Softening points

The softening point of residua and asphalt is the temperature at which asphalt attains a particular degree of sofmess under specified conditions of test. 

This test (ASTM D529) evaluates the relative weather resistance of asphalt used for protective-coating applications, especially for roofing. No direct measure of outdoor life or service can be obtained from this test. Methods for preparing test panels (ASTM D1669) and failure-endpoint testing (ASTM D1670) are available. 

Coke does not offer the same potential environmental issues as other petroleum products (Chapter 10 and above). It is used predominantly as a refinery fuel unless other uses for the production of a high-grade coke or carbon are desired. In the former case, the constituents of the coke that will release environmentally harmful gases such as nitrogen oxides, sulfur oxides, and particulate matter should be known. In addition, stockpiling coke on a site where it awaits use or transportation can lead to leachates as a result of rainfall (or acid rainfall) which are highly detrimental. In such a case, application of the toxicity characteristic leaching procedure 

Needle coke Ribbonlike parallel-ordered anisotropic domains that can also occur as folded structures 

Lenticular/granular Lenticular anisotropic domains of various sizes that are not aligned parallel to the particle surface 

The softening point is generally determined by slowly heating a test piece under constant load until it experiences a certain deformation. The temperature at which this occurs is known as the softening point. Since the methods used involve empirical and arbitrarily chosen test parameters, the softening point is 

The most widely used method is that of Vicat in which a blunt steel needle (area of point 1 mm ) is applied vertically to the surface of a test piece (about 1 cm and 3-4 mm thick) under a load of 49 N. The oven temperature is then raised at 50 °C/h and the temperature determined at which the needle has simk 1 mm into the test piece this is taken as the softening point (Vicat temperature). 

In the method of Martens a test rod is mounted upright in a support and the upper free end is put under a bending stress via a small weighted lever. The rod is slowly heated in an oven until a specified deflection is attained. The softening point determined in this way is called the Martens temperature. 

Finally, in the English-speaking countries, there is another extensively used method in which a rod is supported at its two ends and a load is placed on the center this is slowly heated in a liquid bath until a certain distortion is attained the temperature at which this occurs is called the heat distortion temperature (HDT). These methods are applicable both to thermoplastics and to crosslinked polymers. Interconversion of the softening temperatures determined by the different techniques is not possible. 

There are several methods commonly employed to measure the softening point, such as the ring-and-ball method and Durran s mercury methods. These measure the temperature at which the resin reaches an arbitrary softness. 

Since epoxy resins are not single crystalline structures and have a broad molecular weight distribution, sharp melting points are generally not noticeable. Any value for the 

FIGURE 20.1 Digital Brookfield viscometer allows the measurement of viscosity and torque. (Photo courtesy of Brookfield Laboratories.) 

FIGURE 20.2 Typical softening point values for uncured DGEBA epoxy versus molecular weight.1 

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The principal characteristics of bitumen are its softening point and its needle penetrability. In France the latter has always been the basis for bitumen classification and class designation. Yet, the former is more representative of a bitumen s capacity to deform when the service temperature increases. The other properties have more or less importance depending on the application. 

Softening point for bitumen (ring and ball method) NF T 66-008 (future NF EN 1427) ASTM D 36 Temperature at which a ball passes through tin asphalt sample disk attached to a ring... 

Ethylene. Under the influence of pressure and a catalyst, ethylene yields a white, tough but flexible waxy sohd, known as Polythene. Polyethylene possesses excellent electric insulation properties and high water resistance it has a low specific gravity and a low softening point (about 110°). The chemical inertness oi Polythene has found application in the manufacture of many items of apparatus for the laboratory. It is a useful lubricant for ground glass connexions, particularly at relatively high temperatures. 

Mechanical and Thermal Properties. The first member of the acrylate series, poly(methyl acrylate), has fltde or no tack at room temperature it is a tough, mbbery, and moderately hard polymer. Poly(ethyl acrylate) is more mbberflke, considerably softer, and more extensible. Poly(butyl acrylate) is softer stiU, and much tackier. This information is quantitatively summarized in Table 2 (41). In the alkyl acrylate series, the softness increases through n-octy acrylate. As the chain length is increased beyond n-octy side-chain crystallization occurs and the materials become brittle (42) poly( -hexadecyl acrylate) is hard and waxlike at room temperature but is soft and tacky above its softening point. 

Thermoforming. Thermoforming is the most common method of fabricating sheet into three-dimensional packaging. In conventional thermoforming, the sheet is heated to its softening point or just below the melting temperature. The softened plastic is forced by differential air pressure into an open-top mold to assume the shape of the female mold. The mold is chilled and the plastic sheet solidifies and is then removed from the mold. 

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). 

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. 

Cationic polymerization of coal-tar fractions has been commercially achieved through the use of strong protic acids, as well as various Lewis acids. Sulfuric acid was the first polymerization catalyst (11). More recent technology has focused on the Friedel-Crafts polymerization of coal fractions to yield resins with higher softening points and better color. Typical Lewis acid catalysts used in these processes are aluminum chloride, boron trifluoride, and various boron trifluoride complexes (12). Cmde feedstocks typically contain 25—75% reactive components and may be refined prior to polymerization (eg, acid or alkali treatment) to remove sulfur and other undesired components. Table 1 illustrates the typical components found in coal-tar fractions and their corresponding properties. 

Blends of piperylenes and amylenes (mixed 2-methyl-1-butene and 2-methyl-2-butene) or UOP propylene dimers can be adjusted to produce softening points of 0—100°C and weight average molecular weights of <1200 (32,33). Careful control of the diolefin/branched olefin ratio is the key to consistent resin properties (34). 

Due to the fact that BF is a weaker Lewis acid than AlCl, stmcturaHy distinct resins are obtained upon the respective polymerization of a piperylenes-2-methyl-2-butene system with the two different Lewis acids. Much lower levels of branched olefin are required to achieve a softening point of <40° C with the BF catalyzed system (33,36). In fact, due to its weaker acidity, BF is not useful for producing high softening point resins based on C-5 hydrocarbon feeds. 

Levels of cyclopentadiene (CPD) and dicyclopentadiene (DCPD) in C-5 feedstreams have a great effect on the softening point, as well as the color and thermal stabiUty of the resin. Typically, DCPD is added to C-5 feedblends to increase softening point. However, increased DCPD incorporation... 

G-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

Although most aromatic modified C-5 resins are typically higher softening point resins, certain appHcations, such as adhesives, require lower softening points. Copolymerization of a C-8—C-10 vinyl aromatic fraction with piperylenes in the presence of a C-4—C-8 mono-olefin chain-transfer stream yields resins with softening points ranging from 0—40°C (44). A particular advantage of these Hquid resins is the fact that they eliminate the need for plasticizers or oils in some pressure sensitive adhesive appHcations. 

The increase in softening point measured after heating each resin at 220°C for 3 h. The smaller the increase, the better the heat stability. 

In order to increase the solubiUty parameter of CPD-based resins, vinyl aromatic compounds, as well as other polar monomers, have been copolymerized with CPD. Indene and styrene are two common aromatic streams used to modify cyclodiene-based resins. They may be used as pure monomers or contained in aromatic steam cracked petroleum fractions. Addition of indene at the expense of DCPD in a thermal polymerization has been found to lower the yield and softening point of the resin (55). CompatibiUty of a resin with ethylene—vinyl acetate (EVA) copolymers, which are used in hot melt adhesive appHcations, may be improved by the copolymerization of aromatic monomers with CPD. As with other thermally polymerized CPD-based resins, aromatic modified thermal resins may be hydrogenated. 

Reduction of the aromatic nuclei contained in catalytic C-9 resins has also been accomplished in the molten state (66). Continuous downward concurrent feeding of molten resin (120°C softening point) and hydrogen to a fixed bed of an alumina supported platinum—mthenium (1.75% Pt—0.25% Ru) catalyst has been shown to reduce approximately 100% of the aromatic nuclei present in the resin. The temperature and pressure required for this process are 295—300°C and 9.8 MPa (lOO kg/cni2), respectively. The extent of hydrogenation was monitored by the percent reduction in the uv absorbance at 274.5 nm. 

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