Rheology of SiO2/(acrylic polymer/epoxy) suspensions. I. Linear viscoelasticity

Linear viscoelastic properties of SiO₂/(AP/EP) suspension with various SiO₂ volume fractions (ϕ) in a blend of acrylic polymer (AP) and epoxy (EP) were investigated at various temperatures (T). The AP/EP contained 70 vol.% of EP. The SiO₂ particles were treated with epoxy silane coupling agent. The effects of the SiO₂ particles are more pronounced in the terminal zone: a transition from viscoelastic liquid (ϕ ≤ 30 vol.%) to viscoelastic solid (ϕ ≥ 40 vol.%) was observed which can be interpreted as a critical gelation occurring at a critical particle content and critical gel temperature. The SiO₂/(AP/EP) systems exhibited a critical gel behavior at ϕ ≅ 35 vol.% and T ≅ 100°C characterized with a power–law relationship between the storage and loss moduli (G ^′ and G ^″) and frequency (ω); G ^′ = G ^″/tan(nπ/2) ∝ ω ⁿ . The critical gel exponent (n) was estimated to be about 0.45. The gelation occurred with increasing T.     

In situ monitoring the sol–gel transition for polyacrylamide gel

The effects of heating rate and shear stress on the sol–gel transition for a polyacrylamide gel during in situ preparation were investigated by dynamic rheology. The gelation evolution was also studied through monitoring of the static gelation process by means of temperature, pH, and conductivity variation. The gels were prepared by polymerization of acrylamide crosslinked with N,N′-methylenebisacrylamide using a redox initiation based on potassium persulfate/ascorbic acid. In situ gelation process was studied using oscillatory deformation tests at constant frequency of 0.1 Hz for different heating rate (from 0.5 to 5 °C/min) and shear stress (in the range of 0.1 to 10 Pa). The paper was presented at the third annual rheology conference, AERC 2006, Crete, Greece, 27–29 April 2006.     

A rheological approach to the study of concentrated milk clotting

The aim of the present work is to analyze the complex phenomena involved in the concentrated milk clotting process in order to define general criteria applicable to the design of a continuous coagulator. A full characterization of the rheological properties of completely hydrolyzed milk as a function of two different parameters, i.e., the coagulator temperature and the concentration degree of the milk, is presented. The dynamic evolution of loss, G′′, and storage, G′, moduli has been obtained at different frequency values and for different concentration degrees during the clotting process. Time cure tests have been performed on completely hydrolyzed milk samples showing that the rate of curing is very high and that the time for rheological experiments is much too short for testing Winter's theory of gelation. To overcome this problem, the intersect of loss and storage moduli was used for estimating the coagulation. Coagulation is faster when higher temperatures are used and the consistency of the final curd is greater if a more concentrated milk is used. A tentative physical explanation based on the network theories is presented. If an observation time far enough from the crossover point is chosen it can be seen that the curd strength estimated at 40 °C is about 50 times higher than that one evaluated at 25 °C. Among the considered temperatures, a good processing value was evaluated at 40 °C. Received: 6 February 2000 Accepted: 24 October 2000     

Thermoreversible gels in oil/EVA systems

In this work we investigate the gel formation of EVA/recycled motor oil systems as a route to obtain synthetic binders which could be used instead of natural bitumen, as well as mixed with natural bitumen to modify adequately its viscoelastic response. The EVA copolymer studied in this work has a vinyl acetate content of 18 wt% and solutions of EVA/motor oil have been prepared up to a concentration of 50 wt%. Dynamic viscoelastic frequency sweeps between 10⁻² Hz and 10² Hz have shown that above 3 wt%, at 25 °C, EVA/motor oil systems form gels. It has been possible to define an elastic equilibrium modulus, G_e, for each gel. The dependence of G_e on concentration has been compared with that of PVC/DOP and SBS/oil gels on the basis of the De Gennes model. Thermal stability of EVA/motor oil gels has also been analyzed, indicating that for the highest polymer concentrations gel point is above 80 °C. Received: 23 December 1999 Accepted: 13 June 2000     

Heat transfer during transient cooling of high temperature surface with an impinging jet

 An experimental study of transient boiling heat transfer during a cooling of a hot cylindrical block with an impinging water jet has been made at atmospheric pressure. The experimental data were taken for the following conditions: a degree of subcooling of ΔT _sub = 20–80 K, a jet velocity of u _j  = 5–15 m/s, a nozzle diameter of d _j  = 2 mm and three materials of copper, brass and carbon steel. The block was initially and uniformly heated to about 250 °C and the transient temperatures in the block were measured at eight locations in r-direction at two different depths from the surface during the cooling of hot block. The surface heat flux distribution with time was evaluated using a numerical analysis of 2-D heat conduction. Behavior of the wetting front, which is extending the nucleate boiling region outward, is observed with a high-speed video camera. A position of wetting region is measured and it is correlated well with a power function of time. The changes in estimated heat flux and temperature were compared with the position of wetting region to clarify the effects of subcooling, jet velocity and thermal properties of block on the transient cooling. Received on 17 March 2000     

Rheological properties of gluten plasticized with glycerol: dependence on temperature, glycerol content and mixing conditions

The rheological behaviour of a gluten plasticized with glycerol has been studied in oscillatory shear. The mixing operation in a Haake batch mixer leads to a maximum torque for a level of specific energy (500–600 kJ/kg) and temperature (50–60 °C) quite independent of mixing conditions (rotor speed, mixing time, filling ratio). The gluten/glycerol dough behaves as a classical gluten/water dough, with a storage modulus higher than the loss modulus over the frequency range under study. A temperature increase induces a decrease of moduli, but the material is not thermorheologically simple. Glycerol has a plasticizing effect, which can be classically described by an exponential dependence. Mixing conditions influence the viscoelastic properties of the material, mainly through the specific mechanical energy input (to 2000 kJ/kg) and temperature increase (to 80 °C). Above 50 °C, specific mechanical energy highly increases the complex modulus. The aggregation of proteins, as evidenced by size-exclusion chromatography measurements, occurs later as the dough temperature reaches 70 °C. The nature of network interactions and the respective influence of hydrophobic and disulphide contribution is discussed. A general expression is proposed for describing the viscous behaviour of a gluten/glycerol mix, which could seem simplistic for such a complex rheological behaviour, but would remain sufficient for modelling the flow behaviour in a twin screw extruder. Received: 24 November 1997 Accepted: 28 April 1999     

Temperature dependence of the interfacial tension of PS/PMMA, PS/PE, and PMMA/PE blends

The effect of temperature on the interfacial tension for PS/PMMA, PS/PE, and PMMA/PE was measured using the imbedded fiber retraction method. Interfacial tensions for PS/PMMA, PS/PE, and PMMA/PE were measured over temperature ranges of 160–250 °C, 140–220 °C, and 140–220 °C, respectively. The interfacial tension was found to follow a dependence of 3.6–0.013 T dyn/cm, 7.6–0.051 T dyn/cm and 11.8–0.017 T dyn/cm for PS/PMMA, PS/PE, and PMMA/PE, respectively. Comparison of the data with the mean field theory of Helfand and Sapse were made; however, a simple linear fit to the data described the temperature dependence in the experimental window as well as the predictions of the mean field theory. Received: 6 July 1999 Accepted: 23 March 2000     

The modified imbedded disc retraction method for measurement of interfacial tension in polymer melts

The imbedded disc retraction method is used to estimate interfacial tension in LLDPE/PS system with PS as the imbedded disc. Shape evolution of a disc of one material (PS) imbedded into the matrix of another material is observed (LLDPE). Three to five repetitions at three different temperature levels are observed. The Newtonian model of Rundqvist et al. (1996) for the imbedded disc retraction is modified to include elastic effects. The modified model is derived assuming uniaxial extension, starting with the lower convected Maxwell model. Both the original model and modified imbedded disc retraction model are used in data analysis. The mean values of interfacial tension at 190 °C, 200 °C, and 210 °C are 6.8 ± 0.7 mN/m, 3.9 ± 0.3 mN/m, and 3.7 ± 0.2 mN/m, respectively. A method of estimating whether elastic effects will significantly affect the estimated interfacial tension value during retraction for the given polymer pair is provided. Received: 6 August 1999 Accepted: 2 January 2001     

Influence of humidity on the convective heat transfer from small cylinders

 The convective heat transfer from a cylinder to a humid air stream flowing normal to the cylinder was investigated experimentally at atmospheric pressure over a range of variables which is relevant to the use of hot‐wire anemometry: air temperatures between 30 °C and 70 °C and velocities between 12 and 37 m/s. For molar fractions of water vapour up to 0.27, the heat transfer increased with increasing humidity. The ratio of heat transfer rates in humid air and dry air is a unique function of the molar fraction of water vapour, independent of the air temperature and flow velocity. Received: 28 November 1996/Accepted: 5 July 1997     

Dependence of linear viscoelastic critical strain and stress values on extent of gelation for a thermally activated gelling system

A large body of literature is focused on the accurate determination of a gel point for systems undergoing a sol-gel phase transition. Investigation into the limiting strain and stress for linear viscoelastic behaviour at various stages of a phase transition such as gelation is a subject that is rarely commented on. The small amplitude oscillatory rheological behaviour of a biopolymer cross-linker system through a thermally activated sol-gel transition is presented. Mechanical spectra were interpreted through application of the gelation criteria of Chambon and Winter (Winter and Chambon 1986; Chambon and Winter 1987), where the (so-called gel strength) parameter S, and relaxation exponent, n are obtained. A detailed study of the limit of linear viscoelasticity yields important trends in critical stress (σ°_c) and critical strain (γ°_c) limits highlighting the possible experimental difficulties associated with mechanical measurements obtained in close proximity to the gel point. Received: 17 March 2000 Accepted: 2 October 2000     

A New Device for Mechanical Testing of Blood Vessels at Cryogenic Temperatures

As part of an ongoing program to study the thermo-mechanical effects associated with cryopreservation via vitrification (vitreous in Latin means glassy), the current study focuses on the development of a new device for mechanical testing of blood vessels at cryogenic temperatures. This device is demonstrated on a bovine carotid artery model, permeated with the cryoprotectant cocktail VS55 and a reference solution of 7.05M DMSO, below glass transition. Results are also presented for crystallized specimens, in the absence of cryoprotectants. Results indicate that the elastic modulus of a specimen with no cryoprotectant, at about −140°C (8.6 and 15.5°C below the glass transition temperature of 7.05M DMSO and VS55, respectively), is 1038.8 ± 25.2 MPa, which is 8 and 3% higher than that of a vitrified specimen permeated with 7.05M DMSO and VS55, respectively. The elastic modulus of a crystallized material at −50°C is lower by ∼20% lower from that at −140°C.     

2D temperature measurements in the wake of a heated cylinder using LIF

A technique is described to measure the instantaneous 2D temperature distribution in the wake of a heated cylinder using `laser-induced fluorescence'. Rhodamine B, a fluorescent dye, is used as a temperature indicator. The relation between fluorescence intensity and temperature is determined by means of calibration experiments in the temperature range of 20–35 °C with an accuracy of ±0.1 °C. The temperature distribution behind the heated cylinder is well visible and can be measured with a high spatial resolution. Corrections for variation in laser energy and intensity distribution in the laser sheet have to be made to further improve the accuracy of the measuring method. Received: 3 January 2001/Accepted: 18 May 2001     

Experimental investigation of mixed convection heat transfer in a horizontal and inclined rectangular channel

 Mixed convection heat transfer in rectangular channels has been investigated experimentally under various operating conditions. The lower surface of the channel is subjected to a uniform heat flux, sidewalls are insulated and adiabatic, and the upper surface is exposed to the surrounding fluid. Experiments were conducted for Pr=0.7, aspect ratios AR=5 and 10, inclination angles 0° ≤ θ ≤ 30°, Reynolds numbers 50 ≤ Re ≤ 1000, and modified Grashof numbers Gr*=7.0 × 10⁵ to 4.0 × 10⁷. From the parametric study, local Nusselt number distributions were obtained and effects of channel inclination, surface heat flux and Reynolds number on the onset of instability were investigated. Results related to the buoyancy affected secondary flow and the onset of instability have been discussed. Some of the results obtained from the experimental measurements are also compared with the literature, and a good agreement was observed. The onset of instability was found to move upstream for increasing Grashof number and increasing aspect ratio. On the other hand, onset of instability was delayed for increasing Reynolds number and increasing inclination angle. Received on 19 March 2001 / Published online: 29 November 2001     

Supersonic leeside flow topology on delta wings revisited

The leeside vortex structures on delta wings with sharp leading edges were studied for supersonic flow at the Institute of Theoretical and Applied Mechanics of the Russian Academy of Sciences in Novosibirsk. The experiments were carried out with three wings with sweep angles of χ=68°, 73°, and 78° and parabolic profiles in the 0.6 × 0.6 m² test section of the blow-down wind tunnel T-313 of the institute. The test conditions were varied from Mach numbers M=2 to 4, unit Reynolds numbers from Re _l=26 × 10⁶ to 56 × 10⁶ m⁻¹, and angles of attack from α=0° to 22°. The results of the investigations revealed that for certain flow conditions shocks are formed above, below, and between the primary vortices. The experimental data were accurate enough to detect the onset of secondary and tertiary separation as well as other boundaries. The various flow regimes discussed in the literature were extended in several cases. The major findings are reported. Received: 6 September 1999/Accepted: 24 January 2000     

The viscosity of water at high pressures – especially at subzero degrees centigrade

New experimental data for the viscosity of water at high pressures up to 700 MPa in the temperature range of −13 °C to 20 °C are presented. The measurements were carried out with two different types of viscometer, both gravity driven. The set-up of the viscometers and the pressure-dependent corrections are briefly described. The viscosity data are compared with available literature data. Reasons for the deviations are discussed. Models to describe pressure-viscosity behavior of water are applied to the data. The applicability to the moderate temperature viscosity data is discussed and it is checked whether the range of validity of the models can be extended to subzero temperatures. Received: 8 March 2000 Accepted: 28 June 2000     

Irradiation-Induced Solute Clustering in a Low Nickel FeMnNi Ferritic Alloy

Understanding the radiation embrittlement of reactor pressure vessel (RPV) steels is required to be able to operate safely a nuclear power plant or to extend its lifetime. The mechanical properties degradation is partly due to the clustering of solute under irradiation. To gain knowledge about the clustering process, a Fe−1.1 Mn−0.7 Ni (at.%) alloy was irradiated in a test reactor at two fluxes of 0.15 and 9 ×10¹⁷ n _E > 1MeV .m^− 2.s^− 1 and at increasing doses from 0.18 to 1.3 ×10²⁴ n _E > 1MeV .m^− 2 at 300°C. Atom probe tomography (APT) experiments revealed that the irradiation promotes the formation in the α iron matrix of Mn/Mn and/or Ni/Ni pair correlations at low dose and Mn–Ni enriched clusters at high dose. These clusters dissolve partially after a thermal treatment at 400°C. Based on a comparison with thermodynamic calculations, we show that the solute clustering under irradiation can just result from an induced mechanism.     

Dynamic rheological behavior of DBS-induced poly(propylene glycol) physical gels

Physical gelation can be induced in various organic and silicone-based liquids, as well as in polymeric melts, upon addition of 1,3:2,4-dibenzylidene sorbitol (DBS). Such gels are stabilized by the formation of a percolated DBS network composed of highly interconnected nanofibrils. In this study, we explore several factors affecting the rheological properties of poly(propylene glycol) (PPG) gelled by DBS. To ascertain the effect of PPG molecular weight (M_PPG) on gel formation and rheology, we have investigated three series of DBS-induced PPG gels in which M_PPG varies from 425 g/mol to 4000 g/mol. Dynamic stress measurements reveal that the DBS concentration identifying the onset of PPG gelation decreases with increasing M_PPG. Since the solubility parameter (δ_s) of PPG decreases sharply as M_PPG increases over this M_PPG range, this observation suggests that DBS gelation is sensitive to δ_s of the matrix liquid, in agreement with previously reported data collected from DBS-gelled solvents. Moreover, the elastic modulus and yield stress are found to increase with increasing (i) DBS concentration for the three series of PPG/DBS gels examined here and (ii) recovery time after cessation of an introductory shear. Received: 22 February 2000 Accepted: 9 August 2000     

Curing effects on the acoustical properties of epoxy polymers

This paper presents an experimental method for measuring the attenuation and the velocity of longitudinal ultrasonic waves propagating through flat epoxy polymer samples. The study takes place in the first phase of epoxy polymer's polymerization, where these materials pass slowly from liquid state to the solid state. For this purpose an experimental setup was introduced, suitable for the accurate evaluation of the acoustic properties Δα andc _ℓ ^e , when the epoxy polymers are in their first phase of polymerization, while they are cured for 24 hours at room temperature (20°C). The ultrasonic method used is the pulse echo-through transmission technique. From the variation ofc _ℓ ^e and Δα during the first phase of epoxy polymers curing, the three characteristic states: liquid, semi-solid and solid, are clearly determined. It is also observed that plasticizer reduces the testability and the semi-solid state shows greater attenuation than either the liquid or the solid state.     

Experimental studies on drag reduction and rheology of mixed cationic surfactants with different alkyl chain lengths

Experimental studies of the effects of mixtures of cationic surfactants on their drag reduction and rheological behaviors are reported. Cationic alkyl trimethyl quaternary ammonium surfactants with alkyl chain lengths of C₁₂ and C₂₂ were mixed at different molar ratios (total surfactant concentrations were kept at 5 mM with 12.5 mM sodium salicylate (NaSal) as counterion). Drag reduction tests showed that by adding 10% (mol) of C₁₂, the effective drag reduction range expanded to 4–120 °C, compared with 80–130 °C with only the C₂₂ surfactant. Thus mixing cationic surfactants with different alkyl chain lengths is an effective way of tuning the drag reduction temperature range. Cryo-TEM micrographs revealed thread-like micellar networks for surfactant solutions in the drag reducing temperature range, while vesicles were the dominant microstructures at non-drag reducing temperatures. High extensional viscosity was the main rheological feature for all solutions except 50% C₁₂ (mol) solution, which also does not show strong viscoelasticity. It is not clear why this low extensional viscosity solution with relatively weak viscoelasticity is a good drag reducer. Received: 3 November 1999/Accepted: 5 January 2000     

Temperature dependence of the viscosity of highly starch-filled poly(hydroxy ester ether) biodegradable composites

 The temperature dependence of the viscosity of starch-filled poly(hydroxy ester ether) (PHEE) biodegradable composites was analyzed using Arrhenius and WLF equations. Corn starch/PHEE materials were extruded using a twin screw extruder with starch volume fractions from 0.27 to 0.66. Dynamic strain sweep measurements were carried out at 10 rad/s at six different temperatures from 100 °C to 150 °C. Both Arrhenius and WLF equations model equally well the temperature effect on viscosity of PHEE and starch/PHEE composites with starch volume fractions up to 0.36. Arrhenius equation with stress correction describes the stress dependence of viscosity of starch/PHEE composites with higher starch volume fractions. The activation energy using both Arrhenius equation and Arrhenius equation with stress correction is 62.7 kJ/mol for pure PHEE and starch/PHEE composites. Received: 10 September 1999 Accepted: 27 March 2000