Cellular polymer

Cellular ebonite Cellular phones Cellular plastics Cellular polyethylene Cellular polymers... 

The first cellular synthetic plastic was an unwanted cellular phenol—formaldehyde resin produced by early workers in this field. The elimination of cell formation in these resins, as given by Baekeland in his 1909 heat and pressure patent (2), is generally considered the birth of the plastics industry. The first commercial cellular polymer was sponge mbber, introduced between 1910 and 1920 (3). 

Cellular polymers have been commercially accepted in a wide variety of appHcations since the 1940s (10—19). The total usage of foamed plastics in the United States has risen from 441 X ICf t in 1967 to 1.6 x 10 t in 1982, and has been projected to rise to about 2.8 X 10 t in 1995 (20). 

The gas phase in a cellular polymer is distributed in voids, pores, or pockets called cells. If these cells are intercoimected in such a manner that gas can pass from one to another, the material is termed open-ceUed. If the cells are discrete and the gas phase of each is independent of that of the other cells, the material is termed closed-ceUed. 

The nomenclature of cellular polymers is not standardized classifications have been made according to the properties of the base polymer (22), the methods of manufacture, the cellular stmcture, or some combination of these. The most comprehensive classification of cellular plastics, proposed in 1958 (23), has not been adopted and is not consistent with some of the common names for the more important commercial products. 

A summary of the methods for commercially producing cellular polymers is presented in Table 1. This table includes only those methods thought to be commercially significant and is not inclusive of all methods known to produce cellular products from polymers. 

One method (116) of producing cellular polymers from a variety of latexes uses primarily latexes of carboxylated styrene—butadiene copolymers, although other elastomers such as acryUc elastomers, nitrile mbber, and vinyl polymers can be employed. 

Syntactic Cellular Polymers. Syntactic cellular polymer is produced by dispersing rigid, foamed, microscopic particles in a fluid polymer and then stabilizing the system. The particles are generally spheres or microhalloons of phenoHc resin, urea—formaldehyde resin, glass, or siUca, ranging 30—120 lm dia. Commercial microhalloons have densities of approximately 144 kg/m (9 lbs/fT). The fluid polymers used are the usual coating resins, eg, epoxy resin, polyesters, and urea—formaldehyde resin. 

The resin, catalyst, and microhalloons are mixed to form a mortar which is then cast into the desirable shape and cured. Very specialized electrical and mechanical properties may be obtained by this method but at higher cost. This method of producing cellular polymers is quite appHcable to small quantity, specialized appHcations because it requires very tittle special equipment. 

Sintering has been used to produce a porous polytetrafluoroethylene (16). Cellulose sponges are the most familiar cellular polymers produced by the leaching process (123). Sodium sulfate crystals are dispersed in the viscose symp and subsequently leached out. Polyethylene (124) or poly(vinyl chloride) can also be produced in cellular form by the leaching process. The artificial leather-tike materials used for shoe uppers are rendered porous by extraction of salts (125) or by designing the polymers in such a way that they precipitate as a gel with many holes (126). 

Cell Structure. A complete knowledge of the cell stmcture of a cellular polymer requires a definition of its cell sizes, cell shapes, and location of each cell in the foam. 

Density and polymer composition have a large effect on compressive strength and modulus (Fig. 3). The dependence of compressive properties on cell size has been discussed (22). The cell shape or geometry has also been shown important in determining the compressive properties (22,59,60,153,154). In fact, the foam cell stmcture is controlled in some cases to optimize certain physical properties of rigid cellular polymers. 

Fig. 3. Effect of density on compressive modulus of rigid cellular polymers. A, extmded polystyrene (131) B, expanded polystyrene (150) C-1, C-2, polyether polyurethane (151) D, phenol—formaldehyde (150) E, ebonite (150) E, urea—formaldehyde (150) G, poly(vinylchloride) (152). To convert...

Thermal Conductivity. More information is available relating thermal conductivity to stmctural variables of cellular polymers than for any other property. Several papers have discussed the relation of the thermal conductivity of heterogeneous materials in general (187,188) and of plastic foams in particular (132,143,151,189—191) with the characteristic stmctural variables of the systems. 

As a good first approximation (187), the heat conduction of low density foams through the soHd and gas phases can be expressed as the product of the thermal conductivity of each phase times its volume fraction. Most rigid polymers have thermal conductivities of 0.07-0.28 W/(m-K) and the corresponding conduction through the soHd phase of a 32 kg/m (2 lbs/fT) foam (3 vol %) ranges 0.003-0.009 W/(m-K). In most cellular polymers this value is deterrnined primarily by the density of the foam and the polymer-phase composition. Smaller variations can result from changes in cell stmcture. 

Table 5. Thermal Conductivity at 20°C of Gases Used in Cellular Polymers ...

There is ordinarily no measurable convection in cells of diameter less than about 4 mm (143). Theoretical arguments have been in general agreement with this work (151,191). Since most available cellular polymers have cell diameters smaller than 4 mm, convection heat transfer can be ignored with good justification. Studies of radiant heat transfer through cellular polymers have been made (143,151,191,196,197). 

The variation in total thermal conductivity with density has the same general nature for ah. cellular polymers (143,189). The increase in at low densities is owing to an increased radiant heat transfer the rise at high densities to an increasing contribution of k. ... 

The thermal conductivity of a cellular polymer can change upon aging under ambient conditions if the gas composition is influenced by such aging. Such a case is evidenced when oxygen or nitrogen diffuses into polyurethane foams that initially have only a fluorocarbon blowing agent in the cells (32,130,143,190,191,198-201). 

SpeciTc Heat. The specific heat of a cellular polymer is simply the sum of the specific heats of each of its components. The contribution of the gas is small and can be neglected in many cases. 

Coefficient of Linear Thermal Expansion. The coefficients of linear thermal expansion of polymers are higher than those for most rigid materials at ambient temperatures because of the supercooled-liquid nature of the polymeric state, and this applies to the cellular state as well. Variation of this property with density and temperature has been reported for polystyrene foams (202) and for foams in general (22). When cellular polymers are used as components of large stmctures, the coefficient of thermal expansion must be considered carefully because of its magnitude compared with those of most nonpolymeric stmctural materials (203). 

Maximum Service Temperature. Because the cellular materials, like their parent polymers (204), gradually decrease in modulus as the temperature rises rather than undergoing a sharp change in properties, it is difficult to precisely define the maximum service temperature of cellular polymers. The upper temperature limit of use for most cellular polymers is governed predominantly by the plastic phase. Fabrication of the polymer into a... 

Modification of cellular polymers by incorporating amide, imide, oxa2ohdinone, or carbodiimide groups has been attempted but only the urethane-modified isocyanurate foams are produced in the 1990s. PUIR foams often do not require added fire retardants to meet most regulatory requirements (34). A typical PUIR foam formulation is shown in Table 6. 

Physically, additives may be divided into four groups, solids, rubbers, liquids and gases, the last of these being employed for making cellular polymers. In terms of function there are rather larger numbers of groups, of which the following are the most important ... 

The term filler is usually applied to solid additives incorporated into the polymer to modify its physical (usually mechanical) properties. Air and other gases which could be considered as fillers in cellular polymers are dealt with separately. A number of types of filler are generally recognised in polymer technology and these are summarised in Figure 7.1. 

Products with very low dielectric constant (about 1.45) can be obtained by the use of cellular polymers. Blowing agents such as 4,4 -oxybisbenzenesulphono-hydrazide and azocarbonamide are incorporated into the polymer. On extmsion the blowing agent decomposes with the evolution of gas and gives rise to a cellular extrudate. Cellular polyethylene is a useful dielectric in communication cables. 

Complete imidation will not occur but that which does will be accompanied by the formation of a cellular structure to produce a rigid cellular polymer. 

The foams, marketed by Rohm as Rohacell, are stable at room temperature to hydrocarbons, ketones, chlorinated solvents and 10% sulphuric acid. They may be used under load at temperature up to 160°C. Uses quoted for these materials include bus engine covers, aircraft landing gear doors, radar domes, domes, ski cores and tennis racket cores. Their potential is in applications demanding a level of heat deformation resistance, solvent resistance and stiffness not exhibited by more well-known cellular polymers such as expanded polystyrene and the polyurethane foams. 

It should be realized that flammability of foams is a complex subject area and the "mechanism by which cellular polymers with different physical forms (cell sizes, etc.) lose heat at high temperatures have received surprisingly little attention" [19]. The... 

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