Modelling thermal degradation of composite materials

A one–dimensional, transient thermal degradation heat transfer model for the response of composite materials when exposed to fire is presented. The model can handle layers of different materials. Material properties are functions of temperature. The reaction can be specified using Arrhenius‐type parameters or by inputting a density–temperature relationship determined by any experimental technique such as thermogravimetric analysis. The model is validated against the experimental data presented in Boyer's 1984 dissertation. Overall, the model provides excellent agreement with the experimental data. It is shown that very little difference is found between results arrived at by Arrhenius kinetics and results obtained by specifying the easier to measure density–temperature relationship. From this it is concluded that this technique is a viable alternative to Arrhenius‐type models. Copyright © 2006 John Wiley & Sons, Ltd.     

A dynamic linear programming approach to market allocation of renewable resources in the italian energy system: The case of solar thermal and biogas technologies

In Italy solar thermal energy and energy from biogas are two possible means of reducing dependence on energy imports. Using a multiperiod LP model (MARKAL) the authors assessed the likely potential of both technologies under various circumstances. The study covered the period 1980–2005, in five segments of five years. It focused only on the subsystem of the energy end-uses which can be substituted for by solar thermal and biogas technologies. The overall non-renewable sources which can be saved in 20 years by these technologies total 450 PJ (1 PJ = 10^{1 5} J) if the fuel prices rise at 0 per cent average annual, 1450 PJ if the fuel prices rise at 4.2 per cent average annual, 1860 PJ if the fuel prices rise at 7.2 per cent average annual and 3780 PJ if the fuel prices rise at 15 per cent average annual. However the most competitive technologies appear to be solar water heaters used mainly in the private and commercial sectors and biogas systems used mainly in the agricultural sector. The study was carried out by APRE under ENEA (formerly CNEN) contract and was intended to serve as an analytical basis for establishing an overall development and demonstration strategy for end-use renewable technologies in Italy.     

Thermal Evaluation of Scorched Graphite-Epoxy Panels by Infrared Scanning

A simple measurement system is described for evaluating damage to graphite-epoxy panels, such as those used in high-performance aircraft. The system uses a heating laser and infrared imaging system to measure thermal performance. Thermal conductivity or diffusivity is a sensitive indicator of damage in materials, allowing this thermal measurement to show various degrees of damage in graphite-epoxy composites. Our measurements track well with heat-flux damage to graphite epoxy panels. This measurement system, including analysis software, could easily be used in the field, such as on the deck of an aircraft carrier or at remote air strips.     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Copolymerization of bromophenylmaleimide with ethyl or butyl methacrylate

N‐p‐Bromophenylmaleimide (BrPMI) does not polymerize in solution by conventional free radical mechanism. However, it readily polymerized in bulk when mixed with a free radical initiator and heated in a microwave oven for 7–8 min. Copolymerization of ethyl methacrylate or butyl methacrylate with BrPMI was conducted in dioxane. The copolymers were characterized by IR and ¹H NMR spectroscopy and gel permeation chromatography. The monomer reactivity ratios were calculated by a non‐linear least‐square analysis. Thermal analysis indicated a great improvement in thermal stability of the copolymers compared with the methacrylate homopolymers. BrPMI was also polymerized in bulk in the DSC pan, which allowed the calculation of the activation energy of its polymerization. Copyright © 2003 Society of Chemical Industry     

Thermomechanical stress fields in high-temperature fibrous composites. I: Unidirectional laminates

This two-part paper presents a closed-form procedure for evaluation of estimates of local thermomechanical stress fields in two-phase fibrous composites and laminates. The first part is concerned with a unidirectional elastic laminate subjected to uniform mechanical loads and to uniform changes in temperature. Both phases are assumed to be elastic, with temperature-dependent moduli and expansion coefficients; the solution reflects the influence of thermomechanical interactions. Exact solutions are not possible for any real system, because the local geometry is not known in detail. Instead, estimates of the fields are found from a modified Mori-Tanaka approximation. Examples are presented for two SiC/Ti---Al---Nb composites. Local stresses of interest are found after cooling from fabrication to room temperature. The presence of local yielding, and the influence of coupling terms on the local stress magnitudes are examined. Extension of the results to laminated plates is presented in Part II (Dvorak, G.J., Chen, T. & Teply, J., Composites Science and Technology, 43 (1992) 359–368, this issue).     

Synthesis and characterization of poly(siloxane-urethane)s

A series of polyurethane block copolymers based on hydroxy-terminated polydimethylsiloxane and poly(propylene glycol) soft segments of molecular weights 1818 and 2000, respectively, were synthesized. The hard segments consisted of 4,4′-diphenylnethane diisocyanate and 1,4-butanediol as the chain extender. Samples with different molar ratios were prepared. We tried to synthesize polydimethylsiloxane-based polyurethanes (PDMS-PU) containing a hard block as major fraction and a soft block as minor fraction for preparing toughened rigid systems. After a study of the pure polydimethylsiloxane-based polyurethane and poly(propylene glycol)-based polyurethane (PPG-PU), (mixed polyol)-based block copolymers and blends of PDMS-PU and PPG-PU were synthesized, and characterized by means of differential scanning calorimetry, tensile testing and scanning electron microscopy. In (mixed polyol)-based copolymers and lower hard-segment content blends, macro-phase separation occurred, but blends with higher hard-segment contents showed significant reduction in amounts of phase separation.     

Phenol novolac/poly(4- hydroxyphenylmaleimide) blend hardeners for DGEBA-type epoxy resin

Phenol novolac/poly (4-hydroxyphenylmaleimide) (PHPMI) blends were used as an epoxy resin hardener. The curing behavior of the above system and the thermal and mechanical properties of the cured epoxy resin were studied. It was not necessary to use a curing accelerator for this system, because PHPMI caused acceleration of the curing reaction. The curing mechanism of this system was investigated by using model compounds. Test pieces from the neat resins and the glass fiber reinforced resins were evaluated in terms of thermal and mechanical properties, respectively. It was found that heat resistance and mechanical properties were improved by increasing the amount of PHPMI in the hardener.     

Early detection of ageing in solder joints through laser probe thermal analysis of the peltier effect

We have recently developed an optical contactless method for testing the quality of solder joints during accelerated thermal cycling ageing processes.¹ The method was based upon the measurement of the dynamic thermal behaviour of the joint to short bursts of Joule heating. It has proved to be efficient in revealing the formation of cracks at the lead-solder interface. We present a method to evaluate ageing at a much earlier stage in the cycling process. We have observed in earlier work,¹ that before cracks appear, structural changes occur in the solder at the lead-solder interface. The thermal response of the solder joint is recorded over time to a Peltier heat perturbation produced by flowing a current pulse through the interface where structural changes occur. The key point in this method is to discriminate the Peltier effect from the Joule thermal response because both effects generate heat. The variation of the early Peltier response in the thermal cycling ageing tests is seen as a quantitative signature of the structural changes in the lead-solder interface.     

The effect of additives on the thermal stability of poly(vinyl chloride)

The effect of a range of organic additives on the thermal stability of poly(vinyl chloride), both with and without a chloroparaffin extender, was studied using a number of experimental techniques. Of the additives used the best overall balance was provided by pentaerythritol, which increased stability when the extender was present and had no effect when it was absent. The congo red test emerged as the most suitable technique, being consistent and inexpensive and able to screen several additives simultaneously. Isothermal differential thermal analysis correlated with the congo red test but required more expensive equipment, was time-consuming and demanded good mixing of the poly(vinyl chloride) compound to give reproducible results. Thermogravimetry was not sufficiently sensitive and the heat stability test was the least useful of all.