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.     

A constant heat-flux calorimeter for measuring heat transfer data

A new isothermal calorimeter, designed especially for simultaneously measuring the heat of reaction and the heat transfer data in a reaction solution, is described. The system, called a Constant Heat-Flux Calorimeter, is similar to a differential scanning calorimeter in terms of direct calorimetric measurement of the energies of reaction, but differs from the conventional calorimeters described in the literature. With this device, one recorded output in a temperature control circuit is a linear function of change in energies of reaction, and second in a differential temperature control circuit is found to be proportional to a resistance to heat transfer in a solution. The performance of the calorimeter was evaluated on the basis of some results on heat transfer data of aqueous solution of polyethylene glycol and on solution polymerization of styrene at constant temperatures.     

磺酰化修饰聚苯乙烯的合成及芳香烃萃取性能

利用自由基聚合反应合成了低分子量聚苯乙烯, 经过端基氧化和磺酰化反应, 制备出一系列极性砜基修饰的低分子量聚苯乙烯. 通过红外光谱(FTIR)、 核磁共振谱(NMR)、 差示扫描量热分析(DSC)以及热重分析(TGA)等手段对聚合物的结构和性能进行了表征, 并通过混合烃萃取分离实验对其芳香烃选择性进行了测试. 结果表明, 随着磺化比例的增加, 甲苯的选择系数和分布系数均显著提高, 表明极性修饰聚苯乙烯对多种芳香烃/链烷烃混合物均具有明显的芳香烃选择性.     

一种用于研究金属氢化反应的量热系统

将RD-1型量热计的样品管改装成能测量金属氢化反应热效应的量热系统,量热计常数经电能标定,峰高法和面积法所测结果的相对精度为0.5-1％。     

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.     

Differential scanning calorimetry (DSC) of semicrystalline polymers

Differential scanning calorimetry (DSC) is an effective analytical tool to characterize the physical properties of a polymer. DSC enables determination of melting, crystallization, and mesomorphic transition temperatures, and the corresponding enthalpy and entropy changes, and characterization of glass transition and other effects that show either changes in heat capacity or a latent heat. Calorimetry takes a special place among other methods. In addition to its simplicity and universality, the energy characteristics (heat capacity C _P and its integral over temperature T—enthalpy H), measured via calorimetry, have a clear physical meaning even though sometimes interpretation may be difficult. With introduction of differential scanning calorimeters (DSC) in the early 1960s calorimetry became a standard tool in polymer science. The advantage of DSC compared with other calorimetric techniques lies in the broad dynamic range regarding heating and cooling rates, including isothermal and temperature-modulated operation. Today 12 orders of magnitude in scanning rate can be covered by combining different types of DSCs. Rates as low as 1 μK s⁻¹ are possible and at the other extreme heating and cooling at 1 MK s⁻¹ and higher is possible. The broad dynamic range is especially of interest for semicrystalline polymers because they are commonly far from equilibrium and phase transitions are strongly time (rate) dependent. Nevertheless, there are still several unsolved problems regarding calorimetry of polymers. I try to address a few of these, for example determination of baseline heat capacity, which is related to the problem of crystallinity determination by DSC, or the occurrence of multiple melting peaks. Possible solutions by using advanced calorimetric techniques, for example fast scanning and high frequency AC (temperature-modulated) calorimetry are discussed.     

Synthesis and thermodynamic properties of a metal-organic framework: [LaCu6(μ-OH)3(Gly)6im6](ClO4)6

A metal-organic complex, which has the potential property of absorbing gases, [LaCu₆(μ-OH)₃(Gly)₆im₆](ClO₄)₆ was synthesized through the self-assembly of La³⁺, Cu²⁺, glycine (Gly) and imidazole (Im) in aqueous solution and characterized by IR, element analysis and powder XRD. The molar heat capacity, C_p,m, was measured from T = 80 to 390 K with an automated adiabatic calorimeter. The thermodynamic functions [H_T − H_298.15] and [S_T − S_298.15] were derived from the heat capacity data with temperature interval of 5 K. The thermal stability of the complex was investigated by differential scanning calorimetry (DSC).     

State variables in calorimetric investigations: Experimental results and their theoretical impact

Use of state variables (p, V, T) in scanning calorimetric measurements is demonstrated by results obtained for various condensed systems, such as dense liquids of various physicochemical natures, polymers, and liquid crystals. The simultaneous determination of thermal and mechanical responses of the investigated system, perturbed by a variation of an independent thermodynamic variable while the other independent variable is kept automatically constant, allows the determination of thermodynamic derivatives over wide ranges of pressure and temperature, impossible to obtain by other known techniques. It is demonstrated that through appropriate molecular models for respective thermodynamic derivatives or models on which the respective EOS are constructed, the pVT-controlled scanning calorimetry is a useful means of relating microscopic molecular properties with macroscopic observations.     

Solution calorimetry to monitor swelling and dissolution of polymers and polymer blends

The observed rate of drug release from a polymeric drug delivery system is governed by a combination of diffusion, swelling and erosion. It is thus not a simple task to determine the effects of the polymer on the observed drug release rate, because the swelling characteristics of the polymer are inferred from the drug release profile. Here we propose to use solution calorimetry to monitor swelling. Powdered polymer samples (HPMC E4M, K4M, K15M and NaCMC, both alone and in a blend) were dispersed into water or buffer (pH 2.2 and 6.8 McIlvaine citrate buffers) in a calorimeter and the heat associated with the swelling phenomena (hydration, swelling, gelation and dissolution) was recorded. Plots of normalised cumulative heat (i.e. q_t/Q, where q_t is the heat released up to time t and Q the total amount of heat released) versus time were analysed by the power law model, in which a fitting parameter, n, imparts information on the mechanism of swelling.

For all systems the values of n were greater than 1, which indicated that dissolution occurred immediately following hydration of the polymer. However, while not suitable for determining reaction mechanism, the values of n for each polymer were significantly different and, moreover, were observed to vary both as a function of particle size and dissolution medium pH. Thus, the values of n may serve as comparative parameters. Properties of the polymer blends were observed to be different from those of either constituent and correlated with the behaviour seen for polymer tablets during dissolution experiments. The data imply that solution calorimetry could be used to construct quantitative structure–activity relationships (QSARs) and hence to optimise selection of polymer blends for specific applications.     

基于光微热量-荧光光谱联用技术研究光催化热力学和动力学的温度效应

利用光微热量-荧光光谱联用技术,对光催化过程的热谱和光谱信息同步监测,获取了五个温度下,g-C_3N_4@Ag@Ag_3PO_4光催化降解罗丹明B的原位热动力学、光谱动力学信息,探究了温度对相关参数的影响。结果表明,催化降解反应分为三个阶段:(i)污染物和催化剂的光响应过程;(ii)光响应吸热和污染物降解放热的竞争过程;(iii)保持稳定的放热率。吸热和放热的竞争过程符合一级动力学,降解速率随着温度的升高而增大;稳定放热阶段为拟零级反应,在283.15 K、288.15 K、293.15 K、298.15 K、303.15 K下的放热速率分别为0.4668±0.3875μJ·s~(-1)、0.5314±0.3379μJ·s~(-1)、0.5064±0.3234μJ·s~(-1)、0.5328±0.3377μJ·s~(-1)、0.5762±0.3452μJ·s~(-1)。本研究为探究光催化过程的原位热力学、热动力学及光谱信息及机理的推测提供科学依据。     

Thermodynamics of CaCO3 phase transitions

Thermodynamic quantities of the aragonite → calcite transition, were evaluated using results of calorimetric investigations. (1) Dissolution enthalpies of the CaCO₃ polymorphs aragonite and calcite measured near room temperature with different calorimeter, (2) the enthalpy of the spontaneous phase transformation obtained by differential scanning calorimetry, (3) heat capacities and heat capacity differences determined with a heat flux calorimeter as well as previously determined, (4)e.m.f. data on Gibbs-energies of the phase transition were processed simultaneously with an optimization routine developed recently. The optimized data set (25°C) given below corresponds reasonably with CODATA recommendations, however, the precision has markedly improved.     

Heat capacity of molten polymers

Heat capacities of molten polyethylene, polypropylene, poly-1-butene, polystyrene, and poly(methyl methacrylate) were measured over a wide range of temperature by using a differential scanning calorimeter. The upper limit of temperature was established for each polymer at about 10°K below the beginning of thermal decomposition. For poly-1-butene and poly(methyl methacrylate) the solid-state heat capacity was also measured starting from room temperature. Several samples of each polymer were used so that average values of heat capacities could be established (reported in 10°K intervals). The data revealed for all polymers a nearly linear increase of heat capacity with increasing temperature over the whole temperature range investigated.     

Modulated capillary titration calorimeter

A modulated capillary titration calorimeter has been developed. New software and optimization of the calorimetric unit CTD2156 are used as a basis of the modulated capillary titration calorimeter. The scanning mode of the calorimeter has been theoretically substantiated. The scanning of chambers temperature is provided due to the fact that the shield temperature is linearly varied at heating and cooling. The reversing and kinetic part of the total heat flow are measured at heating of a diluted collagen solution. The main advantage of the calorimeter is its ability to operate in a modulation mode, in an isothermal mode, in modes of linear heating and cooling of homogeneous and dispersoid liquid samples at an effective mixing of reagents in calorimetric chambers.     

Evaluation method for heat transfer coefficient of a contact interface across a microscale thin liquid polymer film

The research presented here evaluates the heat transfer coefficient of the contact interface of a thin liquid polymer film between a pair of columnar aluminum bodies with an initial temperature difference of approximately 160 K. We measured the unsteady temperature changes inside the columns. The heat transfer test was performed with three types of liquid polymers: squalane, oleic acid, and silicone oil. The heat transfer coefficient of the polymer films as a fitting parameter was obtained by ensuring the numerically computed time evolution of the columns’ temperature corresponded with the experimentally measured data. The interfacial heat transfer coefficients of the thin polymer films (mean thickness: 60 μm) for all three polymers used were 1.75 kW/m²·K, 2.75 kW/m²·K, and 4.10 kW/m²·K. The present estimating method for determining interfacial heat transfer coefficients was suitable for a material-polymer film-material contact model. The time evolution of the temperature at the contact surfaces was also effectively evaluated using the numerical simulation.     

Kinetics of polymer crystallization from the melt (calorimetric approach)

Crystallization kinetics for 12 polymers including polyolefins, polyesters, polyurethanes, polysiloxanes was measured by the evolution of heat in a modified Calvet-type calorimeter over wide temperature ranges. The results are analyzed in terms of the Avrami equation and a comparison between calorimetric and dilatometric results is carried out. It is concluded that, although in the majority of cases experimental results do not obey the Avrami equation, for some polymers the agreement is rather good. The Avrami parameter obtained, however, depends on the experimental technique. Possible reasons for this disagreement are discussed. Analysis of the calorimetric crystallization rate in the vicinity of the melting point by using the kinetic theory of crystallization shows that the growth is controlled by surface (two-dimentional) nucleation. Energy parameters for the crystallites were determined and it is shown that the surface energy of the crystallites depends on the molecular structure of the polymer. Temperature dependence of the calorimetric crystallization rate of the polymers for which crystallization rates could be determined above and below the maximum rate are analyzed using a kinetic equation with common approximations for the transport term. The influence of melting conditions on the crystallization rate was studied. The results indicate heterogeneous nucleation in the polymer melt. It is concluded that this may be due both to impurities and to high regularity of macromolecules in the polymer melt.     

Heat capacities of the tungsten oxides WO3, W20O58, W18O49 and WO2

The heat capacities of the tungsten oxides WO₃, W₂₀O₅₈, W₁₈O₄₉ and WO₂ have been measured over the temperature range 340–999 K using differential scanning calorimetry. The lower oxides were prepared by controlled reduction of WO₃ in H₂/H₂O gas atmospheres. Previous calorimetric work on WO₃ is confirmed in the temperature range 340–800 K, however, significant increases in heat capacity were observed in the range 800–999 K prior to the orthorhombic—tetragonal phase transition. W₂₀O₅₈ is shown to behave similarly to WO₃. A high temperture phase change is evident, however, this appears to be complete by 970–990 K. The measured values of heat capacity for W₁₈O₄₉ are in close agreement with estimated data for W₁₈O₄₉. There is no evidence of any phase transitions for this oxide in the temperature range studied. The heat capacity data for WO₂ confirm previous drop calorimetry measurements and give no evidence of any phase changes for WO₂ in the temperature range 340–990 K.     

Thermodynamic functions for U0.45Pu0.55N

Enthalpy increments of U_0.45Pu_0.55N were measured in the temperature range of 1025–1775 K by inverse drop calorimetry using a high temperature differential calorimeter. The enthalpy increments were fitted to a polynomial in temperature and the heat capacity, entropy and Gibbs energy functions were computed. The results are presented and discussed in comparison with literature data.     

Caloric properties of dilute nonelectrolyte solutions: A success story

Selected aspects of the thermodynamics of very dilute solutions of gases in liquids, in particular aqueous solutions, are reviewed and connected with recent high-precision experimental techniques [vapor-liquid equilibrium measurements (VLE), calorimetry and densimetry]. Some of the problems encountered in data reduction and data correlation over large temperature ranges, including the critical region, are discussed. The focus is on caloric properties, such as partial molar enthalpy changes on solution, ΔH^∞₂, and partial molar heat capacity changes on solution, ΔC^∞_P,2: direct calorimetric methods are compared with indirect methods based on VLE studies as a function of temperature (van't Hoff approach).     

两种量热模式下物质热分解的动力学补偿效应

热分析量热仪主要包括动态、等温、恒温及绝热四种操作模式。很多学者基于动态及等温模式的测试结果,采用Arrhenius速率常数进行动力学计算,进而发现了所谓的“动力学补偿效应”。为了解绝热模式下是否也存在动力学补偿效应,分别采用绝热加速量热法(ARC)及动态差示扫描量热法(DSC)研究了过氧化二异丙苯(DCP)、40%(质量分数,下同)DCP溶液、葡萄糖、45%葡萄糖溶液的热分解特性,在此基础上基于Arrhenius公式计算了对应的表观活化能E和指前因子A,并对计算结果进行了分析。结果表明:绝热模式下,不同质量的同种样品及其溶液的最佳动力学参数,或者同一组数据采用不同的反应级数获得的lnA和E之间均存在明显的线性关系。此外,尽管由动态DSC数据计算获得的E和lnA普遍小于绝热模式的结果,但两种模式下获得的lnA和E之间仍然存在动力学补偿效应。由此可以推断,具有相同或类似反应机理的反应,虽然实验模式不同,但其E和lnA之间存在明显的动力学补偿效应。     

Calorimetric sensing in bioanalytical chemistry: Principles, applications and trends

Calorimetry has shown great potential in bioanalytical chemistry as most biochemical processes involve a change in enthalpy. Two types of approach have been developed: (1) adiabatic calorimetry, which relies on the absence of heat exchange between the reaction vessel and the external environment, and (2) heat conduction calorimetry, involving measurement of the heat transferred from the vessel to a surrounding heat sink. Both principles, with their respective advantages and drawbacks, have been applied to microcalorimetry for the analysis of (bio)chemical compounds. Immobilization of the biomaterial in the vicinity of, or directly onto a small temperature or heat sensitive transducer has led to the concept of a calorimetric biosensor. In comparison to the traditional calorimeter, the calorimetric biosensor is better suited to continuous monitoring and size reduction. This simplified but sensitive device is expected to solve numerous problems in various fields of analytical chemistry.