Hard phase

Under equiUbrium conditions, magnesium can contain as much as 12.7% aluminum in soHd solution at the eutectic temperature. However, the slow diffusion of aluminum to the grain boundary leads to a coring effect in primary crystals and a hard-phase magnesium—aluminum compound(17 12)... 

Mg yA1 2> or P-(MgAl). Thus aluminum occurs in magnesium alloys both in soHd solution and as the intermediary intermetaUic phase. The latter is clear white and in slight rehef in poHshed and etched samples. In as-cast alloys, the hard phase occurs in massive form, but when precipitated from sohd solution a lamellar stmcture is formed similar to peadite in steel. When produced by aging at low temperatures, it appears as fine particles. 

The pseudocross-links, generated by the hard-segment interactions, are reversed by heating or dissolution. Without the domain crystallinity, thermoplastic polyurethanes would lack elastic character and be more gum-like in nature. In view of the outlined morphology, it is not surprising that many products develop their ultimate properties only on curing at elevated temperature, which allows the soft- and hard-phase segments to separate. 

Abrasive wear is encountered when hard particles, or hard projections on a counter-face, are forced against and moved relative to a surface. In aUoys such as the cobalt-base wear aUoys which contain a hard phase, the abrasion resistance generaUy increases as the volume fraction of the hard phase increases. Abrasion resistance is, however, strongly influenced by the size and shape of the hard-phase precipitates within the microstmcture, and the size and shape of the abrading species (see Abrasives). 

Thermoplastic elastomers are often multiphase compositions in which the phases are intimately dispersed. In many cases, the phases are chemically bonded by block or graft copolymerization. In others, a fine dispersion is apparentiy sufficient. In these multiphase systems, at least one phase consists of a material that is hard at room temperature but becomes fluid upon heating. Another phase consists of a softer material that is mbberlike at RT. A simple stmcture is an A—B—A block copolymer, where A is a hard phase and B an elastomer, eg, poly(styrene- -elastomer- -styrene). 

It is somewhat difficult conceptually to explain the recoverable high elasticity of these materials in terms of flexible polymer chains cross-linked into an open network structure as commonly envisaged for conventionally vulcanised rubbers. It is probably better to consider the deformation behaviour on a macro, rather than molecular, scale. One such model would envisage a three-dimensional mesh of polypropylene with elastomeric domains embedded within. On application of a stress both the open network of the hard phase and the elastomeric domains will be capable of deformation. On release of the stress, the cross-linked rubbery domains will try to recover their original shape and hence result in recovery from deformation of the blended object. 

There is also growing interest in multi-phase systems in which hard phase materials are dispersed in softer polyether diols. Such hard phase materials include polyureas, rigid polyurethanes and urea melamine formaldehyde condensates. Some of these materials yield high-resilience foams with load deflection characteristics claimed to be more satisfactory for cushioning as well as in some cases improving heat resistance and flame retardancy. 

It should also be pointed out that the Tg of the soft blocks, which consist of fairly short polymer chains, will be somewhat lower than for a corresponding homopolymer of high molecular weight, for the reasons given in Section 4.2. This effect may, however, be more than compensated by the loss of molecular freedom due to the presence of and interaction with the hard phase polymer present. 

Oil resistance demands polar (non-hydrocarbon) polymers, particularly in the hard phase. If the soft phase is non-polar but the haid phase polar, then swelling but not dissolution will occur (rather akin to that occurring with vulcanised natural rubber or SBR). If, however, the hard phase is not resistant to a particular solvent or oil, then the useful physical properties of a thermoplastic elastomer will be lost. As with all plastics and rubbers, the chemical resistant will depend on the chemical groups present, as discussed in Section 5.4. 

Most of the thermoplastic elastomers can be produced in a wide hardness range without resort to additives. If it is practical to use soft and hard phases in any proportions, then the hardness range will be from that of the soft phase... 

The density of the polymer will clearly depend on the density of the soft phase (usually low), and the density of the hard phase (generally higher with crystallisable polar blocks) and the ratio of the soft and hard phases present. It will also clearly depend on the additives present and to some extent on the processing conditions, which may affect the crystalline morphology. 

Type Soft phase T, ro Hard phase Pg or T ro Oil resistance Hardness range Specific gravity... 

Coran and Patel [33] selected a series of TPEs based on different rubbers and thermoplastics. Three types of rubbers EPDM, ethylene vinyl acetate (EVA), and nitrile (NBR) were selected and the plastics include PP, PS, styrene acrylonitrile (SAN), and PA. It was shown that the ultimate mechanical properties such as stress at break, elongation, and the elastic recovery of these dynamically cured blends increased with the similarity of the rubber and plastic in respect to the critical surface tension for wetting and with the crystallinity of the plastic phase. Critical chain length of the rubber molecule, crystallinity of the hard phase (plastic), and the surface energy are a few of the parameters used in the analysis. Better results are obtained with a crystalline plastic material when the entanglement molecular length of the... 

FIGURE 5.7 Phase separation in styrene-butadiene-styrene (SBS) triblock copolymer. The isolated spherical styrene domains form the hard phase, which act both as intermolecular tie points and filler. The continuous butadiene imparts the elastomeric characteristics to this polymer. MW = molecular weight. (From Grady, B.P. and Cooper, S.L., Science and Technology of Rubber, Mark, J.E., Erman, B., and Eirich, F.R. (eds.). Academic Press, San Diego, CA, 1994. With permission.)... 

TPE Type Soft Rubber Phase Tg (°C) Hard Phase Tg or Tn, (°C)... 

When plastics act as a physical cross-link and strength properties are indirectly related to the modulus of hard phase and morphology of the blend, the filler effect is analyzed by the following equation ... 

The elasticity of thermoplastic polyurethane rubbers (which are also known as thermoplastic urethanes or TPUs) is a function of their morphology which comprises hard and soft phases. The hard phases consist of hydrogen bonded clusters of chain segments, which are linked by flexible chain segments that make up the soft phase. The hard blocks, which are the minor phase, exist as separate domains within a continuous matrix of the majority soft phase, as shown schematically in Fig. 25.9. 

Tor instance crystalline phase, amorphous phase, hard phase, soft phase, phases formed by different polymeric components in blends or block copolymers. 

Again, crystallinity may be replaced by hard phase fraction , soft phase fraction , or whatever designation applies better to die material that is studied. 

PEE s are commonly characterized by two numbers (e.g., 1500/50). The first number reports the minimum quantization of the polyether blocks (meaning the polyether blocks are multiples of 1500 g/mol ), the second number indicates the mass fraction of the polyester hard phase (e.g., 50 wt.-% of polyester). 

How should such rigid domain coupling work In principle domains can only be rigidly coupled by a bridge of hard-phase material which has a different density. We know that the polyester hard-phase is semicrystalline. So the observation is indicative for a structure in which the hard domains are subdivided into crystalline and amorphous zones. 

Therefore, at room temperature Fluoro-PSB-II a thermoplastic elastomer with a soft polymer phase (fluorinated block) and a hard phase (PS-block), similar to the parental polystyrene-6-polybutadiene block copolymer. Depending on the relative volume fraction of both components and the continuity of the phases, the resulting bulk material is rubbery or a high-impact solid. 

Thermoplastic elastomers (TPE), 9 565-566, 24 695-720 applications for, 24 709-717 based on block copolymers, 24 697t based on graft copolymers, ionomers, and structures with core-shell morphologies, 24 699 based on hard polymer/elastomer combinations, 24 699t based on silicone rubber blends, 24 700 commercial production of, 24 705-708 economic aspects of, 24 708-709 elastomer phase in, 24 703 glass-transition and crystal melting temperatures of, 24 702t hard phase in, 24 703-704 health and safety factors related to, 24 717-718... 

Note 1 The behaviour of the hard phase domains as junction points is thermally reversible. 

Atomic force microscopy and attenuated total reflection infrared spectroscopy were used to study the changes occurring in the micromorphology of a single strut of flexible polyurethane foam. A mathematical model of the deformation and orientation in the rubbery phase, but which takes account of the harder domains, is presented which may be successfully used to predict the shapes of the stress-strain curves for solid polyurethane elastomers with different hard phase contents. It may also be used for low density polyethylene at different temperatures. Yield and rubber crosslink density are given as explanations of departure from ideal elastic behaviour. 17 refs. 

Macromers have been used to produce thermoplastic elastomers. Generally, the backbone serves as the elastomeric phase while the branches serve as the hard phases. These structures are often referred to as comb -shaped because of the similarity between the rigid part of the comb and its teeth and the structure of these graft polymers. 

Example 5-23) and of ABS-polymers (made from acrylonitrile, butadiene, and styrene), whereby grafting occurs in situ at the beginning of the polymerization process. The formed graft copolymers act in two ways As emulsifiers during the polymerization process and, secondly, in the solid end product as compatibilizer between the thermoplastic hard phase and the rubber-elastic dipersed phase (already in concentrations below 3%). 

Unlike simple mixtures of polystyrene and polybutadiene such blends can be thermoplastically processed without phase separation ( splicing ) Furthermore, they can to a certain extent withstand mechanical impact without disintegration. This is because the above-mentioned graft polymers function also as compatibilizer at the borderline of the hard phase and the rubber-elastic dispersed phase (already at concentrations below 3%). 

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