Differential scanning calorimetry analysis of thermoset cure kinetics: Phenolic resole resin

The Differential Scanning Calorimetry (DSC) trace for a commercial phenolic resole resin shows two distinct peaks. Assuming that these represent two independent cure reactions results in a kinetic model of the form: with κ_i = κ_io exp(-B_i/T). The Arrhenius parameters were estimated from a plot of ln(β/T) versus 1/T_p. The parameters, p, n₁, and n₂ were obtained by writing the DSC response predicted by the equation above in terms of a function which contains temperature as the only variable. with $ \theta _i = \left({1/\beta} \right)\int_{T_0}^T {\kappa _i dT \le r_i} $ dT ? r_i and r_i = 1/(1-n_i). Fitting this equation to the DSC response measured at a scan rate of 4°C/min obtains p ≈ 0.66; n₁ ≈ 0.55; n₂ ≈ 2.2; B₁ ≈ 8285; B₂ ≈ 7480; κ₁ ≈ 1. 12 × 10⁸ s^?1; κ₂ ≈ 0.99 × 10⁶ S^?1.     

The apparent rate constant model for kinetics of radical chain copolymerization: Chemical-controlled process

In this article the kinetics of chemical-controlled radical-chain copolymerization have been reduced to pseudohomopolymerization kinetics by introducing the apparent rate constants, The methods for the determinations of the values of the apparent rate constants, mode of termination, and the methods for the calculation of molecular weights and distributions are proposed. The data required for these determinations and calculations are simply obtained by the usual steady-state method. According to the traditional kinetics along with the definitions of the apparent rate constants, these apparent rate constants as functions of traditional rate constants, monomer compositions, and copolymer compositions are derived. Further utilizing the theoretical expressions obtained, we show that the apparent rate constants are the general rate constants for both radical chain homo- and copolymerizations. The bulk radical copolymerizations of methyl methacrylate and styrene at various monomer feed compositions at 60°C are used to test the proposed model. The empirical apparent rate constants obtained are described well, by the following expressions, and and the mode of termination on the combination termination is where K and K denote the apparent rate constants of propagation and termination, respectively. The term f₁(= 1 ? f₂) stands for the mole fraction of styrene in the monomer solution fed. F₁ is the copolymer composition produced at f₁. β is the mode of termination.     

The kinetics and mechanism of the chloride-chlorate reaction

The kinetics of the reaction have been studied at 25°C. in strong acid solution; the effects of acidity, chloride, chlorate and chlorine are reported. A mechanism is postulated to interpret the peculiar features of this reaction as well as the stoichiometry and some of the kinetics of the parallel reaction The mechanism involves HClO₂ and HOCl as intermediates General rate expressions are derived for the formation of chlorine dioxide and chlorine, and the individual rate constants are calculated. An expression is obtained for the relationship between the ratio of chlorine dioxide to chlorine produced and the ratio of chlorate to chloride.     

A modified correlation to predict the minimum velocity required to elutriate solids from a liquid-fluidized bed

The consideration of sphericity of solids for the prediction of u_me gives rise to some improvement of the correlation proposed earlier by the author. In the absence of wall-effect, the following correlation is obtained: which gives a standard deviation of ± 16.3% for 138 different experiments as against ± 21.6% for 134 runs by the correlation reported earlier. The ranges of the various groups are      

Spin coating behavior of polyimide precursor solutions

Experimental data confirm the utility of the following simple equation in predicting the spin coating behavior of polyimide precursor solutions: in which .     

Predicting elastic moduli of heterogeneous polymer compositions

A new method for predicting elastic moduli M of heterogeneous polymer compositions is proposed. It is based on a phenomenological adjustment between parallel and series models for upper and lower bound moduli M_U and M_L. Thus, where ?_H is the volume fraction of hard phase, ?_S is the volume fraction of soft phase, and n is the only adjustable parameter since the upper and lower bound moduli are given by and where M_H and M_S are the moduli of the pure hard and soft phases, respectively. Predicted values of M are in agreement with measured values in a number of systems which include polyblends and composite materials of fixed morphology. The significance of n is discussed relative to concentrations in the area of a phase transition for the polyblends or relative to phase morphology in the case of fixed morphology compositions. Interestingly, the relationship, by analogy, is in agreement with measured values of polyblend melt viscosities.     

Catalytic oxidation of benzene to maleic anhydride in a continuous stirred tank reactor

The kinetics of the vapor phase oxidation of benzene has been studied over an industrial catalyst in a continuous stirred tank reactor in the temperature range from 280 to 430°C and at atmospheric pressure. The products obtained are maleic anhydride, carbon oxides and water. The rate of the overall reaction (disappearance of benzene) is represented by the following expression based upon a steady state adsorption model The rate of formation of maleic anhydride is correlated by the equation which allows for a homogeneous depletion of maleic anhydride. The rate constants k_B, k_O, k_2(g) were found to follow Arrhenius behavior.      

Heat transfer to agitated non-newtonian fluids

Heat transmission to agitated non-Newtonian liquids in a jacketed vessel has been studied. Heat transfer tests were conducted under unsteady-state conditions with pseudo-plastic solutions (behavior index range: 0.343 to 0.633). For a generalized Reynolds number ranging from 100 to 5000, two correlations were found: The use of a generalized Sieder and Tate number resulted in an equation combining both heating and cooling data with a somewhat higher mean deviation (19.3%):      

Some aspects of liquid-solid fluidized beds

Hydrodynamic characteristics of randomly packed fluidized beds were investigated using particles of different sizes and densities fluidized with water. The minimum fluidization velocity was found to be independent of the initial bed height. The minimum fluidization velocity was found to be Bed expansion followed the Richardson Zaki relationship and the exponent 'n' has been correlated as:      

Drop size distribution in a graesser contactor

An investigation was conducted of drop size distribution in a Graesser contactor, employing five liquid – liquid systems, viz., kerosene/water, benzene/water, xylene/water, hexane/water and n–butyl acetate/water. A 100 mm (4 inch) diameter Graesser contactor was used for this purpose It was found that the drop size distribution in a Graesser contactor obeys the upper – limit distribution expressed as: where A correlation was developed relating the Sauter mean diameter (d₃₂) to other effective groups      

Influence of different water soluble polymers and poly(ethylene oxide)/ionene complexes on sedimentation of suspended particles and filter cake resistance

The objective of the investigations was to compare flocculating properties of three different water soluble resins: poly(ethylene oxide), PEO, with molecular mass M_v = 3.94 · 10⁶ g/mol; polyacrylamide, PAAm, M_v = 2.1 · 10⁶ g/mol, and tetramethyl-2,6-ionene bromide, ionene, M_w = 1500 g/mol. In each case the Healy-La Mer theory proved to be valid due to the appearence of maximum points on both the subsidence w vs. polymer concentration c, and acceleration a_Q vs. c curves. The ratios of these maximum values determined on aluminium silicate suspensions are as follows: Contrary to aluminium silicate suspension dispersed TiO₂ particles are not flocculated by PEO, although zeta potentials in both cases were found to be close up to each other, i.e. ?16.68 and ?16.38 mV, respectively. Nonetheless, the investigations carried out revealed the possibility to convert the high molecular weight PEO from being a stabilizer of the TiO₂ suspension into a flocculant by means of interpolymer complexation with the ionene, i.e. a polyammonium salt. The ratios of maximum values related to complexes prepared with different unit mole ratios (u.m.r., values indicated in parantheses) are as follows: and Values at u.m.r. = 0 refer to uncomplexed PEO and at u.m.r. = ∞ to the uncomplexed ionene, respectively.     

Densities of hydrocarbons in their saturated vapor and liquid states

The Sum and differences of the saturated vapor and liquid densities of 23 hydrocarbons were used to develop the following reduced density relationships for these saturated states The hydrocarbons considered included n-parafins, olefins, diolefins, naphthenes, and aromatics. Constants β, γ, and δ, and exponent n were found to be dependent on,. Equation (a) can reproduce liquid densities with an overall average deviation of 1.1 % over the entire temperature range, while Equation (b) was found to apply only in the interval 0.900 ≤ T_R ≤ 1.00 with an average deviation of 2.2%. For temperatures of T_k < 0.90, the saturated vapor density was found to depend on temperature as follows where k and m were also found to be Z_c dependent. Values calculated using Equation (c), when compared with 81 available experimental densities for 12 hydrocarbons, produced an average deviation of 3.0%.     

Flow transition for natural convective heat transfer in a porous medium saturated with water near 4°C

In this paper, the problem of buoyancy-induced convection flow in water-saturated porous media near 4°C is examined using a numerical model. Darcy's law is used to model flow behavior and a single equation convective heat transfer model is used for the energy equation. As the Boussinesq approximation is not valid for this case, a parabolic dependence of density on the temperature is used. Natural convection is generated and sustained by a uniform heat source. Flow behavior is governed by three natural parameters appearing in the model. They are: (i) dynamical parameter, (ii) geometric parameter, γ = b/a; and (iii) wall temperature, in relation to the reference temperature at the density extremum. For certain ranges of θ_w (<0) and Gr, interesting density inversion effects are possible. Transient solutions are obtained for various aspect ratios and modified Grashof number values. For a wide range of Grashof number, steady state solutions could not be obtained. Flow mutations into periodic and chaotic solutions are investigated for a range of Grashof number (100 to 40,000) and aspect ratio values (1 to 10).     

One-point method for determination of number-average molecular weight

The following well-known equation permits the ready determination of M _n from a single osmotic pressure measurement at a known concentration, if the second virial coefficient is previously given: On this basis, the one-point method was investigated to determine the number-average molecular weight. It was found that this method was applicable to commercial polymers. However, in this application, the dependence of Γ₂ on molecular weight distribution has to be kept in mind.     

A three-parameter equation for molecular weight distribution of low-density polyethylene

A new three-parameter distribution function is proposed which fits best the experimental molecular weight distribution curves of branched lowdensity polyethylenes. The data were interpreted from GPC measurements, and a special computer program was utilized in order to derive the best values of the empirical constants a, b, and c.     

A one-point intrinsic viscosity method for polyethylene and polypropylene

A statistical analysis of dilute solution viscosity data for a wide range of polyethylene and polypropylene samples in Decalin at 135°C has shown that the Martin equation fits the experimental data better than the Huggins equation at higher values of [η]c. A grand average k of 0.139 is applicable to both polymers. Based upon this, tables have been calculated permitting the ready determination of [η] from a single relative viscosity measurement at a known concentration. The Martin equation has been put into a universal form, permitting [η] to be calculated from a measured η_sp if k and c are known. Graphs relating η_sp to [η] are included for use of the Martin equation over wide ranges of both k and c. It was found that the Solomon and Ciuta equation fits the experimental polyethylene and polypropylene data, and the reasons for this are discussed.     

The glassy state,ideal glass transition,and second‐order phase transition

According to Ehrenfest classification, the glass transition is a second‐order phase transition. Controversy, however, remains due to the discrepancy between experiment and the Ehrenfest relations and thereby their prediction of unity of the Prigogine‐Defay ratio in particular. In this article, we consider the case of ideal (equilibrium) glass and show that the glass transition may be described thermodynamically. At the transition, we obtain the following relations: and with Λ = (α_gβ_l − α_lβ_g)²/β_lβ_gΔα²; and The Prigogine‐Defay ratio is with Γ = TV(α_lβ_g − α_gβ_l)²/β_lβ_gΔβ, instead of unity as predicted by the Ehrenfest relations. Dependent on the relative value of ΔC_V and Γ, the ratio may take a number equal to, larger or smaller than unity. The incorrect assumption of perfect differentiability of entropy at the transition, leading to the second Ehrenfest relation, is rectified to resolve the long‐standing dilemma perplexing the nature of the glass transition. The relationships obtained in this work are in agreement with experimental findings. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 143–150, 1999     

Momentum and heat transfer characteristics of liquid-liquid dispersions in turbulent flow

The momentum and heat transfer characteristics of unstable, liquid-liquid dispersions flowing turbulently in a circular tube were investigated. Two mineral oils, a light oil with viscosity of 15 centipoise, and a heavy oil with viscosity of 200 centipoise were used as the dispersed phase while the continuous phase was tap water. At room temperature only, the relative fluidity of the dispersion follows the relation At Reynolds numbers above 60,000 the heat transfer coefficients of all dispersions studied follow the relation where the Prandtl number is that of the continuous phase and the Reynolds number is based upon the viscosity of the dispersion. All properties are evaluated at the film temperature.     

Elutriation characteristics of solids from liquid fluidized bed systems Part I: Onset of elutriation

Experimental data for the minimum elutriation velocity u_me of solids for 134 different systems have been correlated by The ranges of the different groups investigated were as follows: For all of the experiments, the fluidizing liquid was water and the tube had an inside diameter of 4.92 cm. The standard deviation for the above correlation is 21.6 per cent.