Polystyrene stressed

PLA is a polymer that may not be well suited to injection moulding. Its rate of crystallisation is too slow to allow cycle times typical of those for commodity thermoplastics such as polystyrene. Stress induced crystallisation that can enhance PLA crystallisation is better suited to processes such as fibre spinning or biaxial orientation of film. 

When chemicals are weak solvents for polystyrene, stress cracks are formed in the products. Chemical resistances to practical chemicals are compared in Table 18.5. HIPS-SPS blend exhibits better resistance to chemicals which are used in the kitchen and bathroom. In HIPS/SPS blend, SPS may work to prevent the formation of crazes and their propagation to cracks initiated from contact with chemicals. 

According to more recent theories, the toughness of high impact polystyrene is caused by flow and energy dissipation processes in the continuous polystyrene phase. The rubber particles act as initiating elements. Considerable differences in the thermal expansion coefficients and in the moduli of the polystyrene phase on the one hand and of the rubber particles on the other lead to an inhomogeneous stress distribution in impact polystyrene. Stress maxima create zones of lower density, called crazes (3), in which the polystyrene molecules are extended parallel to the direction of stress. Macroscopi-cally craze formation appears as whitening the flow processes result in irreversible deformation (cold flow). 

The isothermal curves of mechanical properties in Chap. 3 are actually master curves constructed on the basis of the principles described here. Note that the manipulations are formally similar to the superpositioning of isotherms for crystallization in Fig. 4.8b, except that the objective here is to connect rather than superimpose the segments. Figure 4.17 shows a set of stress relaxation moduli measured on polystyrene of molecular weight 1.83 X 10 . These moduli were measured over a relatively narrow range of readily accessible times and over the range of temperatures shown in Fig. 4.17. We shall leave as an assignment the construction of a master curve from these data (Problem 10). 

Figure 4.17 Experimental stress relaxation moduli of polystyrene measured over about two orders of magnitude in time at the temperatures indicated. [Reprinted with permission from H. Fujita and K. Ninomiya, J. Polym. Sci. 24 233 (1957).]...

Creep. The creep characteristic of plastic foams must be considered when they are used in stmctural appHcations. Creep is the change in dimensions of a material when it is maintained under a constant stress. Data on the deformation of polystyrene foam under various static loads have been compiled (158). There are two types of creep in this material short-term and long-term. Short-term creep exists in foams at all stress levels however, a threshold stress level exists below which there is no detectable long-term creep. The minimum load required to cause long-term creep in molded polystyrene foam varies with density ranging from 50 kPa (7.3 psi) for foam density 16 kg/m (1 lb /ft ) to 455 kPa (66 psi) at foam density 160 kg/m (10... 

The particular type of thermoplastic elastomer (TPE) shown in Figure 3 exhibits excellent tensile strength of 20 MPa (2900 psi) and elongation at break of 800—900%, but high compression set because of distortion of the polystyrene domains under stress. These TPEs are generally transparent because of the small size of the polystyrene domains, but can be colored or pigmented with various fillers. As expected, this type of thermoplastic elastomer is not suitable for use at elevated temperatures (>60° C) or in a solvent environment. Since the advent of these styrenic thermoplastic elastomers, there has been a rapid development of TPEs based on other molecular stmctures, with a view to extending their use to more severe temperature and solvent environments. 

Proportion of Hard Segments. As expected, the modulus of styrenic block copolymers increases with the proportion of the hard polystyrene segments. The tensile behavior of otherwise similar block copolymers with a wide range of polystyrene contents shows a family of stress—strain curves (4,7,8). As the styrene content is increased, the products change from very weak, soft, mbbedike materials to strong elastomers, then to leathery materials, and finally to hard glassy thermoplastics. The latter have been commercialized as clear, high impact polystyrenes under the trade name K-Resin (39) (Phillips Petroleum Co.). Other types of thermoplastic elastomers show similar behavior that is, as the ratio of the hard to soft phase is increased, the product in turn becomes harder. 

Whether or not a polymer is rubbery or glass-like depends on the relative values of t and v. If t is much less than v, the orientation time, then in the time available little deformation occurs and the rubber behaves like a solid. This is the case in tests normally carried out with a material such as polystyrene at room temperature where the orientation time has a large value, much greater than the usual time scale of an experiment. On the other hand if t is much greater than there will be time for deformation and the material will be rubbery, as is normally the case with tests carried out on natural rubber at room temperature. It is, however, vital to note the dependence on the time scale of the experiment. Thus a material which shows rubbery behaviour in normal tensile tests could appear to be quite stiff if it were subjected to very high frequency vibrational stresses. 

In common with other thermoplastic melts polystyrene exhibits pseudoplastic behaviour. At shearing stresses below 60/M,J, MPa (where = average molecular weight), the ratio of shear stress to shear rate is almost constant and the melt is substantially Newtonian. Above this shear stress non-Newtonian... 

Although it is not difficult to make injection mouldings from polystyrene which appear to be satisfactory on visual examination it is another matter to produce mouldings free from internal stresses. This problem is common to injection mouldings of all polymers but is particularly serious with such rigid amorphous thermoplastics as polystyrene. 

The latter equation contains constants with well-known values and can therefore be used to predict the fracture stress of most polymers. For example, the bond dissociation energy Do, is about 80 kcal/mol for a C-C bond. For polystyrene, the modulus E 2 GPa, A. 4, p = 1.2 g/cm, = 18,000, and we obtain the fracture stress, o A1 MPa, which compares well with reported values. Polycarbonate, with similar modulus but a lower M. = 2,400 is expected to have a fracture stress of about 100 MPa. In general, letting E 1 GPa, p = 1.0 g/cm, and Do — 335 kJ/mol, the tensile strength is well approximated by... 

At low strains there is an elastic region whereas at high strains there is a nonlinear relationship between stress and strain and there is a permanent element to the strain. In the absence of any specific information for a particular plastic, design strains should normally be limited to 1%. Lower values ( 0.5%) are recommended for the more brittle thermoplastics such as acrylic, polystyrene and values of 0.2-0.3% should be used for thermosets. 

Example 2.20 A cylindrical vessel with an outside radius of 20 mm and an inside radius of 12 mm has a radial crack 3.5 mm deep on the outside surface. If the vessel is made from polystyrene which has a critical stress intensity factor of 1.0 MN calculate the maximum permissible pressure in this vessel. 

Another serious effect occurs with liquids which are not in themselves solvents but which may wet the polymer surfaces. These facilitate relief of frozen-in stresses by surface cracking which can be a severe problem in using many injection and blow mouldings with specific chemicals. Examples of this are white spirit with polystyrene, carbon tetrachloride with polycarbonates and soaps and silicone oils with low molecular weight polyethylenes. 

Of the instances of so-called solvent cracking of amorphous polymers known to the author, the liquid involved is not usually a true solvent of the polymer but instead has a solubility parameter on the borderline of the solubility range. Examples are polystyrene and white spirit, polycarbonate and methanol and ethyl acetate with polysulphone. The propensity to solvent stress cracking is however far from predictable and intending users of a polymer would have to check on this before use. 

How does yield stress depend on the size of particles We have mentioned above that increasing the specific surface, i.e. decreasing an average size of particles of one type, causes an increase in yield stress. This fact was observed in many works (for example [14-16]). Clear model experiments the purpose of which was to reveal the role of a particle s size were carried out in work [8], By an example of suspensions of spherical particles in polystyrene melt it was shown that yield stress of equiconcentrated dispersions may change by a hundred of times according to the diameter d of non-... 

Modification of filler s surface by active media leads to the same strong variation in viscosity. We can point out as an example the results of work [8], in which the values of the viscosity of dispersions of CaC03 in polystyrene melt were compared. For q> = 0.3 and the diameter of particles equal to 0.07 nm a treatment of the filler s surface by stearic acid caused a decrease in viscosity in the region of low shear rates as compared to the viscosity of nontreated particles more than by ten times. This very strong result, however, should not possibly be understood only from the point of view of viscometric measurements. The point is that, as stated above, a treatment of the filler particles affects its ability to netformation. Therefore for one and the same conditions of measuring viscosity, the dispersions being compared are not in equivalent positions with respect to yield stress. Thus, their viscosities become different. 

There are other conditions that result from the frozen-in stresses. In materials such as crystal polystyrene, which have low elongation to fracture and are in the glassy state at room temperature, a frequent result is crazing it is the appearance of many fine microcracks across the material in a direction perpendicular to the stress direction. This result may not appear immediately and may occur by exposure to either a mildly solvent liquid or vapor. Styrene products dipped in kerosene will craze quickly in stressed areas. 

The other effect of having a stretched area is a reduction in resistance to stress cracking. Crazing is a possibility in such areas such as in polystyrenes, and environmental stress cracking caused by solvent substances will occur in the stretched areas. This is a particularly important consideration in vacuum formed products used for packaging food that frequently has some solvent action on the plastics. 

The correct explanation of the peculiar behaviour of the butadiene-styrene system was provided by O Driscoll and Kuntz 144). As stated previously, under conditions of these experiments butadiene is indeed more reactive than styrene, whether towards lithium polystyrene or polybutadiene, contrary to a naive expectation. This was verified by Ells and Morton 1451 and by Worsfold 146,147) who determined the respective cross-propagation rate constants. It is germane to stress here that the coordination of the monomers with Li4, assumed to be the cause for this gradation of reactivities, takes place in the transition state of the addition and should be distinguished from the formation of an intermediate complex. The formation of a complex ... 

Addition of rubber particles of 30% to 100% by weight to cement with a grain size of approximately 40 to 60 mesh (0.4 to 0.25 mm) will produce a lightweight cement. The addition of rubber particles also creates a low permeability. The compositions are advantageous for cementing zones subjected to extreme dynamic stresses such as perforation zones and the junctions of branches in a multi-sidetrack well. Recycled, expanded polystyrene lowers the density of a hydraulic cement formulation and is an environmentally friendly solution for downcycling waste materials. 

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