Melt viscosities

The melt viscosity of a polymer at a given temperature is a measure of the rate at which chains can move relative to each other. This will be controlled by the ease of rotation about the backbone bonds, i.e. the chain flexibility, and on the degree of entanglement. Because of their low chain flexibility, polymers such as polytetrafluoroethylene, the aromatic polyimides, the aromatic polycarbonates and to a less extent poly(vinyl chloride) and poly(methyl methacrylate) are highly viscous in their melting range as compared with polyethylene and polystyrene. 

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When sulphur is melted viscosity changes occur as the temperature is raised. These changes are due to the formation of long-chain polymers (in very pure sulphur, chains containing about 100 (X)0 atoms may be formed). The polymeric nature of molten sulphur can be recognised if molten sulphur is poured in a thin stream into cold water, when a plastic rubbery mass known as plastic sulphur is obtained. This is only slightly soluble in carbon disulphide, but on standing it loses its plasticity and reverts to the soluble rhombic form. If certain substances, for example iodine or oxides of arsenic, are incorporated into the plastic sulphur, the rubbery character can be preserved. 

The properties of SAN resins depend on their acrylonittile content. Both melt viscosity and hardness increase with increasing acrylonittile level. Unnotched impact and flexural strengths depict dramatic maxima at ca 87.5 mol % (78 wt %) acrylonitrile (8). With increasing acrylonitrile content, copolymers show continuous improvements in barrier properties and chemical and uv resistance, but thermal stabiUty deteriorates (9). The glass-transition... 

Because of the high melt viscosity of polyolefins, normal spinning melt temperatures are 240—310°C, which is 80—150°C above the crystalline melting point. Because of the high melt temperatures used for polyolefin fiber spinning, thermal stabilizers such as substituted hindered phenols are added. In the presence of pigments, the melt temperature must be carefully controlled to prevent color degradation and to obtain uniform color dispersion. 

Peifluorinated ethylene—piopjiene (FEP) lesin [25067-11-2] is a copolymer of tetiafluoioethylene [116-14-3] (TFE) and hexafluoiopiopylene [116-15-4] (HEP) thus its blanched stmctuie contains units of —CF2—CF2— and units of —CF2—CF(CF2)—. It retains most of the desirable characteristics of polytetrafluoroethylene (PTFE) but with a melt viscosity low enough for conventional melt processing. The introduction of hexafluoropropylene lowers the melting point of PTFE from 325°C to about 260°C. 

Hexafluoiopiopylene and tetiafluoioethylene aie copolymerized, with trichloiacetyl peroxide as the catalyst, at low temperature (43). Newer catalytic methods, including irradiation, achieve copolymerization at different temperatures (44,45). Aqueous and nonaqueous dispersion polymerizations appear to be the most convenient routes to commercial production (1,46—50). The polymerization conditions are similar to those of TFE homopolymer dispersion polymerization. The copolymer of HFP—TFE is a random copolymer that is, HFP units add to the growing chains at random intervals. The optimal composition of the copolymer requires that the mechanical properties are retained in the usable range and that the melt viscosity is low enough for easy melt processing. 

Hexafluoropropylene—tetrafluoroethylene copolymers are available in low melt viscosity, extmsion grade, intermediate viscosity, high melt viscosity, and as dispersions. The low melt viscosity (MV) resin can be injection molded by conventional thermoplastic molding techniques. It is more suitable for injection molding than other FEP resins (51). 

The high MV resia is used as liners for process equipmeat. Its melt viscosity is significantly higher than that of other resias and therefore it is unsuitable for conventional iajection molding. Stress-crack resistance and mechanical properties are superior to those of the other three products (52)... 

Fabrication and Processing. PVDF is available in a wide range of melt viscosities as powder or pellets to fulfill typical fabrication requirements latices are also commercially available. 

The various lubricants formulated into PVC to improve the processing can also enhance the performance of the stabilizet. In pigmented apphcations, calcium soaps, eg, calcium stearate, ate commonly used as internal lubricants to promote PVC fusion and reduce melt viscosity. This additive is also a powerfiil costabilizer for the alkyl tin mercaptide stabilizers at use levels of 0.2 to 0.7 phr. Calcium stearate can significantly improve the eady color and increase the long-term stabiUty at low levels however, as the concentration increases, significant yellowing begins to occur. 

C. Characteristically, these nematic melts show the persistence of orientational order under the influence of elongational flow fields which result in low melt viscosities under typical fiber formation conditions even at high molecular weights. 

Most hydrocarbon resins are composed of a mixture of monomers and are rather difficult to hiUy characterize on a molecular level. The characteristics of resins are typically defined by physical properties such as softening point, color, molecular weight, melt viscosity, and solubiHty parameter. These properties predict performance characteristics and are essential in designing resins for specific appHcations. Actual characterization techniques used to define the broad molecular properties of hydrocarbon resins are Fourier transform infrared spectroscopy (ftir), nuclear magnetic resonance spectroscopy (nmr), and differential scanning calorimetry (dsc). 

Melt Viscosity. Viscosities of resins at standard temperatures yield information about molecular weight and molecular weight distribution, as weU as valuable information with respect to appHcation logistics. Some customers prefer to receive resins in molten form. Melt viscosities help to determine the required temperature for a resin to be pumpable. Temperature—viscosity profiles are routinely suppHed to customers by resin manufacturers. In general, a molten viscosity of 1—1.1 Pa-s (1000—1100 cP) or less at process temperatures is convenient for the pumping and handling of molten resin. 

Styrenic block copolymers (SBCs) are also widely used in HMA and PSA appHcations. Most hot melt appHed pressure sensitive adhesives are based on triblock copolymers consisting of SIS or SBS combinations (S = styrene, I = isoprene B = butadiene). Pressure sensitive adhesives typically employ low styrene, high molecular weight SIS polymers while hot melt adhesives usually use higher styrene, lower molecular weight SBCs. Resins compatible with the mid-block of an SBC improves tack properties those compatible with the end blocks control melt viscosity and temperature performance. 

Table 9 compares the most important properties of substrate materials based on BPA-PC, PMMA, and CPO (three different products) (216,217). The future will prove if the current disadvantages of CPO against BPA-PC regarding warp, processibiUty (melt viscosity), and especially cost can be alleviated. CycHc polyolefins (CPO) and, especially cycloolefin copolymers (COC) (218) and blends of cycloolefin copolymers with suitable engineering plastics have the potential to be interesting materials for substrate disks for optical data storage. 

Melt Viscosity. As shown in Tables 2 and 3, the melt viscosity of an acid copolymer increases dramatically as the fraction of neutralization is increased. The relationship for sodium ionomers is shown in Figure 4 (6). Melt viscosities for a series of sodium ionomers derived from an ethylene—3.5 mol % methacrylic acid polymer show that the increase is most pronounced at low shear rates and that the ionomers become increasingly non-Newtonian with increasing neutralization (9). The activation energy for viscous flow has been reported to be somewhat higher in ionomers than in related acidic... 

Polyoxymethylene Ionomers. Ionic copolymers have been prepared from trioxane and epichlorohydrin, followed by reaction with disodium thioglycolate (76). The ionic forces in these materials dismpt crystalline order and increase melt viscosity (see Acetalresins). 

Melt Index or Melt Viscosity. Melt index describes the flow behavior of a polymer at a specific temperature under specific pressure. If the melt index is low, its melt viscosity or melt flow resistance is high the latter is a term that denotes the resistance of molten polymer to flow when making film, pipe, or containers. ASTM D1238 is the designated method for this test. 

Rheology of LLDPE. AH LLDPE processiag technologies iavolve resia melting viscosities of typical LLDPE melts are between 5000 and 70, 000 Pa-s (50,000—700,000 P). The main factor that affects melt viscosity is the resia molecular weight the other factor is temperature. Its effect is described by the Arrhenius equation with an activation energy of 29—32 kj/mol (7—7.5 kcal/mol) (58). 

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