Advanced Calorimetric Techniques in Polymer Engineering

Summary: In polymer synthesis, reaction calorimetry (RC) is an appropriate technique for on-line process monitoring, since polymerization reactions are highly exothermic. Measurements are noninvasive, rapid, and straightforward. Nowadays RC is the technique recognized as the most powerful way to study such process in near-to-the- industrial conditions. Our approach was focused on temperature oscillation calorimetry (TOC). Two different reaction calorimeters were used, i.e. a isoperibolic calorimeter and a Calvet type high sensitivity differential calorimeter, respectively. A special attention was paid to the interpretation of the measured signals in order to obtain reliable calorimetric data. The evolution of heat transfer coefficient UA was followed by performing appropriate Joule effect calibrations, before and after the reaction. A convolution differential method of the measured heat flow by the generated one was used for determining the time constants and deconvoluting the measured heat flow.     

Reaction calorimetry for the development of chemical reactions

A new reaction calorimeter is described that has been developed to study chemical reaction processes on a laboratory scale. It provides precise measurements of kinetic and thermal data, of heat transfer data, as well as of the physical properties of the reaction product. The reaction calorimeter is applied successfully in the development of chemical processes, in the evaluation of hazards and risks of chemical synthesis.Working principles and evaluation are described using the example of the nitration of benzaldehyde.     

On-line Calibration and Determination of the Heat of Reaction for Laboratory Scale Heat Transfer Calorimeters

A simple method for the on-line calibration, in which both the heat transfer coefficient and the heat capacity of the reactor contents are determined, is described for laboratory scale heat transfer calorimeters. The calorimeter is operated in the isoperibolic mode for the calibration and a constant power is supplied to a resistor placed inside the reactor. The reactor heat balance differential equation is used to produce a set of linear simultaneous equations with each data acquisition cycle giving one equation. The heat transfer coefficient and the heat capacity are obtained from this set of equations by linear least squares. The application of the calibration procedure is illustrated by experiments in which the heat of reaction is determined on-line fora simulated reaction with first order kinetics and for the hydrolysis of acetic anhydride. This revised version was published online in July 2006 with corrections to the Cover Date.     

A new reaction calorimeter and calorimetric tools for safety testing at laboratory scale

Calorimetry combined with thermal analysis is an essential tool for the evaluation of thermal risks linked with chemical reactions at industrial scale. The energies of synthesis reactions or decomposition reactions as well as the heat capacities of reaction masses can be measured using such techniques. The capacity of the SETARAM differential reaction calorimeter (DRC) to determine essential safety data has been demonstrated with the measurement of heat capacities of cyclohexane and propanoic acid. Results of an industrial reaction are also presented.     

Using the Transfer Function of an Isoperibolic Reaction Calorimeter for Thermo-kinetic Analysis

It is an aim of the present work to determine the chemical heat flow rate of a reaction without explicitly solving the heat balance equations. Therefore, it is necessary to calculate the heat flow rate directly from the temperature course of an experimentally determined reaction. For this transformation the transfer function of the calorimeter is needed 1 . An isoperibol reaction calorimeter was used for the experiments. With different calibrations and gained transfer functions, it is shown that the chemical heat flow rate can be determined from the temperature course of a reaction. The evaluation is fast and easy to use, which improves automation and prevents possible input errors.     

A direct isoperibol aneroid calorimeter

An aneroid isoperibol calorimetric apparatus is described which is particularly suitable for measurement of the reaction heat among solids. Such an apparatus contains four calorimeters and allows to carry out differential measurements. Each calorimeter includes two small electric furnaces employed for heating the solid mixture until the reaction begins and for the successive electric calibrations, respectively. The temperature trend of each calorimeter is followed by 80 thermocouples in series. The instrument characteristics are briefly discussed. Examples of its employment in the alloy thermochemistry are given.     

Heat exchange type of titration calorimetry with on-line analogue compensation for the effect of titrant addition

A theoretically exact method of compensation for the effect of titrant addition is developed for the previously reported heat exchange type of calorimetry. An adequate modification is made on the calorimeter vessel, covering a part of the heat exchanger surface for thermal insulation, to make the relevant differential equations simpler. The differential equations are realized in the form of an operational amplifier circuit, where the resistance of a variable resistor increases in parallel with the movement of the piston of a burette. The effect of titrant addition at a rate up to 7 cm³ min^?1 can be completely compensated. For illustration the heat of reaction of THAM with a standard HCl solution is estimated in a titrimetric procedure and a satisfactory result is obtained.     

The use of advanced calorimetric techniques in polymer synthesis and characterization

Progress in the understanding of polymer synthesis, including the crucial step of initiation and undesired side reactions, and in characterization of polymers, especially their thermal behaviour, are directly related to advances in calorimetric technologies.

In polymer synthesis, since polymerization reactions are highly exothermic, reaction calorimetry (RC) is an appropriate technique for on-line process monitoring. Measurements are non-invasive, rapid, and straightforward. Viscosity increase and fouling at the reactor wall are typical features of many polymerizations. The global heat transfer coefficient, UA, also changes drastically when viscosity increases and affects the accuracy of calorimetric measurements. Our approach was focused on oscillating temperature calorimetry (TOC). Reactions were performed with two different reaction calorimeters, i.e. an isoperibolic calorimeter and a Calvet-type high sensitivity differential calorimeter, respectively. Special attention was paid to the interpretation of the measured signals to obtain reliable calorimetric data. The evolution of heat transfer coefficient was followed by performing two Joule effect calibration experiments, before and after the reaction, and the two values interpolated to obtain the desired profile of UA. A differentiation method based on the convolution of the measured heat flow by the generated one was used for determining the time constants and deconvoluting the measured heat flow.

With respect to polymer characterization, pressure-controlled scanning calorimetry, also called scanning transitiometry, is now a well established technique. The transitiometer was coupled to an ultracryostat to work at low temperature. The assembly was used to follow the pressure effect on phase change phenomena such as fusion/crystallization and glass transition temperature T_g of low molecular weight substances or high molecular weight polymers.     

简易示差扫描量热计的研制

<正> 示差扫描量热计(DSC)是在示差热分析仪(DTA)基础上发展起来的新型热分析仪,它在高分子方面已取得广泛应用.我们自1975年起研制了适合有机、高分子应用的DSC,取得一些经验,简介如后. 图1是DSC的结构示意图.DSC独有的单元是量热部.它由一对小加热器组成的试料部(量热部Ⅰ)和由热量补偿回路等组成的热量补偿部(量热部Ⅱ)构成.我们研制以此单元为主,其它部分均以商品仪器配用.     

New developments and applications in titration calorimetry and reaction calorimetry

Isothermal titration calorimetry (ITC) and reaction calorimetry (RC) have been used to construct the solid-liquid equilibrium line in ternary systems containing the solute to precipitate and an aqueous mixed solvent, and to study polymerization reactions under real process conditions, respectively. Phase diagrams have been established over the whole concentration range for some benzene substituted derivatives, including o-anisaldehyde, 1,3,5-trimethoxybenzene and vanillin, in {water + alcohol}mixtures at different temperatures. Acrylamide polymerization in aqueous solution using potassium permanganate/acid oxalic redox system as initiator was investigated on a homemade calorimeter, which works according to the isoperibolic mode. A Calvet type differential RC was used to illustrate the applicability of temperature oscillation calorimetry (TOC) for the evaluation of the heat transfer coefficient during the course of reaction.     

Isothermal calorimeter for studies of polymer solution processes

A simple differential, isothermal calorimeter has been built to study the thermodynamics of interactions associated with a variety of polymer solution processes. The calorimeter is readily operated at temperatures ranging from ambient to about 200°C., temperature adjustments are rapid, and the apparatus is rugged enough to permit application to commercial process studies. Though less sensitive than microcalorimeters, it represents an attractive combination of satisfactory accuracy, speed, and flexibility of operation. The operation of the calorimeter is demonstrated by measurements of the heat of solution of sodium chloride in water and the heats of solution of various polyolefins in Tetralin and α-chloronaphthalene. The latter tend to confirm the presence of polymer aggregates in chloronaphthalene solutions below the thermodynamic melting temperature of the polymer.     

Estimation of kinetic parameters from thermochemical data

A method is described by which kinetic parameters may be calculated from the measured temperature changes caused by the heat produced during a chemical reaction. An isoperibol titration calorimeter with an ampoule-breaking facility is used to obtain the temperature data. The temperature changes resulting from the reaction between tri-isopropyl phosphite and sulphur (S(8)) are used as an example to demonstrate the effectiveness of the method. The temperature changes are used to calculate an enthalpy of reaction. From the enthalpy of reaction and intermediate heats, instantaneous concentrations of the reactants may be calculated.     

A fully automated adiabatic calorimeter for heat capacity measurement between 80 and 400 K

A fully automated adiabatic calorimeter controlled on line by a computer used for heat capacity measurements in the temperature range from 80 to 400 K was constructed. The hardware of the calorimetric system consisted of a Data Acquisition/Switch Unit, 34970A Agilent, a 7 1/2 Digit Nano Volt /Micro Ohm Meter, 34420A Agilent, and a P4 computer. The software was developed according to modern controlling theory. The adiabatic calorimeter consisted mainly of a sample cell equipped with a miniature platinum resistance thermometer and an electric heater, two (inner and outer) adiabatic shields, two sets of six junction differential thermocouple piles and a high vacuum can. A Lake Shore 340 Temperature Controller and the two sets of differential thermocouples were used to control the adiabatic conditions between the cell and its surroundings. The reliability of the calorimeter was verified by measuring the heat capacities of synthetic sapphire (α-Al₂O₃), Standard Reference Material 720. The deviation of the data obtained by this calorimeter from those published by NIST was within ±0.1% in the temperature range from 80 to 400 K.     

The thermochemical characteristics of cellulose and its mixtures with water

The heat capacity of cotton microcrystalline cellulose was measured on an adiabatic vacuum calorimeter over the temperature range 80–330 K, and the differential thermal analysis data on the substance were obtained from 80 to 550 K. The enthalpy of cellulose interaction with water was measured at 303 K using a differential microcalorimeter. The standard enthalpies of combustion and formation of microcrystalline cellulose and wood celluloses with different crystallinity indices were determined. The concentration of saturated water solution in microcrystalline cellulose at 273 K was determined calorimetrically from the enthalpy of fusion of the excess water phase.     

Thermochemical study of aqueous solutions of lithium diclofenac at 293.15–318.15 K

The enthalpies of solution and dilution of aqueous solutions of lithium diclofenac (LiDC) are measured in the concentration range of 0.002–0.047m at 293.15, 298.15, 308.15, and 318.5 K using an isoperibolic calorimeter. The heat capacity of solid LiDC in the temperature range of 273.15–373.15 K is determined using a DSC 204 F1 Phoenix differential scanning calorimeter (NETZSCH, Germany). The virial coefficients of the enthalpy characteristics of a water-LiDC solution are derived in terms of the Pitzer model to calculate a wide range of thermodynamic properties of both the solution and its components. Changes in these characteristics as a function of concentration and temperature are discussed.     

Excess molar heat capacities of (<Emphasis Type="Italic">L</Emphasis>-glutamine aqueous solution+<Emphasis Type="Italic">D</Emphasis>-glutamine aqueous solution) at temperatures between 293.15 and 303.15 K

Summary Excess molar heat capacities of (L-glutamine aqueous solution+D-glutamine aqueous solution) were determined by using a differential scanning calorimeter at temperatures between 293.15 and 303.15 K. Excess molar heat capacities are all negative. Excess molar heat capacities decrease with increasing temperature.     

Calorimetric investigation of polymerization reactions. III. Curing reaction of epoxides with amines

The curing reactions of epoxy resin with aliphatic diamines and the reaction of phenyl glycidyl ether with butylamine as a model for the curing reactions were investigated with a differential scanning calorimeter (DSC) operated isothermally. The heat of reaction of phenyl glycidyl ether with butylamine is equal to 24.5 ± 0.6 kcal/mole. The rate of reaction was followed over the whole range of conversion for both model and curing reactions. The reactions are accelerated by the hydrogen-bond donor produced in the system. The rate constants based on the third-order kinetics were determined and discussed for the model reaction and for the chemically controlled region of curing reactions. The activation energies for these rate constants are 13-14 kcal/mole. At a later stage of conversion, the curing reactions become controlled by diffusion of functional groups. The final extent of conversion is short of completion for most isothermally cured and even for postcured samples because of crosslinking. It was quantitatively indicated that the final conversion of isothermal cure corresponds to the transition of the system from a viscous liquid to a glass on the basis of the theory of glass transition temperature of crosslinked polymer systems.     

Estimation of temperature transients for biomass pretreatment in tubular batch reactors and impact on xylan hydrolysis kinetics

A combined heat transfer/kinetic model was developed to quantify temperature variations in small tubular batch reactors and estimate the effect of deviations from isothermal operation on the kinetics of biomass pretreatment. Assuming that heat transfer was dominated by conduction in the radial direction, a classic parabolic time-dependent partial differential equation was applied to describe the temperature in the system and dedimensionalized to provide a single solution for application to all situations. A dimensionless expression for the reaction kinetics for xylan hydrolysis was then developed, and a single parameter expressed as the dimensionless ratio of the first-order rate constant times the tube radius squared divided by the thermal diffusivity was found to control the reaction rate. Three different characterizations of the deviation between the concentration profile predicted for isothermal xylan hydrolysis and that based on the transient temperature were directly related to this dimensionless rate constant parameter for both catalyzed and uncatalyzed hydrolysis kinetics. These results were then used to project the relationship between deviations in yield from isothermal results and the tube radius and reaction time.     

Uncertainty analysis of theoretical methods for adiabatic temperature rise determination in calorimetry

The main methods for the determination of the temperature rise in calorimetric experiments corrected of heat losses to surroundings (called adiabatic temperature rise) are described thereafter. This corrected temperature rise is obtained analytically from experimental temperature–time curves. The general scheme reported by Henri Régnault and Leopold Pfaundler for the first time in the 19th century is considered as the basis for all methods elaborated afterwards. A bibliographical study raised five methods including Régnault–Pfaundler’s. These methods have been applied on five experimental temperature–time curves obtained with an isoperibolic reference gas calorimeter at the French national metrology and testing institute (LNE) on combustion of pure methane. This paper deeply details a new analytical method elaborated at LNE exposing best heat transfer phenomena representation occurring in the water bath calorimeter. A comparative study of the five methods of the temperature rise determination and of their associated uncertainties is here presented.     

Equilibrium and non-equilibrium transitions studied by adiabatic calorimetry

The principle and recent technical development of adiabatic low temperature calorimetry are described with experimental results taken mostly from the authors' laboratory. Topics on the equilibrium and quasi-equilibrium heat capacities include the separation of the Schottky heat capacity from the experimental data on bromo-hydroxyphenalenone and non-Debye excess heat capacity of a glassy hydrocarbon. Relaxation of glassy crystals of rubidium cyanide and C₆₀ and stabilization of a supercooled phase of methylammonium hexachlorotellurate are discussed. A unique adiabatic calorimeter of top-loading construction recently completed in the authors' laboratory is described along with an experimental result on a glassy liquid prepared at a cooling rate 100 times greater than was possible with a calorimeter of the conventional design.