Amorphous transition temperature

This reaction is irreversible. Epitaxial silicon is deposited. Polycrystalline silicon is obtained in the range of 610-630°C, which is close to the crystalline-amorphous transition temperature. 

For polymers, the expression is slightly different because the term e/ksT cannot be considered a constant close to the amorphous transition temperature [13]. Like viscosity, it is a function of the temperature. A simple mathematical approximation [7] is given by... 

Irregularities such as branch points, comonomer units, and cross-links lead to amorphous polymers. They do not have true melting points but instead have glass transition temperatures at which the rigid and glasslike material becomes a viscous liquid as the temperature is raised. 

Molecular Weight. The values of the mechanical properties of polymers increase as the molecular weight increases. However, beyond some critical molecular weight, often about 100,000 to 200,000 for amorphous polymers, the increase in property values is slight and levels off asymptotically. As an example, the glass-transition temperature of a polymer usually follows the relationship... 

PVF displays several transitions below the melting temperature. The measured transition temperatures vary with the technique used for measurement. T (L) (lower) occurs at —15 to —20 " C and is ascribed to relaxation free from restraint by crystallites. T (U) (upper) is in the 40 to 50°C range and is associated with amorphous regions under restraint by crystallites (63). Another transition at —80° C has been ascribed to short-chain amorphous relaxation and one at 150°C associated with premelting intracrystalline relaxation. 

As appHed to hydrocarbon resins, dsc is mainly used for the determination of glass-transition temperatures (7p. Information can also be gained as to the physical state of a material, ie, amorphous vs crystalline. As a general rule of thumb, the T of a hydrocarbon resin is approximately 50°C below the softening point. Oxidative induction times, which are also deterrnined by dsc, are used to predict the relative oxidative stabiHty of a hydrocarbon resin. 

Eig. 15. Time—temperature transformation ia a thin-phase change layer during recording/reading/erasiug (3,105). C = Crystalline phase A = amorphous phase = melting temperature = glass-transition temperature RT = room temperature. 

The TPX experimental product of Mitsubishi Petrochemical Ind. (221) is an amorphous, transparent polyolefin with very low water absorption (0.01%) and a glass-transition temperature comparable to that of BPA-PC (ca 150°C). Birefringence (<20 nm/mm), flexural modulus, and elongation at break are on the same level as PMMA (221). The vacuum time, the time in minutes to reach a pressure of 0.13 mPa (10 torr), is similarly short like that of cychc polyolefins. Typical values of TPX are fisted in Table 11. A commercial application of TPX is not known as of this writing. 

Properties. One of the characteristic properties of the polyphosphazene backbone is high chain dexibility which allows mobility of the chains even at quite low temperatures. Glass-transition temperatures down to —105° C are known with some alkoxy substituents. Symmetrically substituted alkoxy and aryloxy polymers often exhibit melting transitions if the substituents allow packing of the chains, but mixed-substituent polymers are amorphous. Thus the mixed substitution pattern is deUberately used for the synthesis of various phosphazene elastomers. On the other hand, as with many other flexible-chain polymers, glass-transition temperatures above 100°C can be obtained with bulky substituents on the phosphazene backbone. 

Table 1. Glass-Transition Temperature of Amorphous Thermoplastics ...

Polycarbonates are an unusual and extremely useful class of polymers. The vast majority of polycarbonates are based on bisphenol A [80-05-7] (BPA) and sold under the trade names Lexan (GE), Makrolon (Bayer), CaUbre (Dow), and Panlite (Idemitsu). BPA polycarbonates [25037-45-0] having glass-transition temperatures in the range of 145—155°C, are widely regarded for optical clarity and exceptional impact resistance and ductiUty at room temperature and below. Other properties, such as modulus, dielectric strength, or tensile strength are comparable to other amorphous thermoplastics at similar temperatures below their respective glass-transition temperatures, T. Whereas below their Ts most amorphous polymers are stiff and britde, polycarbonates retain their ductiUty. 

A reexamination of polycarbonate chemistry was carried out about 50 years after the first aromatic polycarbonates of resorcinol and hydroquinone were discovered. In independent investigations at Bayer AG and General Electric, it was discovered that the polycarbonates of BPA could be prepared (eq. 2). Unlike the ahphatic polycarbonates prepared earlier, which were either hquids or low melting sohds, the aromatic polycarbonates were amorphous sohds having elevated glass-transition temperatures. 

The melt temperature of a polyurethane is important for processibiUty. Melting should occur well below the decomposition temperature. Below the glass-transition temperature the molecular motion is frozen, and the material is only able to undergo small-scale elastic deformations. For amorphous polyurethane elastomers, the T of the soft segment is ca —50 to —60 " C, whereas for the amorphous hard segment, T is in the 20—100°C range. The T and T of the mote common macrodiols used in the manufacture of TPU are Hsted in Table 2. 

As-polymerized PVDC does not have a well-defined glass-transition temperature because of its high crystallinity. However, a sample can be melted at 210°C and quenched rapidly to an amorphous state at <—20°C. The amorphous polymer has a glass-transition temperature of — 17°C as shown by dilatometry (70). Glass-transition temperature values of —19 to — 11°C, depending on both method of measurement and sample preparation, have been determined. 

As shown in Table 3, the glass-transition temperatures of the amorphous straight-chain alkyl vinyl ether homopolymers decrease with increasing length of the side chain. Also, the melting points of the semicrystalline poly(alkyl vinyl ether)s increase with increasing side-chain branching. 

Table 3. Glass-Transition Temperature of Amorphous Poly(Vinyl Ether)s and Melting Points of Crystalline Poly(Vinyl Ether)s ...

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