Gelation study of high processability and high reliability ternary systems based on benzoxazine, epoxy, and phenolic resins for an application as electronic packaging materials

 Fourier transform mechanical spectroscopy technique (FTMS) is utilized as a powerful tool to study the sol-gel transition of covalent bonded polymeric network. Winter and Chambon criteria resulting from the fractal-geometry characteristic of the gel networks allow the determination of the gel point with only single experiment using this technique. The gelation behaviors of low melt viscosity ternary systems of benzoxazine, epoxy, and phenolic resins are investigated and analyzed by the technique in order to study the effect of epoxy diluent on the rheological property development before and after the gel points. The gel time at 140 °C ranges from 5 min to 30 min and less than 5 min at 180 °C for all tested ternary system compositions. The gelation of the ternary mixture shows an Arrhenius-type behavior and the gel time can be well-predicted by the Arrhenius equation. Received: 23 November 1999 Accepted: 2 January 2001     

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     

Rheological behavior of dilute solutions of a side-chain liquid-crystalline polysiloxane in 4,4′-n-octylcyanobiphenyl

The electrorheological (ER) behavior and stress transient response of dilute solutions of a side-chain liquid-crystalline polysiloxane (LCP) in 4,4′-n-octylcyanobiphenyl (8CB) is studied. In the flow-tumbling regime of 8CB, i.e. from T = 34–38 °C, the stress transients of both 8CB and LCP/8CB solutions show oscillatory responses, but with shorter oscillation periodicities for the solution. In the flow-aligning regime of 8CB, i.e. at 39 and 40 °C, a transformation to flow-tumbling is observed in the stress transients of the LCP/8CB solution. In both cases, analysis of the transient responses indicates that the change in Leslie viscosity coefficients on dissolving the LCP are δα₂ < 0 and δα₃ > 0. The amplitude of the ER response, defined as the viscosity difference between the on and off states, Δη = η_on − η_off, is only weakly affected by the dissolution of LCP. These rheological results can be interpreted consistently using a modified version of a hydrodynamic theory by Brochard, provided an additional dissipation mechanism is included, which derives from the presence of an elastic torque between director rotation and LCP orientation. Received: 8 September 1999/Accepted: 13 December 1999     

Thermorheological properties near the glass transition of oligomeric poly(methyl methacrylate) blended with acrylic polyhedral oligomeric silsesquioxane nanocages

Two distinct oligomeric species of similar mass and chemical functionality (M _w≈2,000 g/mol), one a linear methyl methacrylate oligomer (radius of gyration R _g≈1.1 nm) and the other a hybrid organic–inorganic polyhedral silsesquioxane nanocage (methacryl-POSS, r≈1.0 nm), were subjected to thermal and rheological tests to compare the behaviors of these geometrically dissimilar molecules over the entire composition range. The glass transition temperatures of the blends varied monotonically between the glass transition temperatures of the pure oligomer (T _g=−47.3°C) and the pure POSS (T _g=−61.0°C). Blends containing high POSS contents (with volume fraction φ _POSS≥0.90) exhibited enhanced enthalpy relaxation in differential scanning calorimetry (DSC) measurements, and the degree of enthalpy relaxation was used to calculate the kinetic fragility indices m of the oligomeric MMA (m=59) and the POSS (m=74). The temperature dependences of the viscosities were fitted by the free-volume based Williams–Landel–Ferry (WLF) and Vogel–Fulcher–Tammann (VFT) framework and a dynamic scaling relation. The calculated values of the fragility from the WLF–VFT fits were similar for the POSS (m=82) and for the oligomer (m=76), and the dynamic scaling exponent was similar for the oligomeric MMA and the POSS. Within the range of known fragilities for glass-forming liquids, the temperature dependence of the viscosity was found to be similarly fragile for the two species. The difference in shape of the nanocages and oligomer chains is unimportant in controlling the glass-forming properties of the blends at low volume fractions (φ _POSS<0.20). However, at higher volume fractions, adjacent POSS cages begin to crowd each other, leading to an increase in the fractional free volume at the glass transition temperature and the observed enhanced enthalpy relaxation in DSC.     

Application of 2-D LIF temperature measurements in water using a Nd : YAG laser

 The application of Laser Induced Fluorescence (LIF) for temperature measurements in water using a Nd : YAG laser is investigated. A natural convection problem is used to test the applicability of LIF in the temperature range of 20–60°C. The measured temperature field is compared with numerical results and the influences of shadowgraph effects on the measured temperature field are investigated. An accuracy of 1.7°C is attained if shadowgraph effects can be neglected. This only holds if correction for photobleaching and variation of laser power output is applied. Received: 8 July 1998/Accepted: 3 February 1999     

Determination of the WLF constants of cooked soy flour and their dependence on the extent of cooking

The Williams, Landel and Ferry (WLF) equation is useful in predicting the temperature-induced changes in foods near the glass transition temperature. WLF constants have been found to be material properties rather than ‘universal values’. Adequate information on the magnitude of the WLF constants as a function of polymeric property changes, such as degree of crosslinking, during processing and storage is not available in the food polymer literature. The objective of the present study is to determine the variation of the WLF constants of cooked soy flour with the extent of cooking (and therefore crosslinking) of the soy flour. WLF constants in this paper were determined using time–temperature superposition principles and Ferry’s reduction method. The WLF constants for soy flour were found to be different from the universal values reported for synthetic polymers and show significant differences across degree of crosslinking markers selected and the variation was correlated using available semi-quantitative methods.     

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     

Influence of molecular parameters on the stress dependence of viscous and elastic properties of polypropylene melts in shear

The stress dependencies of the steady-state viscosity η and, particularly, that of the steady-state elastic compliance J _e of various linear isotactic polypropylenes (PP) and one long-chain branched PP are investigated using creep-recovery tests. The creep stresses applied range from 2 to 10,000 Pa. In order to discuss the stress-dependent viscosity η and elastic compliance J _e with respect to the influence of the weight average molar mass M _w and the polydispersity factor M _w/M _n the PP are characterized by SEC–MALLS. For the linear PP, linear steady-state elastic compliances J_e⁰J_{\rm e}^0 in the range of 10^− 5–10^− 3 Pa^− 1 are obtained depending on the molar mass distribution. J_e⁰J_{\rm e}^0 of the LCB-PP is distinctly higher and comes to lie at around 10^− 2 Pa^− 1. J_e⁰J_{\rm e}^0 is found to be independent of M _w but strongly dependent on polydispersity. η and J _e decrease with increasing stress. For the linear PP, J _e as a function of the stress τ is temperature independent. The higher M _w/M _n the stronger is the shear thinning of η and the more pronounced is the stress dependence of J _e. For the LCB-PP, the strongest stress dependence of η and J _e is observed. Furthermore, for all PP J _e reacts more sensitively to an increasing stress than η. A qualitative explanation for the stronger stress dependence of J _e compared to η is given by analyzing the contribution of long relaxation times to the viscosity and elasticity.     

Simultaneous determination of shear and extensional viscosities and wall slip by on-line rheometry with parameter fitting: an application to EPDM rubber

Shear and extensional viscosities and wall slip are determined simultaneously under extrusion processing conditions using an on-line rheometer. Because it is not possible to independently control flow rate and temperature, classical methods for interpretation of capillary data cannot be used with on-line rheometry. This limitation is overcome using computational optimization to fit parameters in a flow model. This consists of three parts, representing shear viscosity, extensional viscosity, and wall slip. Three-parameter, power law forms, based on local instantaneous deformation rates and including temperature dependence, are used for each, and analytic solutions applied for entry flow and flow in the capillary. For entry flow, the Cogswell–Binding approach is used, and for developed flow in the capillary a solution incorporating wall slip is derived. The rheometer, with interchangeable capillaries, is mounted in place of the die on a rubber profile extrusion line. Pressure drops and temperatures for extrusion of an EPDM rubber through 2 mm diameter capillaries of length 0, 2, 3, 4, and 5 mm are logged and flow rates determined for a range of extruder speeds (5 to 20 rpm). Pressures ranged from 60 to 75 bar and temperatures from 86 to 116 °C. Mean flow velocity in the capillaries was between 5 × 10⁻³ and 5 × 10⁻¹ m s⁻¹. The nine material parameters are optimized for best fit of the analytic pressure drops to experimental data, using about 100 data points, with the Levenberg–Marquardt method. It is concluded that flow is dominated by extension and wall slip. Shear flow appears to play little part. The slip model indicates that slip velocity increases much more rapidly than the wall shear stress (in the range 0.5–1 MPa) and decreases with temperature for a given stress level. Results for the (uniaxial) extensional viscosity represent an engineering approximation to this complex phenomenon at the high strains (approximately 200) and high extension rates (up to 800 s⁻¹) applying in the extrusion. Results indicate a slight extension hardening and a decrease with temperature. Results are put into the context of the available studies in the literature, which, particularly with regard to wall-slip and extensional flow, consider conditions far removed from those applying in industrial extrusion. The present methods provide a powerful means for flow characterization under processing conditions, providing data suitable for use in computer simulations of extrusion and optimization of die design.     

On the Mathematical Modelling of a Compressible Viscoelastic Fluid

Thermodynamical considerations have largely been avoided in the modelling of complex fluids by invoking the assumption of incompressibility. This approximation allows pressure to be defined as a Lagrange multiplier, and therefore its natural connection with other thermodynamic variables such as density and temperature is irretrievably lost. Relaxing this condition to allow more realistic modelling involves much more than prescribing an equation of state. Even for a simple isothermal viscoelastic model, as explored in this paper, the transition to a compressible model is non-trivial. This paper shows that pressure enters the governing equations in a non-intuitive way. Furthermore, a fluid volume element, which is no longer constant, radically changes the way the basic element of the constitutive equations is viewed—stress is no longer the fundamental constitutive link between the momentum equations and velocity. The importance of geometry in fluid modelling is emphasised through the use of the Lie derivative, which is of a more fundamental character than the “upper” and “lower” convected derivatives prevalent in the literature and which are found to be almost redundant for a compressible fluid. There is now a strong body of non-equilibrium thermodynamics theory for flowing systems, which proves indispensible for this development. These fundamental principles are described herein using methodology and examples, that are sometimes conflicting, from the literature. The main conflict arises from the relationship between thermodynamic pressure and the trace of Cauchy stress, where the current preferred choice is (up to a constant) to set them equal—this is shown to be incorrect. Other issues such as the dependence of viscosity on density, bulk viscosity, integral modelling, the principle of objectivity and convected derivatives, are also clarified and resolved.     

A numerical simulation of suspension flow using a constitutive model based on anisotropic interparticle interactions

We report a Brownian configuration field implementation of a recent constitutive equation for suspensions, reported by Phan-Thien et al. 1999. The numerical method is a hybrid technique, which combines a modification of the Brownian configuration field method described by Hulsen et al. 1997 and the adaptive viscosity split stress formulation proposed by Sun et al. 1996. The implementation is used to examine the flow past a sphere in a tube. The relative viscosity derived from the drag force/sedimentation velocity agrees well with a well-known empiricism. In addition, the ratio of the pressure force to the drag on the sphere seems to be weakly dependent on the volume fraction, and is somewhat higher than Brenner's results of 1962, which were derived for Newtonian fluids. Received: 5 April 1999/Accepted: 27 September 1999     

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     

Evaluation of drag correction factor for spheres settling in associative polymers

Drag correction factors are calculated for the creeping motion of spheres descending in various associative polymers of different concentration with various sphere-container ratios and Weissenberg numbers. The simple-shear rheology and linear viscoelasticity of these polymeric fluids have been previously presented and modeled with the BMP (Bautista–Manero–Puig) equation of state (Mendoza-Fuentes et al., Phys Fluids 21:033104, 2009). The drag on the sphere is initially kept nearly constant for small Weissenberg numbers, We < 0.1. As the Weissenberg number increases, We < 0.1, a reduction in drag is found. Experimental results show the presence of a critical Weissenberg number at which a drag reduction occurs. The reduction in the drag correction factor is associated to the onset of extension-thinning, which coincides with the formation of a negative wake. No increase in the drag correction factor was observed, due to the simultaneous opposing effects of extension-thickening and shear-thinning viscosity. The shape of the drag correction factor curve may be predicted considering the extensional properties of the solutions, as suggested elsewhere (Chen and Rothstein, J Non-Newton Fluid Mech 116:205–215, 2004).     

Pressure-dependent viscosity and free volume of atactic and syndiotactic polystyrene

The effect of pressure on viscosity is an important but often overlooked aspect of the flow properties of polymeric materials. In this work, two polymers (an atactic and a syndiotactic Polystyrene) were characterized to determine the effect of pressure on viscosity. In particular, a device was adopted to increase the exit pressure of a standard capillary rheometer, thus obtaining data of viscosity under high pressure and high shear rates. The Simha-Somcynsky equation of state was applied to the pressure–volume–temperature experimental data of both materials to obtain the dependence of free volume on temperature and pressure. The Doolittle equation was eventually employed to verify the dependence of viscosity on free volume. It was found that, for both materials, a linear relationship holds between the logarithm of zero-shear-rate viscosity (at several temperatures and pressures) and the inverse of free volume.     

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     

Nonisothermal two‐ and three‐dimensional flow simulations of inelastic and viscoelastic fluids by a finite‐volume method

This paper applies the finite‐volume method to computations of steady flows of viscous and viscoelastic incompressible fluids in complex two and three‐dimensional geometries. The materials adopted in the study obey different constitutive laws: Newtonian, purely viscous Carreau–Yasuda as also Upper‐Convected Maxwell and Phan‐Thien/Tanner differential models, with a Williams–Landel–Ferry (WLF) equation for temperature dependence. Specific analyses are made depending on the rheological model. A staggered grid is used for discretizing the equations and unknowns. Stockage possibilities allow us to solve problems involving a great number of degrees of freedom, up to 1 500 000 unknowns with a desk computer. In relation to the fluid properties, our numerical simulations provide flow characteristics for various 2D and 3D configurations and demonstrate the possibilities of the code to solve problems involving complex nonlinear constitutive equations with thermal effects. Copyright © 2009 John Wiley & Sons, Ltd.     

Flow of a viscous incompressible fluid of temperature dependent viscosity past a permeable wedge with uniform surface heat flux

 The effect of uniform suction on the steady two-dimensional laminar forced flow of a viscous incompressible fluid of temperature dependent viscosity past a wedge with uniform surface heat flux is considered. The governing equations for the flow are obtained by using suitable transformations and are solved by using an implicit finite difference method. Perturbation solutions are also obtained near the leading edge and in the downstream regime. The results are obtained in terms of the local skin friction coefficient and the rate of heat transfer for various values of the pertinent parameters, such as the Prandtl number, Pr, the velocity gradient parameter, m, the local suction parameter, ξ, and the viscosity variation parameter, ɛ. Perturbation solutions are compared with the finite difference solutions and are found to be in excellent agreement. The effect of ξ, m and ɛ on the dimensionless velocity profiles and viscosity distribution are also presented graphically for Pr = 0.7 and 7.0, which are the appropriate values for gases and water respectively. Received on 22 July 1999     

Steady shear rheology of dilute polystyrene particle gels

This paper describes an experimental study on dispersions of monodisperse polystyrene (PS) spheres with a typical radius of 1 μm, dispersed in an electrolyte at high ionic strength, screening the electrostatic repulsion. These suspensions gelate at rest even at low volume fractions of PS particles. The density of the particles is matched with the solvent by using deuterium oxide for volume fractions φ≤0.117. Steady-state flow curves, viscosity as a function of shear rate, are measured and reported for 0.014<φ<0.322. The measured flow curves are analyzed on the basis of two models: 1. In the giant floc model (van Diemen and Stein 1983, 1984; Schreuder et al. 1986, 1987; Laven et al. 1988), at low shear rates, the shear is not distributed homogeneously but is limited to certain shear planes; the energy dissipation during steady flow is due primarily to overcoming the viscous drag on the suspended particles during motion caused by encounters of particles in the shear planes. Though this model was developed for higher solid volume fractions (0.35–0.425), we found that it also describes the rheology of dilute particle gels for 0.15≤φ≤0.3, using the same values for the parameters in the model as in the high solid volume fraction region. For φ<0.15, the model also describes the data if the fraction of distance by which a moving particle entrains its neighbors, is assumed to increase in this φ region. 2. The model of de Rooij (de Rooij et al. 1993, 1994) considers aggregates in shear flow to be monodisperse impermeable spheres with a fractal structure. The permeability is taken into account by considering a hydrodynamic radius smaller than the gyration radius in the Krieger-Dougherty expression for the hydrodynamic contribution to the viscosity. Through the use of a yield criterion the aggregate radius is modeled as a function of shear rate. We found that the model describes our experimental results, with a combination of parameter values used already by de Rooij, but only for φ<0.15. Received: 7 May 1998 Accepted: 22 December 1998     

Effect of melt viscosity of polypropylene on fibrillation of thermotropic liquid crystalline polymer in in situ composite film

 Various grades of polypropylene were melt blended with a thermotropic liquid crystalline polymer, a block copolymer of p-hydroxy benzoic acid and ethylene terephthalate (60/40 mole ratio). The blends were extruded as cast films at different values of draw ratio (slit width/film thickness). Fibrillation of TLCP dispersed phase with high fiber aspect ratio (length/width) was obtained with the matrix of low melt flow rate, i.e., high viscosity and with increasing film drawing. Melt viscosities of pure components and blends measured using capillary rheometer were found to decrease with increasing shear rate and temperature. Viscosity ratios (dispersed phase to matrix phase) of the systems being investigated at 255 °C at the shear rate ranged from 10² to 10⁴ s⁻¹, were found to lie between 0.04 and 0.15. The addition of a few percent of elastomeric compatibilizers; a tri-block copolymer SEBS, EPDM rubber and maleated-EPDM, was found to affect the melt viscosity of the blend and hence the morphology. Among these three compatibilizers, SEBS was found to provide the best fibrillation. Received: 10 January 2000/Accepted: 24 January 2000