Effect of kinetic and thermal parameters on the process of cure of epoxy resin in a cylindrical mould

Various parameters were found to be important in the cure of epoxy resin, those concerned with the kinetics of the heat evolved from the reaction (such as the order, rate constant and activation energy) and those related to the thermal properties of the resin, such as thermal diffusivity and heat capacity. An important parameter in this case was also studied, viz. the coefficient of the heat transfer through the heated fluid-mould interface, controlled by convection. After modelling successfully the process with a numerical method with finite differences, each of the parameters was tested in turn, by considering the temperature and state of cure-history at the middle of the resin cured in a cylindrical mould. Some parameters were found to be significant in the cure, such as the cure enthalpy and heat capacity, the activation energy and the coefficient of heat transferred by convection. This new knowledge allowed further insight into the process of cure for thermosets.     

A Laser Flash Apparatus for Thermal Diffusivity and Specific Heat Capacity Measurements

We have developed a laser flash apparatus for simultaneous measurements of thermal diffusivity and specific heat capacity of solid materials by introducing recent technical progress: uniform heating by a homogenized laser beam using an optical fiber with a mode mixer, measuring transient temperature of a specimen with a calibrated radiation thermometer, analyzing a transient temperature curve with a curve fitting method, to achieve differential laser flash calorimetry. Thermal diffusivity, specific heat capacity and thermal conductivity of glassy carbon and molybdenum were measured in the temperature range from 300 to 1100 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermophysical properties of polypropylene/aluminum composites

This article is dedicated to the study of the thermal parameters of composite materials. A nonlinear least‐squares criterion is used on experimental transfer functions to identify the thermal conductivity and the diffusivity of aluminum‐polymer composite materials. The density measurements were achieved to deduce the specific heat and thereafter they were compared to values given by differential scanning calorimetry measurement. The thermal parameters of the composite material polypropylene/aluminum were investigated for the two different types of aluminum filler sizes. The experimental data were compared with several theoretical thermal conductivity prediction models. It was found that both the Agari and Bruggeman models provide a good estimation for thermal conductivity. The experimental values of both thermal conductivity and diffusivity have shown a better heat transport for the composite filled with large particles. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 722–732, 2004     

A Novel Thermo-Optical Measuring System for the in situ Study of Sintering Processes

A novel thermo-optical measuring system (TOM) is described, which is able to monitor simultaneously and in situ thermal and optical properties of materials during the process of sintering. These are thermal diffusivity, heat capacity, thermal conductivity, transfer of heat radiation and scattering of light. Additionally, the geometric shrinkage is recorded by a non-contact optical dilatometer. The system has been designed for an efficient optimization of time-temperature-atmosphere cycles in sintering processes. Therefore, in the construction of the TOM system transferability of process parameters to other sintering furnaces is an important requirement. Due to this, compromises have been necessary in the layout of the measuring methods. Nevertheless, a high resolution was achieved for the distinction of different sintering states. Besides dilatometry, thermal diffusivity measurement by a laser-flash technique is a promising tool for the in situ monitoring of changes in microstructure during sintering. This revised version was published online in July 2006 with corrections to the Cover Date.     

Reversible Melting of Semi-crystalline Polymers Frequency dependence of the reversible melting enthalpy

Modulated DSC (MDSC) has been used to study the heat flow during melting and crystallisation of some semi-crystalline polymers i.e. different grades of polyethylene (LDPE, LLDPE and HDPE), and polypropylene (PP). The heat capacities measured by MDSC are compared with the hypothetical complex heat capacities of Schawe and it is shown that numerically they are equivalent; nevertheless, the concept of the complex heat capacity is problematic on a thermodynamic basis. A reversing heat flow (proportional to the experimental heat capacity of the material) was present at all conditions used for the study. In the melting zone of the polymers it depends on the modulation frequency and on the amplitude. Higher amplitude and frequency of modulation reduce the ratio of the reversing heat flow to the total heat flow, the latter is nearly independent on these parameters. The reversible component of the melting enthalpy of polymers depends on the modulation frequency, the modulation amplitude and the type of the polymer. It increases by increasing the branching in polyethylene. The existence of the reversible heat flow during the crystallisation and melting is contrary to the current hypotheses and theories of polymer crystallisation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermophysical Properties of Poly(propylene)-based Composite Polymer

The thermal diffusivity and the thermal conductivity of polypropylene-based composite polymer were simultaneously measured with a temperature wave analysis method. We can measure the thermal properties under cooling process which are important to consider the polymer processing. The effect of filler in the composite was analyzed by thermal diffusivity and thermal conductivity as a function of temperature. The thermal conductivity of particle dispersed composite was confirmed as a reasonable value and was explained with a series model. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal properties in cured natural rubber/styrene butadiene rubber blends

Blends of natural rubber (NR) and styrene butadiene rubber (SBR) were prepared with sulfur and n-t-butyl-2-benzothiazole sulfonamide (TBBS) as accelerator, varying the amount of each polymer in the blend. Samples were analysed by rheometer curing at 433 K until their maximum torque was reached. The miscibility among the constituent polymers of the cured compounds was studied in a broad range of temperatures by means of differential scanning calorimetry, analyzing the glass transition temperatures of the samples. The specific heat capacity of the compounds was also determined. Thermal diffusivity of the samples was measured in the temperature range from 130 to 400 K with a new device that performs measurements in vacuum. The thermal results are explained on the basis of the structure formed during the vulcanization of the samples considering the variation of the crosslink density of each phase. Finally, a serial thermal conduction model that takes into account the contribution of each phase to the thermal diffusivity was used to fit the experimental results.     

Chemical shrinkage and thermomechanical characterization of an epoxy resin during cure by a novel in situ measurement method

In this study, a novel technique is presented to enable the characterization of the dimensional changes and evolution of mechanical properties of a resin during cure. This is achieved using an innovative in situ device called thermal flux cell combined with a Dynamical Mechanical thermal Analyser (DMA). With this system, it is now possible to eliminate the sources of error induced while combining two or more instruments. This device consists into a mold containing the resin where the upper and lower surfaces acting as heat flux sensors. Changes in temperature and thermal flux are directly monitored as well as the dynamical displacement and the stiffness during the curing process. In this work, an epoxy DGEBA resin was used to demonstrate the innovative approach. The tested resin was characterized using different vibration frequencies and amplitudes of the DMA. The results were then processed in order to provide accurate data on gel time and cure kinetics behavior. The volume and mechanical changes were also derived from experimental data and linked to the degree of cure. Chemo and thermo-mechanical models were created to predict the changes in chemical shrinkage and stiffness during cure.     

Determination of the rheological behavior of epoxy–amine thermosets by dynamic mechanical analysis: Isothermal methods versus nonisothermal methods

The reticulation process of an epoxy resin using an amine as a cure agent was studied at different temperatures and concentrations of the cure agent with dynamic mechanical thermal analysis. The study was performed under both isothermal and nonisothermal conditions, and a temperature–time–transformation diagram was obtained. The measurements from the two modes gave similar results, although the nonisothermal mode required fewer experiments. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1965–1977, 2003     

Obtaining Modulated Temperature DSC Curves Through a Non-conventional DSC Method

The DSC curve obtained in conventional equipment usually only shows the resultant thermal effect due to simultaneous phenomena, which may occur during isothermal or dynamic analyses. This does not allow one to identify the processes properly and may cause an erroneous interpretation of the resulting curves. Modulated DSC equipment enhances the operating conditions and the analysis capacity of conventional DSC by superimposing a sinusoidal temperature modulation on the linear temperature control. Thus reversing and non-reversing heat flow curves are obtained, which are, respectively, the heat capacity and kinetic components of the DSC curve. Therefore, events that are related to these components can be separately analyzed. A method to obtain curves similar to the MDSC reversing and non-reversing components was developed using conventional DSC equipment in a non-conventional way. It was applied to analyze samples of poly(ethylene terephthalate) (PET) taken from bottles of mineral water. The second PET crystallization step that occurs during its melting was quantified and an apparent initial crystallinity was obtained from the resulting data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of testing conditions on the laser flash thermal diffusivity measurements of ceramics

Several experimental techniques either under steady state or transient heat transfer conditions, have been developed to evaluate thermal conductivity and thermal diffusivity of materials. However, testing difficulties resulting from specimen size, extended testing time and heat losses, have somewhat impaired the applicability of many of them. In this respect, the use of the laser flash technique for thermal diffusivity measurements, is a very convenient alternative, considering its basic modeling equation is independent of the temperature gradient as well as the heat flow, and in addition the heat losses can be analytically treated. Another important advantage of the technique is its rapid experimental execution. In this work, it is presented as an investigation concerning how the testing conditions such as specimen coating, laser power and pulse duration, base line adoption, heat losses correction methods, and specimen thickness, may affect the thermal diffusivity measurements of some ceramic materials using the laser flash technique.     

Experimental investigation of thermal properties and fire behavior of carbon/epoxy laminate and its foam core sandwich composite

According to structural characteristics, composites are classified as laminated structure and sandwich structure. Carbon/epoxy laminate and foam core sandwich composite are the most commonly used laminate and sandwich structure material in the aircraft industry. The flammability of epoxy resins and foam core material is an inherent hazard. Many previous studies focused primarily on their mechanical properties, while the studies on the thermal and fire properties of carbon/epoxy laminate and its foam core sandwich composite have rarely conducted. Therefore, to characterize their thermal and fire properties, a comprehensive experimental investigation and theoretical analysis were carried out in this work using thermogravimetric analysis, cone calorimeter, vertical/horizontal burning tests, limiting oxygen index and scanning electron microscope tests. Several typical characteristic parameters were obtained and analyzed, such as pyrolysis temperature, heat release rate, mass loss, flaming spread rate and limiting oxygen index. These experimental data coupled with theoretical analysis can provide support for fire risk assessment and fire protection design in aircrafts. The carbon/epoxy laminate and foam core sandwich composite are both characterized as the thermally thick materials. The ignition models and mass loss rate models were obtained. Foam core material negatively affects most of the thermal and fire properties of sandwich composite, but the foam core sandwich composite has self-extinguishing behavior during horizontal burning tests, whose LOI is higher than that of carbon/epoxy laminate. Thus, an important conclusion was reached that the ignition position and flame spread direction have critical effect on the fire behavior of foam core material.

     

Applications of some thermo-analytical techniques to glasses and polymers

Thermal characterization of materials provides conclusions regarding the identification of materials as well as their purity and composition, polymorphism, and structural changes. Analytical experimental techniques for thermal characterization comprise of a group of techniques, in which physical properties of materials are ascertained through controlled temperature program. Among these techniques, traditional differential scanning calorimetry (DSC) is a well-accepted technique for analyzing thermal transitions in condensed systems. Modulated DSC (MDSC) is used to study the same material properties as conventional DSC including: transition temperatures, melting and crystallization, and heat capacity. Further, MDSC also provides unique feature of increased resolution and increased sensitivity in the same measurement. “Hot disk thermal constant analyzer”, based on Transient Plane Source (TPS) technique, offers simultaneous measurement of thermal transport properties of specimen, which are directly related to heat conduction such as thermal conductivity (λ) and thermal diffusivity (χ). This method enables the thermal analysis on large number of materials from building materials to materials with high thermal conductivity like iron. The temperature range covered so far extends from the liquid nitrogen point to 1000 K and should be possible to extend further. This review also presents some interesting results of phase transition temperature of miscible (CPI/TPI) and immiscible (PS/PMMA) polymeric systems carried out through dynamic mechanical analyzer along with the thermal transport properties obtained for cis-polyisoprene (CPI), trans-polyisoprene (TPI), and their blends determined by TPS technique.     

Intercomparison of thermal conductivity and thermal diffusivity methods for plastics

An intercomparison of measurements of the thermal conductivity and thermal diffusivity of two poly(methyl methacrylates) is reported. A wide variety of methods were used: temperature wave analysis, laser flash, transient plane source (Hot Disk^®), transient line-source probe, and heat flux meter methods. Very good agreement of thermal conductivity results and, separately, of thermal diffusivity results was obtained. Similarly, good agreement between thermal conductivity and thermal diffusivity results, when converted using specific heat capacity and density values, was also obtained. Typically, the values were within a range of approximately ±10%. Considering the significant differences between the methods and the requirements on specimen dimensions, the level of agreement between results was considered to be good.     

Experimental investigation into the heat capacity measurement using an modulated DSC

Experiments using a commercial modulated DSC (MDSC) for the measurement of specific heat capacity of a sample have been carried out. It is found that because the amplitude of heat flow of MDSC is a complicated non-linear function of various experimental conditions such as the modulation frequency and the heat capacities of a sample and pan, the methodology of heat capacity determination using an MDSC in a single run has not been justified. The experimental results, on the other hand, agree with the theoretical equation of one of the authors. It is therefore concluded that the capabilities of MDSC should be further examined.     

Thermo-mechanical characterisation of in-plane properties for CSM E-glass epoxy polymer composite materials – Part 1: Thermal and chemical strain

The in-plane thermo-mechanical properties and residual stresses of a CSM E-glass/Epoxy material are characterised through the use of DSC and TMA. The measured data is used to generate material models which describe the mechanical behaviour as a function of conversion and temperature. The in-plane thermal expansion coefficient (α) of the composite material decreases above the glass transition temperature (T_g), which is compensated by a higher out of plane deformation above T_g. Comparison of α and chemical shrinkage measurements suggests that chemical bonds between the polymer matrix and the glass fibres are formed prior to shrinkage of the epoxy matrix, i.e., at an early processing stage. This suggests that production of composites with low residual stresses requires focus on reactivity between the matrix and the sizing rather than the matrix cure properties. As a consequence, residual stresses in the composite material are mainly a result of restricted cure shrinkage rather than mismatch between thermal expansion coefficients.     

Effect of thermal decomposition processes on the thermal properties of carbon fiber reinforced cement composites in high-temperature range

Thermal conductivity, specific heat capacity, thermal diffusivity and linear thermal expansion coefficient of two types of carbon fiber reinforced cement composites are measured in the temperature range up to 800°C. Thermal conductivity and thermal diffusivity are also determined for the specimens exposed to thermal load up to 800°C before the measurement. Differential thermal analysis (DTA), mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD) are utilized for the assessment of thermal decomposition processes taking place in the high temperature range under consideration. The high temperature thermal properties of the studied materials are found to be positively affected by the application of the high alumina cement and in the case of the Portland cement based composite also by using the autoclaving procedure in the production process. Also, the randomly distributed carbon fibers that can reduce the damage of the pore structure by the thermal decomposition processes are identified as a positive factor in this respect. A comparison of thermal conductivity vs. temperature curves obtained for the specimens pre-heated to different temperatures is found to be a useful tool in the identification of major dynamic effects in the specimens due to the thermal decomposition reactions. The results are in a good agreement with the DTA, MIP, SEM and XRD analyses. The character of the thermal conductivity measurements that in fact includes the effects of convection and radiation into the thermal conductivity coefficient can be beneficial for a simple assessment of the influence of the fire on a dividing structure.     

Thermal conductivity measurements using the flash method

Thermal diffusivity is the speed with which heat propagates through a material. It has a multitude of direct applications, such as determining heat transfer through brake pads at the moment of contact, etc., but more often it is used to derive thermal conductivity from the fundamental relationship tying it with specific heat capacity and density. Using a new multi-sample configuration system, and testing a reference sample adjacent to the unknown, specific heat capacity can be obtained parallel with thermal diffusivity. Thus, a single test yields thermal diffusivity and thermal conductivity with prior knowledge of density. The method is fast and produces results with high accuracy and very good repeatability. The sample size, 12 to 30 mm diameter and 2 to 5 mm thickness, is easy to handle and is well suited for a broad range of materials, even for composites, often a problem for other methods. Typical data on two polymers, Pyrex glass and Pyroceram 9606 are presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Temperature dependence of the thermophysical properties of polycrystallene chalcogenide glasses

The specific heat (C _p), thermal conductivity (λ), thermal diffusivity (a), and electrical conductivity (σ) were measured for polycrystalline HgS and Sb₂S₃ in the temperature range 300–600 K. The measurements were performed with an experimental apparatus based on a socalled flash method. The results showed that the mechanism of heat transfer is mainly due to phonons, whereas the contribution of electrons and bipolars is very small indeed. The energy gap of the samples was also calculated.     

Kinetic Method by Using Calorimetry to Mechanism of Epoxy-amine Cure Reaction

Using calorimetric method to reaction kinetics in solventless system, the quantitative aspects of the epoxy ring opening in the reaction between phenyl glycidyl ether and aniline have been discussed. Using the Mangelsdorf method we have found that this reaction system gives fairly clean kinetics through whole process. The kinetic picture of this reaction system is akin to diepoxy-diamine cure mechanism. It was detected kinetically, apart from exothermic effect of the reaction of the epoxy ring opening, the existence another exothermic process at the last stages of the reaction. The latter also contributes to the total heat. The contribution of this thermal effect to the total heat is found to be dependent on the reactant ratio. The data for the reaction between phenyl glycidyl ether and aniline could not be fitted well if uncatalyzed mechanism was ignored. Thus, the reaction of epoxy ring opening by aniline occurs by two concurrent pathways: one is uncatalyzed and the other, the main, is autocatalyzed. This revised version was published online in August 2006 with corrections to the Cover Date.