Crystalline Dimensional stability

Typical melt temperatures are in the range 300-360°C (e.g. 320°C). Mould temperatures are usually about 135°C in order to optimise the amount of crystallinity and hence give mouldings of greatest stiffness, dimensional stability, thermal stability and surface finish. It is, however, possible to use relatively cold... 

Liquid crystal polymers (LCP) are a recent arrival on the plastics materials scene. They have outstanding dimensional stability, high strength, stiffness, toughness and chemical resistance all combined with ease of processing. LCPs are based on thermoplastic aromatic polyesters and they have a highly ordered structure even in the molten state. When these materials are subjected to stress the molecular chains slide over one another but the ordered structure is retained. It is the retention of the highly crystalline structure which imparts the exceptional properties to LCPs. 

Miscibility or compatibility provided by the compatibilizer or TLCP itself can affect the dimensional stability of in situ composites. The feature of ultra-high modulus and low viscosity melt of a nematic liquid crystalline polymer is suitable to induce greater dimensional stability in the composites. For drawn amorphous polymers, if the formed articles are exposed to sufficiently high temperatures, the extended chains are retracted by the entropic driving force of the stretched backbone, similar to the contraction of the stretched rubber network [61,62]. The presence of filler in the extruded articles significantly reduces the total extent of recoil. This can be attributed to the orientation of the fibers in the direction of drawing, which may act as a constraint for a certain amount of polymeric material surrounding them. 

As Carfagna et al. [61] suggested, the addition of a mesophasic polymer to an amorphous matrix can lead to different results depending on the properties of the liquid crystalline polymer and its amount. If a small amount of the filler compatible with the matrix is added, only plasticization effect can be expected and the dimensional stability of the blend would be reduced. Addition of PET-PHB60 to polycarbonate reduced the dimensionality of the composite, i.e., it increased the shrinkage [42]. This behavior was ascribed to the very low... 

Dimensional stability is an important thermal property for the majority of plastics. It is the temperature above which plastics lose their dimensional stability. For most plastics the main determinant of dimensional stability is their Tg. Only with highly crystalline plastics is Tg not a limitation. 

Nylon (Polyamide) PA is a crystalline plastic and the first and largest consumption of the engineering thermoplastic. This family of TPs are tough, slippery, with good electrical properties, but hygroscopic and with dimensional stability lower than most other engineering types. Also offered in reinforced and filled grades as a moderately priced metal replacement. 

With DMA the effect of temperature on the modulus can be studied. By increasing the temperature from -150 to 300°C, one encounters several transitions in PA (Fig. 3.1). There is a transition at about —120°C, the y-transition, which is due to the mobilization of methylene units. There is also a transition at —30°C, which is present in wetted aliphatic PA this is due to non-H-bonded amide units and is termed the /J-transition. At about 50°C the glass Uansition (Tg) (a-transition) of the aliphatic polyamides PA-6 and PA-6,6 occurs. At this Uansition, the modulus is lowered considerably. For partially aromatic PA, the Tg occurs above 100°C. The last transition is the flow temperature, at which temperature the material melts the flow temperature and the melt temperature, as measured by DSC, correspond well. The modulus is a measure of dimensional stability and increases with crystallinity and filler content (Fig. 3.12). 

Among the spectrum of melt-spinnable fibers such as polyolefins and nylons, PET stands at the upper end in terms of crystalline melt temperature and glass transition temperature. This provides superior dimensional stability for applications where moderately elevated temperatures are encountered, e.g. in automobile tires or in home laundering and drying of garments. The high thermal stability results from the aromatic rings that hinder the mobility of the polymer chain. 

PBT is used for textile applications due to its stretchability, increased crystallinity and improved dyeability. It is introduced in the production of carpets and stretchable fabrics, where a certain degree of elasticity is desired. PBT is used preferably for the production of engineering plastics due to its combination of dimensional stability, tensile strength, increased flexibility and fast crystallization rate. 

According to Tarascon and co-workers, the swelling of PVdF—HFP by liquid electrolytes was never complete due to the semicrystalline nature of the copolymer, which tends to microphase-separate after the activation by electrolyte. On the other hand, it is those crystalline domains in the gelled PVdF—HFP that provide mechanical integrity for the resultant GPE. Thus, a dual phase structure was proposed for the Bellcore GPE by some authors, wherein the amorphous domain swollen by a liquid electrolyte serves as the ion conduction phase, while tiny crystallites act as dimensional stabilizer. 

Rheological observations of the UHMWPE pseudo-gels of different concentrations under oscillatory shear conditions at different temperatures showed that these systems exhibit considerable drawability at temperatures above ambient. The deformation of the crystalline phase of the gel-like system is not reversible and, as shown in the sequence of photographs Figure 2, for a pseudo-gel of 4% concentration, it was greater when the sample was sheared under the same oscillatory conditions at higher temperatures. The displaced crystals of the UHMWPE pseudo-gel showed remarkable dimensional stability after shear cessation and removal of any compression load in the optical rotary stage. 

Eoams were extruded from low density polyethylene (LDPE) and blends of LDPE with syndiotactic polypropylene (sPP), using isobutane as the blowing agent. The extruded materials were characterised by measurement of dimensional stability at room temperature, density, tensile properties, dynamic stiffness, and crystallinity determined by differential scanning calorimetry. The sPP, with a slow crystallisation rate, did not interfere with the expansion of the LDPE, and enhanced the temperature resistance by in-situ crystallisation. The blends were flexible, dimensionally... 

Crystalline with good mechanical properties, high impact strength, good thermal and oxidative stability, transparent, selfextinguishing, low moisture absorption Good heat resistance, dimensional stability, resistance to cold flow, solvent, dielectric properties... 

Nylons 6/6 and 6 comprise more than 90% of the polyamide market. The two have similar properties but nylon 6 has a lower Tm (223°C). Small amounts of nylons 6/9, 6/10, 6/12, 11, 12, 12/12, and 4/6 are produced as specialty materials. Those with more methylene groups than nylons 6/6 and 6 have better moisture resistance, dimensional stability, and electrical properties, but the degree of crystallinity, Tm, and mechanical properties are lower. Specialty nylons made from dimerized fatty acids find applications as hot-melt adhesives, crosslinking agents for epoxy resins, and thermographic inks. 

In addition to conferring transparency on these polymers, the amorphous noncrystallizable nature of polysulfones assures minimal shrinkage during fabrication of the resins into finished parts. The absence of crystallinity also assures dimensional stability during the service life of the parts where high use temperatures are encountered. Good dimensional stability is important to many structural and engineering applications. 

A related class of polymers is the crystalline, thermoplastic materials. These also are fabricated by heating to a high temperature so diat they flow but when they are cooled ordered regions develop within them, which makes them translucent. They have much tendency to flow because of these mechanical crosslinks" and have good dimensional stability. Polyediylene and polypropylene belong to this class. Here the chain is simple and regular so that different polymer molecules, or different parts of the same molecule, can pack next to each other. The same situation exists with Teflon" (polytetrafl uoroethylene). 

Amorphous nylons are transparent. Heat-deflection temperatures are lower than those of filled crystalline nylon resins, and melt flow is stiffer hence, they are more difficult to process. Mold shrinkage is lower and they absorb less water. Warpage is reduced and dimensional stability less of a problem than with crystalline products. Chemical and hydrolytic stability are excellent. Amorphous nylons can be made by using monomer combinations that result in highly asymmetric structures which crystallize with difficulty or by adding crystallization inhibitors to crystalline resins such as nylon-6 (61). 

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