: Rheology ; hydroxypropylcellulose ; liquid crystalline polymers ; phase separation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Aqueous solutions of hydroxypropylcellulose (HPC) have been widely used as a model system to study liquid crystalline behavior in polymers. The HPC limiting concentration for mesophase formation in water is about 40% wt, quite independent of molecular weight. Most rheo-optical investigations have been carried out in the concentration range from 50% to 65% wt, on the assumption that only the liquid crystalline phase was present. In this study, by using video-enhanced contrast light microscopy, we show that an isotropic phase in form of tiny droplets is also present at concentrations up to 60% wt, both in quiescent and in sheared samples at room temperature. The isotropic phase can be made to disappear by lowering the temperature. The effects of phase separation on the rheology of the HPC/water system are studied by measuring viscosity as a function of temperature and concentration. A slope of Region I of the viscosity curve close to −0.5 is found only at low temperatures, when the sample is fully anisotropic, whereas an anomalous dependence of the viscosity on temperature is observed when phase separation is significant. This study shows that special care is needed when interpreting experimental results from the HPC/water system in terms of theories for liquid crystalline polymers.
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  • 2
    ISSN: 1435-1528
    Keywords: Rheology ; liquid crystal ; monodomain ; instability ; conoscopy ; shear
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract We have measured the shear-induced rotation of the nematic director in a liquid crystalline polymer using poly benzyl glutamate (PBG) as model system. PBG is a well characterized synthetic poly (α amino acid) with rigid chain architecture and well defined conformations. For the experiments it is important to start out with a sample in which the molecules are highly aligned with a uniform director. This so-called monodomain morphology is obtained by use of strong magnetic fields and surface modifications of the sample holders. When shearing the monodomain at a constant rate, the macromolecules rotate initially homogeneously until a periodic director pattern develops. These spatially periodic structures emerge in a narrow range of shear strain and, as shearing continues, disintegrate into a chaotic texture. By varying the initial monodomain director with respect to the flow direction (but within the shear planes) we could show that the periodic patterns do not depend on the shear direction; they are governed by the director of the initial monodomain. We observe conoscopically that at high shear rates the texture becomes uniformly aligned. The molecules are aligned preferentially with an angle of about 4° to the shear direction (against vorticity direction). Interestingly, this agrees very well with predictions made by Larson (1990).
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  • 3
    ISSN: 1432-0819
    Keywords: Key words Kīlauea ; Basalt crystallization ; pāhoehoe ; 'a'ā ; Rheology ; Lava flow morphology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  Samples collected from a lava channel active at Kīlauea Volcano during May 1997 are used to constrain rates of lava cooling and crystallization during early stages of flow. Lava erupted at near-liquidus temperatures (∼1150  °C) cooled and crystallized rapidly in upper parts of the channel. Glass geothermometry indicates cooling by 12–14  °C over the first 2 km of transport. At flow velocities of 1–2 m/s, this translates to cooling rates of 22–50  °C/h. Cooling rates this high can be explained by radiative cooling of a well-stirred flow, consistent with observations of non-steady flow in proximal regions of the channel. Crystallization of plagioclase and pyroxene microlites occurred in response to cooling, with crystallization rates of 20–50% per hour. Crystallization proceeded primarily by nucleation of new crystals, and nucleation rates of ∼104/cm3s are similar to those measured in the 1984 open channel flow from Mauna Loa Volcano. There is no evidence for the large nucleation delays commonly assumed for plagioclase crystallization in basaltic melts, possibly a reflection of enhanced nucleation due to stirring of the flow. The transition of the flow surface morphology from pāhoehoe to 'a'ā occurred at a distance of 1.9 km from the vent. At this point, the flow was thermally stratified, with an interior temperature of ∼1137  °C and crystallinity of ∼15%, and a flow surface temperature of ∼1100  °C and crystallinity of ∼45%. 'A'ā formation initiated along channel margins, where crust was continuously disrupted, and involved tearing and clotting of the flow surface. Both observations suggest that the transition involved crossing of a rheological threshold. We suggest this threshold to be the development of a lava yield strength sufficient to prevent viscous flow of lava at the channel margin. We use this concept to propose that 'a'ā formation in open channels requires both sufficiently high strain rates for continued disruption of surface crusts and sufficient groundmass crystallinity to generate a yield strength equivalent to the imposed stress. In Hawai'i, where lava is typically microlite poor on eruption, these combined requirements help to explain two common observations on 'a'ā formation: (a) 'a'ā flow fields are generated when effusion rates are high (thus promoting crustal disruption); and (b) under most eruption conditions, lava issues from the vent as pāhoehoe and changes to 'a'ā only after flowing some distance, thus permitting sufficient crystallization.
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  • 4
    ISSN: 1573-0603
    Keywords: Biomechanics ; Cell culture ; Endothelium ; Mechanotransduction ; Mechanical stress ; Scientific instruments ; Rheology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Living cells are constantly exposed to a variety of complex mechanical stimuli which are though to be critical in the control of tissue structure and function. Endothelial and smooth muscle cells in the blood vessel are ideal candidates for the study of blood flow-induced cellular regulation. We describe here a cone-plate viscometer apparatus which is specially-designed for studying the effect of fluid shear stress on large populations of adherent cells in vitro. Using conventional polystyrene tissue culture plates, the apparatus is self-contained, fits inside a standard tissue culture incubator, and provides 75–150 cm2 of useful surface area for cell growth. This capability makes it ideal for studying gene regulation using Northern analysis, nuclear runoff transcription, transfection with reporter constructs, as well as immunochemical staining. The closed-volume design of the device is also well-suited for isotopic labelling, pharmacological studies, and for the detection of minute amounts of secreted cell products. The setup allows the use of either steady, time- and direction-varying laminar, or turbulent shear stress. We provide a detailed assembly procedure and review the method for computing shear stress magnitude and Reynolds number. Ink flow analysis, dynamic response characterization, and LDH measurements are presented to confirm the device's fluid mechanical properties and demonstrate the absence of cell injury.
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  • 5
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    Pure and applied geophysics 145 (1995), S. 605-620 
    ISSN: 1420-9136
    Keywords: Rheology ; structures ; strain ; numerical models
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The contrast in rheological properties between layers of different composition or texture, and between stiff inclusions and their matrix, gives rise to perturbations in flow that result in structures. Theory and modeling allow us to understand the conditions necessary for such structures to form and, conversely, we can use the form of the structures to infer possible rheological conditions for the rocks during natural deformation. We review here several structures and their use as indicators of rheological behavior, based on theory, numerical and experimental models, and observations on naturl structures. Theory predicts that a dominant wavelength/thickness (L d /h) exists for both folding and boudinage that depends on the ratio of viscosities of layer to matrix, the homogeneous shortening undergone by the layer, and the exponent,n, in a flow law of power-law type. The measurement of averageL/h, and of the shortening within the layers allows an estimate of the power-law exponent of the stiff layer to be made. Also, numerical modeling shows that fold hinges become sharper asn increases and the limbs become relatively longer and straighter. The dynamic growth of pinch and swell instabilities only overcomes the kinematic decay in nonlinear flow, thus the existence of pinch and swell is by itself evidence of nonlinear behavior. Strain rate and strain, increase more rapidly away from the neutral surface for a layer of power-law rheology (withn〉1) than for a layer of Newtonian rheology. Thus, strain gradient across a fold hinge, at fixed amplitude or limb dip, increases with increasingn. Porphyroclasts in mylonites develop characteristic rims of recrystallized grains that are drawn out into trails of σ or ° shape by the perturbed flow of the, material around the clast. Experimental evidence suggests that σ shapes occur if flow is linear, whereas nonlinear flow may give rise to the δ shape. The inference of rheological behavior from structures is complementary to the determination of rheological properties of rocks in the laboratory. What data there is suggest that constitutive relations for rocks undergoing ductile deformation in which many structures develop are highly nonlinear. There is general qualitative agreement between flow laws inferred on the basis of experimental results and those inferred from observation of structural characteristics.
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  • 6
    ISSN: 1432-0819
    Keywords: Key words Lava dome ; Endogenous ; Basaltic ; Submarine ; Rheology ; Antarctica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  On King George Island during latest Oligocene/earliest Miocene time, submarine eruptions resulted in the emplacement of a small (ca. 500 m estimated original diameter) basalt lava dome at Low Head. The dome contains a central mass of columnar rock enveloped by fractured basalt and basalt breccia. The breccia is crystalline and is a joint-block deposit (lithic orthobreccia) interpreted as an unusually thick dome carapace breccia cogenetic with the columnar rock. It was formed in situ by a combination of intense dilation, fracturing and shattering caused by natural hydrofracturing during initial dome effusion and subsequent endogenous emplacement of further basalt melt, now preserved as the columnar rock. Muddy matrix with dispersed hyaloclastite and microfossils fills fractures and diffuse patches in part of the fractured basalt and breccia lithofacies. The sparse glass-rich clasts formed by cooling-contraction granulation during interaction between chilled basalt crust and surrounding water. Together with muddy sediment, they were injected into the dome by hydrofracturing, local steam fluidisation and likely explosive bulk interaction. The basalt lava was highly crystallised and degassed prior to extrusion. Together with a low effusion temperature and rapid convective heat loss in a submarine setting, these properties significantly affected the magma rheology (increased the viscosity and shear strength) and influenced the final dome-like form of the extrusion. Conversely, high heat retention was favoured by the degassed state of the magma (minimal undercooling), a thick breccia carapace and viscous shear heating, which helped to sustain magmatic (eruption) temperatures and enhanced the mobility of the flow.
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  • 7
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    Planta 204 (1998), S. 515-519 
    ISSN: 1432-2048
    Keywords: Key words: Acid-growth theory (roots) ; Auxin ; Cell wall extensibility ; Rheology ; Root growth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract. The rheological properties of corn (Zea mays L. cv. Garant) root elongation zones were investigated by means of a computer-controlled extensiometer. Creep closely followed a logarithmic time function, which was used to quantify creep activity. Pretreatment with auxin, which inhibits extension growth in roots, lowered the creep activity and the apparent plastic extensibility. While the time course of the inhibition of apparent plastic extensibility lagged behind the cessation of elongation growth, the drop in creep activity matched the growth inhibition more closely. Creep activity and apparent plastic extensibility were not significantly affected by pH. These data support the view that the auxin-induced cell wall stiffening (e.g. by cross-linking processes), while causal for the growth inhibition, is not brought about by a cell wall alkalinization.
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  • 8
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    Colloid & polymer science 277 (1999), S. 583-588 
    ISSN: 1435-1536
    Keywords: Key words Emulsion ; Rheology ; Viscoelastic ; Yield stress ; Concentrated emulsions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  The rheology of high internal phase ratio oil-in-water emulsions was investigated using a controlled-stress rheometer. The dispersed-phase (oil) concentration was varied from 71.24 to 89.61% by volume. Three different types of rheological experiments were conducted for each emulsion, namely: steady shear, oscillatory shear, and creep/recovery experiments. All the emulsions investigated in this study possess a yield stress. The yield-stress values obtained from different rheological experiments for the same emulsion show good agreement with each other. The yield-stress value increases exponentially with an increase in the dispersed-phase concentration. The yield-stress data of this study can be described quite well with the Princen and Kiss equation for high internal phase ratio emulsions provided that the thickness of the interdroplet films is taken into account. For any given emulsion, the storage modulus, measured in the linear viscoelastic region, is found to be constant, independent of the frequency, indicating a solid-like behaviour. The value of the storage modulus increases with an increase in the dispersed-phase concentration. The storage modulus data are interpreted in terms of the Princen and Kiss equation.
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  • 9
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    Colloid & polymer science 277 (1999), S. 798-804 
    ISSN: 1435-1536
    Keywords: Key words End-capped poly(ethylene glycol) ; Viscosity ; Rheology ; Phase behavior ; Microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Generally it is observed that the viscosity of an aqueous solution of a hydrophobically modified polymer increases with concentration; however, here it is shown that the viscosity profile of an end-capped poly(ethylene glycol) polymer passes through a maximum. Thus, a substantial decrease in viscosity is observed at high concentrations (≥50 wt%). The observation is suggested to be due to a gradual change, on the molecular level, from a structure containing micellelike structures that are interconnected via polymer bridges to a more meltlike state, where micro segregation in hydrophilic and hydrophobic regions is less pronounced.
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  • 10
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    Colloid & polymer science 277 (1999), S. 827-836 
    ISSN: 1435-1536
    Keywords: Key words Phase equilibria ; Surfactant solution ; Rheology ; Alkylglucosides ; Synergism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Alkylpolyglucosides (C Y G X ) are industrial products of mixtures consisting of a hydrocarbon chain with Y carbon atoms linked to X sugar residues. Based on detailed analytical investigation of technical grade alkylpolyglucosides (C8–10G X , C12–14G X and C8–16G X )/water systems using high-performance liquid chromatography in combination with a special kind of mass spectroscopy their rheological behaviour is discussed and compared to the rheological behaviour of pure alkyl monoglycosides (C8G1 and C10G1) in water. The rheological properties that exhibit a dependence on the alkyl chain length, Y, and the degree of polymerisation, X, are investigated by rotation and oscillation experiments over an extended concentration range. The Maxwell model fits the frequency dependence of the dynamic functions fairly well. The viscosity shows an Arrhenius-like dependence on temperature. A comparison is drawn between the monoglucosides and the polyglucosides, which shows that the rheological properties are more sensitive to the a change in chain length than in the degree of polymerisation. Phase transitions, especially liquid-crystalline to isotropic solutions, phase split into two coexisting liquid phases, and could be followed using visual observation and rheology. Depending on the difference in the rheological properties of the corresponding phases, viscoelastic measurements showed these transitions clearly. Additionally, the changes in viscosities were measured after addition of a second surfactant.
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  • 11
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    Colloid & polymer science 277 (1999), S. 727-734 
    ISSN: 1435-1536
    Keywords: Key words Gellan gum ; Helix ; Coil transition ; Sol-gel Transition ; Salt ; Rheology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Rheological properties of gellan gum solutions with and without salt have been monitored using oscillatory measurements and steady-shear viscosity measurements. The steady-shear viscosity measurements indicated that gellan gum solutions showed a wide Newtonian plateau when gellan gum molecules took a coil conformation, and that the shear-thinning behaviour became more conspicuous with conformational change of gellan gum molecules from coiled to helical, and the range of the Newtonian plateau became limited only to very low shear rates. When gellan gum solutions showed rheological behaviour as a dilute or concentrated polymer solution, these systems obeyed the Cox–Merz superposition of steady-state viscosity and dynamic viscosity. As gellan gum solutions formed a weak gel, the Cox–Merz rule was not valid; however, the deviation from this superposition was less significant than that of xanthan gum solutions which also show weak-gel behaviour.
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  • 12
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    Plant and soil 211 (1999), S. 87-91 
    ISSN: 1573-5036
    Keywords: Rheology ; root mucilage ; viscoelasticity ; water potential
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Root mucilage was collected from 3–4 day-old axenically-grown maize seedlings (Zea mays L. cv. Freya). The water potential of the hydrated mucilage was measured by thermocouple psychrometry and the rheology at low deformation rates was studied using an oscillating cone and plate rheometer which provides information on both the elastic and viscous components of its behaviour. Water potential decreased as mucilage solute concentration increased, reaching a value of −60kPa at 1.2 mg mL−1. At the lowest oscillation rate, the mucilage had a dynamic viscosity of 145 mPa s and behaved as a weak viscoelastic gel. After filtration to remove suspended root cap cells and other solid plant material, mucilage viscosity was reduced to 5–10 mPa s at low oscillation rates and the behaviour was that of a viscous liquid. The decrease in viscosity which occurs on filtration indicates that the root cap cells form an integral part of the gel system, either by interacting directly with each other or via the polysaccharide. Our observations provide further support for the idea that mucilage plays a major role in maintaining root-soil contact in the rhizosphere.
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  • 13
    ISSN: 1435-1536
    Keywords: Rheology ; gelatin ; anionic surfactants ; interactions ; gelation ; surface tension
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The interactions between gelatin and two anionic surfactants (sodium di-sec-butylnaphthalenesulfonate and sodium dodecylbenzenesulfonate, respectively) were investigated using rheological methods, charge and surface tension measurements. Upon the addition of surfactants, the viscosity of aqueous gelatin solutions increases at pH values higher than the isoelectric point (IEP) of the gelatin, provided that a distinct surfactant concentration is exceeded. The increase in viscosity depends on the structure of the hydrophobic moiety of the surfactant. Surface tension measurements suggest the formation of gelatin-surfactant-complexes. If the surfactant is added in high concentration, the viscosity does not further increase, and free micelles are formed in the solution. Directly at the IEP and at pH values below, the addition of surfactants leads to flocculation because of electrostatic interactions. At all surfactant concentrations, the flow behaviour was strictly Newtonian. As a model of the structure of the complex, a modified ‘bead and necklace’-model is suggested. This model proposes the nucleation of micelles at the hydrophobic gelatin regions (‘micellar surfactant-gelatin complexes’). The number of micelle moieties per gelatin chain could be estimated to be about three. The complex stability is dependent on the extent of hydrophobic interaction. The gelation behaviour of gelatin is strongly affected by the addition of the surfactant. The ratio between the attainable linear storage and loss moduli,G′ andG″, decreases strongly. Gelation is generally hindered, but the effect is stronger at pH values below the IEP than above.
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  • 14
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    Colloid & polymer science 277 (1999), S. 270-275 
    ISSN: 1435-1536
    Keywords: Key words Micelles ; Connections ; Rheology ; Cethyltrimethylammonium chloride ; Organic salts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We report a rheological study on the effect of adding organic salts [sodium tosylate (NaTos) and benzoic acid potassium salt (BaPs)] on the micellar growth and structure of aqueous solutions of cethyltrimethylammonium chloride (CTAC) at a constant molar concentration ratio [salt]/[CTAC]. The rheological data show two well-defined domains of growth characterized by scaling laws for the surfactant concentration. The addition of NaTos leads to an unusual maximum in the viscosity-surfactant concentration curve. Before the maximum (domain 1), the analysis of the data (η0, τR and G 0) suggests the presence of branched micelles (connections). After the maximum (domain 2), however, the exponents of the scaling laws do not reflect either the relaxation of this branched structure or that of an entangled transient network structure. A faster mechanism of relaxation, not yet elucidated governs their dynamics. The exponents of the power laws in the presence of the BaPs are found, however, to be in accordance with the theory of equilibrium polymers.
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  • 15
    ISSN: 1435-1536
    Keywords: Key words Model associative polymers ; Alkali ; Neutralization ; Rheology ; Stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Hydrophobically modified alkali-soluble emulsion (HASE) polymer is solubilized by the addition of a base. When the pH is increased to greater than 6.5, methacrylic acids on the polymer backbone are neutralized and the carboxylated latex polymer goes into solution causing a large increase in the viscosity due to inter-molecular associations of the hydrophobes. The stability of the viscosity of the polymer solution at pH in the range 9–10 was studied in the presence of a strong (NaOH) and a weak [1-amino-1-methylpropanol (AMP)] base. No change in the viscosity or the moduli was observed for the polymer in AMP. Reduction in the viscous and elastic properties of the polymer solution in NaOH was observed after 4 weeks. Such small changes are detectable using the superposition of oscillation on the steady shear technique. The decrease in the viscoelastic properties is attributed to the hydrolysis reaction of the urethane groups of the macromonomer, which resulted in a decrease in the number of hydrophobes per polymer chain. It is recommended that a weak base be used to neutralise the HASE polymer in order to avoid the possibility of compositional changes in the polymer after neutralisation for more than 6 weeks.
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  • 16
    ISSN: 1435-1536
    Keywords: Key words Interaction ; Polymer ; Surface ; Thin film ; Rheology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The forces and viscosity between calcium benzene sulfonate surfactant-coated mica surfaces in various hydrocarbon liquids containing a polyamine-functionalized hydrocarbon polymer (M W≈8000) have been measured using the surface forces apparatus technique. The polymer is found to adsorb to the substrate surfaces by displacing the surfactant layer, and to produce forces that are monotonically repulsive. The forces have a maximum range of 50–100 nm (〉3R H), indicating that tails play a particularly important role in the interaction of this relatively low molecular weight polymer. The forces become steeply repulsive below about 10 nm (∼0.6R H), at which point a “hard-wall” repulsion comes in that can sustain pressures greater than 100 atm. Thin-film viscosity measurements indicate that the far-field positions of the slipping planes ΔH depend on the shear rate, showing that significant shear thinning/thickening effects occur within the outermost tail regions of the adsorbed layers during shear. The position of the slipping plane, or hydrodynamic layer thickness ΔH, varies from 0.6R H to 2R H away from each surface (mica and surfactant-coated mica surfaces). Beyond the hydrodynamic layer the far-field fluid viscosity is the same as that of the bulk polymer solution. At separations below D = 2ΔH the viscosity increases as each polymer layer is compressed. The static forces exhibited various time- and history-dependent effects, which further indicate that a number of different relaxation/equilibration processes are operating simultaneously in this complex multicomponent system. The results reveal that the interactions of tails of functionally adsorbed polymers play a more important role than previously thought. This is especially true in this study where the adsorbed polymers are of low molecular weight and where the tails may represent the largest fraction of interacting segments.
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  • 17
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    Colloid & polymer science 260 (1982), S. 1042-1056 
    ISSN: 1435-1536
    Keywords: Rodlike Micelles ; Micellar Interaction ; Rheology ; Light Scattering ; Electric Birefrugence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Conductivity, kinetic, static and dynamic light scattering, electric birefringence and rheological measurements were carried out on aqueous solutions of Tetradecylpyridinium-n-Heptanesulfonate (C14PyC7SO3) up to high concentrations. In dilute solutions between the critical micelle concentration (cmc) and another characteristic concentration (c t) spherical micelles were detected whose radii were independent of detergent concentration and equal to the length of a detergent molecule; the aggregation numbern of these micelles of about 100 monomers per micelle was also in agreement with the existence of normal spherical micelles of aC 14-detergent. Above the concentrationc t, the spherical micelles were found to grow to rodlike aggregates whose short axis was still independent of concentration and equal to the length of a monomer, while the lengthsL of the rods increased with increasing detergent concentration. When the lengthsL of the rods became comparable with the mean distancea between them, the starting interaction between the rods slowed down their growth. In this concentration range of overlapping rods, the data could be evaluated with a recently developed theory by Doi and Edwards for stiff rods. The rods reached finally a maximum length of about 500 å and decreased again in size upon further increase of concentration when the overlap ratioL/a reached a value of about 1,5.
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  • 18
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    Colloid & polymer science 105 (1997), S. 322-325 
    ISSN: 1435-1536
    Keywords: Rheology ; surfactant solutions ; micelles ; phase transition ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Aqueous solutions of cationic surfactant with binding counterions exhibit a transition under shear. In this paper the steady shear properties of semidilute aqueous micellar solutions (cetylpyridinium chloride and sodium salicylate in brine) are presented as a function of concentration and temperature. The shear thinning behavior of this system could be described by the Carreau model at low shear rate and by a power law at higher shear rate. The temperature dependence of the zero shear viscosity follows an Arrhenius relationship. The critical shear rate at which the viscosity departs from its zero shear value is found to increase with temperature indicating the influence of this parameter on transition.
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  • 19
    ISSN: 1435-1528
    Keywords: Rheology ; gelation ; acrylamide-acrylic acid copolymers ; chromium ions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The gelation kinetics of aqueous solutions of acrylamideacrylic acid copolymers in the presence of chromium ions was studied with different rheometers. The gel time is found to vary with the principle of the apparatus because of a low shear dependence of the elongation of the macromolecules. The variations of the gel time with the experimental conditions of the gel preparation were investigated and we conclude that the gelation is governed by the oligornerization kinetics of the chromium ions which are instantaneously, complexated by the carboxylate groups of the polymer. The variation laws of the gel time and of the elastic modulus with chromium and polymer concentrations, temperature and ionic strength are in qualitative agreement with the structure of the temporary network of the semi-dilute solutions of these copolymers.
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  • 20
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    Rheologica acta 35 (1996), S. 645-655 
    ISSN: 1435-1528
    Keywords: Rheology ; polymers ; poly-dispersity ; linear viscoelasticity ; relaxation time
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The relaxation of slightly poly-disperse linear flexible polymers has been expressed in a simplified blending rule which is presumed to be a weighted linear superposition of the relaxation spectra of mono-disperse components which constitute the blend. Discrete components are characterized by their molecular weight M i,weight fraction w i,and relaxation time spectrum H i(λ). ). In contrast to broadly distributed blends in which the small molecules mobilize the large ones and vice versa, we introduce the term “slightly polydisperse” for blends with molecular weight distributions narrow enough to have very little change in the longest relaxation times of each molecular weight component. The properties of this blending rule are analyzed and dynamic data is calculated for slightly poly-disperse polystyrene. As an application, the blending rule is used to determine the characteristic mono-disperse parameters (BSW parameters) of two materials, poly (vinyl methyl ether) and polycarbonate, for which we could not determine their BSW parameters directly since they were not available in nearly monodisperse form. The proposed blending rule can only be applied to systems in which all components are above the entanglement molecular weight, i.e. M i≫M c.
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  • 21
    ISSN: 1435-1528
    Keywords: Key words Carboxymethylcellulose ; Rheology ; Optical rheometry ; Flow birefringence ; Orientation angle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Sodium carboxymethylcellulose (NaCMC) in solution represents a complex rheological system, since it forms aggregates and associations and hence higher-level structures and, depending on the synthesis, is only found in a molecularly dispersed form in exceptional cases. Rheo-mechanical investigations of the viscoelasticity showed that the Cox-Merz rule is not fulfilled. The aim was therefore to examine whether rheo-optics could be employed to provide more detailed conclusions about the parameters that influence the flow behavior of NaCMC than has hitherto been available with mechanical methods. The flow birefringence, Δn ′, rises as the degree of polymerization increases, and exhibits the same dependence on molar mass as does the viscosity: Δn ′∝M w 3.4. As the degree of polymerization increases while the shear rate remains constant, the polymer segments become more distinctly aligned in the direction of shear. Hence increasing the degree of polymerization also affects the solution structure, i.e. the interaction of the molecules with one another. The stress-optical rule only applies to a limited extent for this system. The stress-optical coefficient, C, is almost independent of the shear rate, but is strongly influenced by the concentration and attains a limiting value of 3 × 10−8 Pa−1. C was determined for a polymer in dilute solution and the curve obtained also enabled transitions in the solution structure to be recognized.
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  • 22
    ISSN: 1435-1528
    Keywords: Key words Phase separation ; Rheology ; Polymer blends ; Dynamic measurements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Phase separation processes in mixtures of poly-α-methylstyrene-co-acrylonitrile (PαMSAN) and poly-methylmethacrylate (PMMA) with lower critical solution temperature (LCST) behavior have been studied, focusing on the manifestation of the interface in oscillatory shear measurements. By using blends of different composition, systems with a droplet-matrix morphology or a co-continuous structure are generated during the phase separation process. The feasibility of probing this morphology development by rheological measurements has been investigated. The development of a disperse droplet phase leads to an increase in the elasticity of the blend at low frequency, showing up as a shoulder in the plot of storage modulus versus frequency. Here, the droplet growth is unaffected by the shear amplitude up to strains of 0.2; therefore the resulting dynamic data are suitable for quantitative analysis. In contrast, for blends in which phase separation leads to a co-continuous structure, the storage modulus shows a power law behavior at low frequency and its value decreases as time proceeds. For the latter systems, effects of the dynamic measurement on the morphology development have been observed, even for strain amplitudes as low as 0.01. To probe the kinetics of morphology evolution in droplet-matrix systems, measurements of the time dependence of the dynamic moduli at fixed frequency should be performed (for a whole series of frequencies). Only from such measurements, curves of the frequency dependence of the moduli at a well defined residence time can be constructed. From fitting these curves to the emulsion model of Palierne, the droplet diameter distribution at that particular stage in the phase separation and growth process can be obtained. It is not appropriate to use a simplified version of the Palierne model containing only the average droplet size, because a morphology with too broad a size distribution is generated.
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  • 23
    ISSN: 1435-1528
    Keywords: Key words Liquid crystalline polymer ; Hydroxypropylcellulose ; Band texture ; Rheo-optics ; Rheology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The band texture occurs in lyotropic and thermotropic main-chain polymers after cessation of flow. This paper begins with a review of work concerned with band texture formation following shear and is followed by the presentation of original results obtained during a recent investigation. The evolution of band texture formation in a Klucel EF, 50% hydroxypropylcellulose (HPC) water solution, has been observed using polarized optical microscopy. The relationship determined between the primary shear rate and the rate of evolution of the band texture is complex and three different behaviours have been observed corresponding to three shear rate regions. Both steady flow and dynamic rheological investigations have been conducted on the HPC solution, the results of which have been related to the optical behaviour of the band texture. Data from steady flow investigations suggest that the viscosity of the solution when the band texture is present, decreases following increasing primary shear rates, is shear thinning and increases linearly with the time following its formation. Dynamic investigations suggest a definite link between the band texture evolution and the evolution of both G′ and G′′. In addition, the perfection of the band texture versus the primary shear rate has been quantified by studying the evolution of tan(δ) following the cessation of the primary shear. Dynamic experiments show that the structure of the band texture remains longer than suggested by the optical aspect of the texture. Small angle light scattering patterns have been correlated with the development of the band texture and confirm the continuing presence of the band texture structure following its optical disappearance.
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  • 24
    ISSN: 1435-1528
    Keywords: Key words Band texture ; Acetoxypropylcellulose ; Liquid crystalline polymer ; Rheo-optics ; Rheology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The optical evolution of the band texture occurring in acetoxypropylcellulose thermotropic polymer has been investigated as a function of temperature and primary shear rate. Two distinct kinds of band texture were observed which are referred to here as the `fast' and `slow' band textures with regard to their rate of evolution. The fast band texture appears very quickly following the cessation of shear and then disappears. The slow band texture is much finer than the fast band texture and appears to exist both during and after the appearance of the fast band texture. The evolution behaviour of the fast band texture is interpreted in terms of the shifting of a three-region evolution curve. Particular attention has been paid to investigating the influence of temperature on the formation of the fast band texture. Rheo-optical experiments show that the minimum shear rate required to form the fast band texture increases as a power-law function of the temperature. By subsequently performing steady flow measurements over a range of temperatures, the minimum shear stress required to form the fast band texture has been found to be independent of temperature and to increase linearly with the molecular weight of the sample. Results obtained from dynamic tests are compared with similar tests conducted previously on a lyotropic hydroxypropylcellulose water solution (Harrison and Navard 1999). The results of the comparison provide evidence in support of a connection between the behaviour of the dynamic functions and the optical evolution of the slow band texture. These results suggest that nematic and cholesteric fluids can relax through several different possible mechanisms, each of which results in a periodic band texture following the cessation of shear.
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  • 25
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    Rheologica acta 35 (1996), S. 556-566 
    ISSN: 1435-1528
    Keywords: Rheology ; polymer blends ; phase separation ; viscoelasticity ; concentration fluctuations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The shear rheology of a binary polymer blend exhibiting a lower critical solution temperature (LCST) phase diagram and a small dynamic asymmetry (difference of glass transition temperatures between its constituents) has been investigated in the vicinity of phase separation; it is a mixture of a random copolymer of styrene and maleic anhydrite and poly(methyl methacrylate). In the linear viscoelastic regime, the material functions are sensitive to phase separation, and the effects of critical concentration fluctuations, which dominate the mechanical response, are quantified, yielding both the binodal and spinodal curves. The weak dynamic asymmetry is apparently responsible for the reduced magnitude of the observed effects, compared to blends exhibiting much larger contrast in glass transition; therefore, this property affects to some degree the accuracy of the rheologically determined phase diagram. The steady shear properties are weakly sensitive to phase separation, and suggest that shear-induced demixing may be possible. They also indicate the importance of the amount of strain energy introduced to the blend in controlling the effects of flow on phase behavior. This investigation demonstrates that the universal effects of concentration fluctuations can be detected in LCST binary polymer blends, provided that some dynamic asymmetry exists, and further they can be quantified in order to characterize the interplay between rheology and thermodynamics of these systems.
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  • 26
    ISSN: 1435-1528
    Keywords: Rheology ; polypara-phenylenetherephthalamide ; liquid crystals ; transients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Nearly all the available information on the transient flow behaviour of liquid crystalline polymers has been obtained on model systems, especially on solutions of polybenzylglutamate (PBG) and hydroxypropylcellulose (HPC). The assessment of rheological models has been based almost entirely on these model systems. It is not clear how much of the available theoretical and experimental knowledge can be applied to systems of industrial relevance, which have quite different molecular structures. Here, an industrial lyotropic system, poly(p-phenylenetherephthalamide) (PpPTA) in sulphuric acid (TWARON from AKZO), is investigated. Various techniques to study transient behaviour are used, these include measurements of transient shear and normal stresses after sudden changes in shear rate, dynamic moduli and stress relaxation after cessation of flow and elastic recoil. At all shear rates studied the PpPTA solution is shear thinning, and the first normal stress difference remains positive. For the stress transients a strain scaling applies reasonably well as it did in model systems. The moduli increase with time upon cessation of flow, indicating that the molecules become less oriented in the previous flow direction. This particular behaviour is similar to that of HPC. Transients also resemble more closely those of HPC rather than those of PBG. This latter difference might be attributed to the higher flexibility of HPC and PpPTA chains as compared with PBG molecules.
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  • 27
    ISSN: 1435-1528
    Keywords: Rheology ; liquid crystalline polymer ; hydroxypropylcellulose ; band texture ; polydomain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The viscosity of a main-chain liquid crystalline polymer (anisotropic aqueous solution of hydroxypropylcellulose) is measured in the case where the liquid crystalline polymer presents a band texture and is compared to the case of a polydomain texture.
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  • 28
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    Colloid & polymer science 259 (1981), S. 908-910 
    ISSN: 1435-1536
    Keywords: Rheology ; concentrated polymer solutions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Ein verallgemeinertes Reptationsmodell wird vorgestellt. Entlang einer Polymerkette berücksichtigt es die gehinderte Difussion von Defekten, die Länge speichern. Dieser Effekt wird beschrieben mittels einer Wartezeitverteilung für die Defektplatzwechselvorgänge. In der Folge findet man für wichtige rheologische Größen Molekulargewichtsabhängigkeiten in Form von Potenzgesetzen mit gebrochenen Exponenten an Stelle der ganzzahligen Exponenten des konventionellen Reptationsmodells.
    Notes: Summary The reptation model is generalized on the basis of a theory which accounts for hindered defect diffusion along the chain. A basic ingredient of the theory is a waiting time distribution for the hops of elementary defects which store length. Important rheological quantities are found to generally depend on fractional powers of the molecular mass rather than on integer powers as in the conventional reptation picture.
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  • 29
    Electronic Resource
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    Colloid & polymer science 106 (1997), S. 180-182 
    ISSN: 1435-1536
    Keywords: Rheology ; suspension ; adsorption ; polystyrene ; depletion flocculation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Storage moduli (G′) of hydrophilic and hydrophobic silica suspensions in trans-decalin and in trans-decalin solutions of polystyrene (PS) have been measured by taking account of PS adsorption. PS were adsorbed on the hydrophilic silica. TheG′ values of the hydrophilic suspensions in the presence of low molecular weight PS are similar to those without PS and they are larger than those in the presence of higher molecular weight PS. On the other hand, any PS chains cannot adsorb on the hydrophobic silica particles. TheG′ values of all hydrophobic suspensions are higher than that in trans-decalin due to depletion flocculation and they are two orders of magnitude larger than those for the hydrophilic silica suspensions.
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