Semicrystalline polymer thermal properties

In contrast to the mature instrumental techniques discussed above, a hitherto nonexistent class of techniques will require substantial development effort. The new instruments will be capable of measuring the thermal (e.g., glass transition temperatures for amorphous or semicrystalline polymers and melting temperatures for materials in the crystalline phase), chemical, and mechanical (e.g., viscoelastic) properties of nanoscale films in confined geometries, and their creation will require rethinking of conventional methods that are used for bulk measurements. 

Poly(ether ether ketone) (PEEK) is an aromatic, high performance, semicrystalline polymer with extremely good thermal stability, chemical resistance, and electrical and mechanical properties. This polymer shows little solubility in organic solvents due to the crystallinity. One of the first ways to characterize PEEK was by sulfonating the polymer. By adding sulfonic acid groups to the backbone, the crystallinity decreased and solubility increased.Commercially available Victrex appears to be one of the more interesting poly(arylene ether) s used for postmodification. 

Composite-based PTC thermistors are potentially more economical. These devices are based on a combination of a conductor in a semicrystalline polymer—for example, carbon black in polyethylene. Other fillers include copper, iron, and silver. Important filler parameters in addition to conductivity include particle size, distribution, morphology, surface energy, oxidation state, and thermal expansion coefficient. Important polymer matrix characteristics in addition to conductivity include the glass transition temperature, Tg, and thermal expansion coefficient. Interfacial effects are extremely important in these materials and can influence the ultimate electrical properties of the composite. 

The thermal properties of the polymers reported in Table A.2 and Table A.3 were obtained by using a Perkin-Elmer Differential Scanning Calorimeter Model DSC-7 using a heating rate of 20°C/min. The specific heat was obtained using a heating rate of 10°C/min. For semicrystalline material, the heat of fusion was obtained from the measured specific heat curves. The crystallization temperature was obtained at 20°C/min cooling rate. 

The effects of morphology (i.e., crystallization rate) (6,7, 8) on the mechanical properties of semicrystalline polymers has been studied without observation of a transition from ductile to brittle failure behavior in unoriented samples of similar crystallinity. Often variations in ductlity are observed as spherulite size is varied, but this is normally confounded with sizable changes in percent crystallinity. This report demonstrates that a semicrystalline polymer, poly(hexamethylene sebacate) (HMS) may exhibit either ductile or brittle behavior dependent upon thermal history in a manner not directly related to volume relaxation or percent crystallinity. 

Researchers have examined the creep and creep recovery of textile fibers extensively (13-21). For example, Hunt and Darlington (16, 17) studied the effects of temperature, humidity, and previous thermal history on the creep properties of Nylon 6,6. They were able to explain the shift in creep curves with changes in temperature and humidity. Lead-erman (19) studied the time dependence of creep at different temperatures and humidities. Shifts in creep curves due to changes in temperature and humidity were explained with simple equations and convenient shift factors. Morton and Hearle (21) also examined the dependence of fiber creep on temperature and humidity. Meredith (20) studied many mechanical properties, including creep of several generic fiber types. Phenomenological theory of linear viscoelasticity of semicrystalline polymers has been tested with creep measurements performed on textile fibers (18). From these works one can readily appreciate that creep behavior is affected by many factors on both practical and theoretical levels. 

The mechanical and thermal properties of a range of poly(ethylene)/po-ly(ethylene propylene) (PE/PEP) copolymers with different architectures have been compared [2]. The tensile stress-strain properties of PE-PEP-PE and PEP-PE-PEP triblocks and a PE-PEP diblock are similar to each other at high PE content. This is because the mechanical properties are determined predominantly by the behaviour of the more continuous PE phase. For lower PE contents there are major differences in the mechanical properties of polymers with different architectures, that form a cubic-packed sphere phase. PE-PEP-PE triblocks were found to be thermoplastic elastomers, whereas PEP-PE-PEP triblocks behaved like particulate filled rubber. The difference was proposed to result from bridging of PE domains across spheres in PE-PEP-PE triblocks, which acted as physical crosslinks due to anchorage of the PE blocks in the semicrystalline domains. No such arrangement is possible for the PEP-PE-PEP or PE-PEP copolymers [2]. 

The remainder of this chapter will focus on the thermal conductivities of amorphous polymers (or the amorphous phase, in the case of semicrystalline polymers). See Chapter 20 for a discussion of methods for the prediction of the thermal conductivities of heterogeneous materials (such as blends and composites) in the much broader context of the prediction of both the thermoelastic and the transport properties of such materials. 

Once again, it should be pointed out that the exact shape of the modulus-temperature curve of a crystalline polymer depends on the thermal history of the sample, particularly on the rate of cooling from the melt and annealing treatment. Two crystalline polymers are mechanically equivalent," for practical purposes, if they have the same values of Tg, Tm chain length, percentage of crystallinity, and crystalline structure. Because this is rarely the case, semicrystalline polymers exhibit a wide spectrum of properties. 

Poly(ethylene terephthalate) Poly(ethylene terephthalate) is a widely used semicrystalline polymer. The macroscopic properties of PET such as thermal, mechanical, optical, and permeation properties depend on its specific internal morphologies and microstructure arrangement. It can be quenched into the completely amorphous state, whereas thermal and thermomechanical treatments lead to partially crystallized samples with easily controlled degrees of crystallinity. The crystallization behavior of thermoplastic polymers is strongly affected by processing conditions [91-93]. 

Linear thermal expansion testing helps to determine if failure by thermal stress may occur in products and materials. Precise knowledge of the CTE can be utilized to estimate the thermal stresses. This aspect makes CTE to an important property of the used fiber for composite materials. A rule of mixtures is sufficient for calculating the CTE of polymers filled with powder or short fibers. In case of long libers, the rule of mixtures is valid perpendicular to the reinforcing fibers. Molecular orientation affects the thermal expansion of polymers. Processing also affects CTE, for semicrystalline polymers this fact is very important. For that reason, CTE measurements are often used to predict shrinkage in injection moulded parts. 

Basic principle underlying the isothermal crystallization of PHAs will be emphasized in this chapter. Crystallization of polymer melts is often accompanied by a heat release in the system. This can be measured using differential scanning calorimeter (DSC). Following the isothermal crystallization of PHAs, the influence of thermal treatment of a semicrystalline polymer on the mechanical properties is also given. 

The large multiplicity of phases, of which many are mesophases, is typical for macromolecules. The old two-phase model for semicrystalline polymers is in need of considerable extension. Most of the phase areas are metastable and have, in addition, only nanometer dimensions [7]. Only when a full characterization has been completed, can an attempt be made to link structure and properties, the central goal of thermal analysis of materials. 

Further, the thermal properties of PL A vary with crystal polymorphism. Similar to other semicrystalline polymers, PLA exhibits a three-phase structure, consisting of the crystal phase and two amorphous fractions which vitrify/devitrify in different temperature ranges [45]. Chain segments in the bulk amorphous phase... 

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