ANNUAL REVIEW
R. B. S E Y M O U R
P R O G R E S S R E P O R T ON THE P L A S T I C S I N D U S T R Y Benejts from previous investments in research prompt a mature plastics industry to emphasize fundamental investigations of macromolecular structures.
n industry that has been unduly criticized, under-
A estimated, misunderstood, and occasionally discredited in its formative years is now recognized as the major source of critical components for almost every space age activity. As a result of the relaxation of outdated building codes, over a million pounds of reinforced plastics and a quarter of a million square feet of acrylic sheet plastics were used in construction a t the New York World’s Fair. These unique designs, which are not adaptable to classical materials, serve as prototypes for a new era in building. Many other architectural problems have been solved through the use of available plastics, the development of new functional polymers, or the use of combinations of plastics and other structural materials. The inherent versatility of these non-critical products and their role in the national economy have assured an important place for plastics in every progressive nation. The Nobel Award in chemistry to Guilio Natta and Karl Ziegler was a timely, significant, and appropriate recognition of the industrial and social importance of basic knowledge of macromolecular structures and polymerization techniques. While this report does not disregard the many advances in practical
plastics technology, it stresses instead progress made in polymer science. The future growth of this giant, versatile industry will be dependent on new advances in basic polymer knowledge and proper design and fabrication of appropriate plastics in the solution of problems in all types of construction. A decade of unprecedented service by reinforced plastic car bodies, pipelines, skylights, floor tile, and building panels has already stimulated new applications ranging from snap-on lids for metal cans to prefabricated motel units and lighthouses. Successful experience with reinforced plastic boats in sizes up to 52 feet has made this the preferred material of construction for small boats in the U. S. Navy and Coast Guard Service. Processes based on both photoconductivity and thermoplasticity have been used to produce grainless images on three-layer films. As a result of a myriad of successful case histories and a host of new unique applications, almost 10 billion pounds of plastics will be produced in the U. S. A. this year. Plastics ranks as the fastest growing and one of the most important industries in major countries throughout the world. The combined production of plastics in Germany, France, Japan and the United Kingdom in 1964 will exceed 10 billion pounds. Plastic Structures
Until recently, plastics growth depended on the production and sale of gadgets, toys, and novelties. Hyatt’s fame was based on the fabrication of a billiard
R. B. Seymour i s Associate Professor of Chemistry at the University of Houston. T h e assistance of F. Smith of Oregon State University in the preparation of this review i s acknowledged. AUTHOR
VOL. 5 6
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A Jilament wound tank installation (Poxyglas). Note that the low thermal conductivity of this material results in a cool surface, though the tank contents are heated with the steam coil shown. For extreme conditions, such tanks can be provided with one or two inches of insulation installed between two shell walls
ball, and the principal initial use of Baekeland’s resin a half century ago was for tobacco pipes. While these outlets continue to exist, the emphasis is on more critical large volume applications. It is anticipated that at least one third of the 15 billion pounds of plastics production predicted for 1970 will be used as materials of construction. A new trade journal “Architectural Plastics International” will be issued to provide essential design information. All structures will not require an architect’s services but even the simplest end product will benefit from design information and standards developed for critical structures. The building industry in Great Britain, which has already published a guidebook and has established 30 new standards, has offered to exchange its know-how in the Common Market. The 400 foot long floating wing of the Bell exhibit at the World’s Fair ~ 7 a sassembled from 12 X 41 foot reinforced plastic panels. While less glamorous and available to fewer viewers, the significance of the 200 X 100 X 58 foot air supported vinyl coated nylon structure a t The Dalles, Ore., and the 12 X 60 foot plastic air pollution control stack in a West Coast kraft paper mill should not be overlooked. The lack of flame resistance of general purpose reinforced plastics has been remedied by the use of flame resistant resins and fillers. Larger blow molded vessels are now possible through the use of liquid carbon dioxide as a coolant. New design information for pressure vessels is available ( 3 A ) . Differential thermal analysis (DTA) has been used for the investigation of basic plastic materials (44). Thermal stability indexes are available for 30 different polymers (5A). The stress-strain behavior of plastic composites has been described Inatherriatically ( I A ) , 44
INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
The elastic modulus, thickness, and degree of deterioration of plastics laminates has been determined by ultrasonic tes;ts (ZA). Composites
Even simple space capsules are composite structures in which each component contributes to the overall properties (77B). The design of 100-foot-diameter inflatable space reflectors and large space vehicles is dependent on more fundamental knowledge of polymer structure and relationships between the components of the composite structure (?5B,ZIB). Non-space structures such as the 36-foot baptismal pool, the enormous suspension roof of the New York State pavilion, and the majestic arches in the Mormon pavilion at the World’s Fair plus the 100,000 cars with reinforced plastic bodies now on U. S. highways serve to demonstrate the effectiveness of this type of construction (77B, 76B). Over 300 million pounds of reinforced plastics will be used in the C . S. A . this year and the annual volume should double by 1971. Composites which utilize the ultimate properties of the components more fully are based on filament winding (79B). This type of construction accounts for only 5% of the present volume of reinforced plastics. However, the use of filament wound barrel staves and other novel construction assures a rapid growth for this type design. Filament wound tanks with capacities of over 2000 gallons demonstate the potential design possibilities. Filled thermoplastics are less versatile than reinforced thermosetting plastics. Yet, such composites extend the usefulness of thermoplastics and will account for over 307, of all engineering plastics in 1970 (4B). Chemical resistant glass fibers are preferred over alkali type or electrical grade glass fibers for corrosion
resistant applications (7B). Improved physical properties have been obtained through the use of hollow glass fibers (3B) and fiber bundles (7B, 6B). Treatment of fibers with silane coupling agents assures bonding of resin and glass (5B, 2OB). The bond may be checked by the use of ultrasonic tests (78B). New information on properties of these products is available (ZB, 9B, 72B). Polyester resins which cure under water have extended the usefulness of composites (70B). Masonry mortars compounded with resins (73B) and mixtures of coal tar pitch and epoxy resins have provided improved highway surfaces. New applications of metalplastic composites have been described (8B). Aluminum-polyethylene laminates may be deep drawn with a heated punch. Hard products have been obtained by using x-radiation to polymerize monomer-impregnated wood. New information on phenolic resin laminates is available (74B). Plastic bearings have been obtained by molding finely pulverized polyfluorocarbon resin in an acetal matrix. The service life of rifles has been extended by a n occasional firing of bullets of polyfluorocarbon filled with powdered glass and metal. Plastics vs. Temperature
When composites are designed for high temperature service, both the resin and filler must be heat resistant. Apparently, nearly perfect crystals called whiskers constitute the ultimate in high temperature reinforcement ( 75C). Resin-bonded aluminum needles, crocidolite asbestos (79C), carbon based fibers, and zirconia polycrystalline fibers are also being used (27C). Reinforced plastics are satisfactory for heat shields and rocket motors but current design does not make optimum use of the inherent physical properties of these composites (2ZC). New tests for ablative materials (3C) and techniques for altering properties of space vehicles (24C) and for the design of self-extinguishing plastics structures have been described (7C, 74C). The choice of materials used depends on the anticipated service (8C, 72C, 2OC). Efforts toward the development of new heat resistant polymers (25C) have resulted in the synthesis of polybenzimidazoles (73C) and related polyimides which are superior to polyfluorocarbon polymers (2C, 9C, 70C) and are available in film form ( I C ) . Other heat resistant products are carborane polymers obtained by copolymerization of the reaction product of decaborane and acetylene derivatives (6C), linear p-phenylene sulfides (23C),sulfur-nitrogen polymers and catenated rings (78C), fluoroalkyl heterocyclic polymers, and coordination (77C) and inorganic polymers (SC). Thermosetting plastics such as heat resistant alkyds (77C), chlorinated polyethylene (76C), and poly-1,2dichloroethylene (4C) are suitable for hot water service temperatures. Chlorinated polyethylene is actually a terpolymer of ethylene, vinyl chloride, and 1,2-dichloroethylene. Non-yellowing, temperature-resistant acrylic plastics are being used for mercury lamp lenses.
Plastics vs. Environment
The classical empirical approach to the study of the effect of environment on plastics is being replaced by more fundamental investigations. Radiation studies have shown that the degree of cross-linking is a function of the temperature (260) and that the resistance to nitric acid is proportional to the degree of cross-linking and, hence, to the relative reduction in crystallization (760). Reproducible humidity aging tests have been used to study the overall aging characteristics of plasticized polyvinyl chloride (790). Significant weight losses are not observed when reinforced plastics are tested (2i’D) but much can be learned from an investigation of unfilled films ( 5 0 ) or from the acidity of hot water extracts of reinforced polyester plastics ( 7 2 0 ) . I n spite of statements to the contrary, the overall effect of aging on polyamide G is not equal to the summation of the effects of the individual components ( 6 0 ) . Activation energy values a t the onset of oxidation may be used to determine the relative effectiveness of antioxidants in polyolefins ( 7 ID). The fundamental changes that occur in the presence of corrosives have been described (220). The concentration of hydrochloric acid released by vinyl chloride polymers on aging can be expressed as a linear function in respect to time (230, 2 4 0 ) . Additional references to the effects of environment on plastics are as follows: changes in hardness of 11 rigid plastics exposed to 27 test chemicals ( 2 7 0 ) ,elastomers us. salt water ( 4 0 ) ) elastomers us. hydrazine fuels (700), polypropylene us. corrosion ( 2 0 0 ) ,plastics us. corrosion ( 7 0 , 7 0 , 9 0 , 770)) plastics us. outer space (730), ultraviolet light stabilizers (30), reinforced phenolic reinforced polyester resins (20, 80, 250), resins (740), hydrogenated bisphenol-A polyester resins ( 7 5 0 ) , and epoxy resins cured with cyclohexane diamines ( 7 8 0 ) . Sheet and Film
Temporary protection against environment is often supplied by plastic films but sheets or laminates are usually required for long term protection. One of the largest plastic laminated film structures is the Echo I1 Sateloon which is contained in a n eleven cubic foot package before being inflated to a 54,000 sq. ft. area. Techniques have been developed for the production of one millimil thick films by the polymerization of ionized monomer vapors under reduced pressure. Polypropylene film 0.1 mil thick is available in roll form. Lettuce and other crops, protected by heavier polyethylene film mulch, mature as much as 2 weeks early. The addition of electrolyte resins to plastic films increases the moisture vapor transmission as much as 10-fold. Film of polytetrafluoroethylene may be formed in the presence of poly-2-methyl furan. Etched polyfluorocarbon film may be adhered to substrates by the use of epoxy resins (5E) and other adhesives (4E). This type film may be deposited from a colloidal slurry by electrophoresis followed by air drying and sintering (ZE). Rigid polyvinyl chloride and sheet metal coated with VOL. 5 6
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AUGUST 1964
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Fundamental investigations have resulted in development
polyvinyl fluoride are being used as siding for residential construction. Adhesion of the plastic films to the metal substrate is improved by the use of primers based on precious metals. Large quantities of flexible polyvinyl chloride sheet serve as barriers protecting dock piles against marine borer attack. Rigid polyvinyl chloride sheet in widths up to 66 inches is available. Corrugated sheet of this plastic is being used for drop ceiling construction and for structural siding. Over 100 million pounds of acrylic sheet will be used this year for signs, doors, two-man submarines, skylights, and domes. A transparent dome 38 feet X 102 feet was erected a t the International Inn at Washington, D. C. Almost 10,000 cast acrylic sheets were used in the construction of the dome at the Houston stadium. Boats up to 14 feet in length are being vacuum formed from polyethylene sheet stock. Liners and containers with capacities up to 45 gallons have been produced by blow molding polyethylene. Larger containers have been produced by the automatic assembly of polyvinyl chloride sheets. Techniques are available for joining plastics by dielectric, induction, and ultrasonic bonding (7E, 3E, 6 E ) . Considerable quantities of polyethylene film are being used for the construction of large shipping bags. Coatings and Linings
Polyvinyl chloride powder blends may be deposited on metal substrates by use of the fluidized bed process (4F, 5F). Adhesion to metal can be improved by the use of a monomolecular film of stearic acid (2F). Coatings may be deposited from solutions or dispersions, by flame spraying, automatic oscillating bed systems, rotational slush molding, and gas phase polymerization of monomers. Powdered polymers may be knife spread and fused. Carpets for almost all 1964 automobiles are backed by a fused coating of powdered polyethylene. The magnitude of the protective coatings industry is demonstrated by the coating of 20,000 miles of pipelines in the U. S. A. in 1963. A new automatic process for the application of thin coatings of styrene-butadiene copolymer has been proposed as an alternate to thick coal tar pipe enamels. The recognition of the importance of conserving water has fostered the lining of irrigation canals (7F) and reservoirs. Monolithic linings of polyvinyl chloride film were used to line a 15-acre lake at Llano Reservoir in Costa Rica and a salt water storage basin a t Snyder, Texas. New information on monolithic linings of polyester and epoxy resins has been published (627). Battery separators have been produced by bubbling ethylene into 46-
INDUSTRIAL A N D ENGINEERING CHEMISTRY
a toluene slurry of cellulose fibers in the presence of a catalyst. Chemically cross-linked polyethylene (7F) and foamed-in-place polyethylene are being used for wire coatings (3F). Cellular Products
The Pieta exhibited at the World’s Fair was undamaged during shipment because it was protected by polystyrene foam. Extruded flame resistant cellular material of this type is being used for roof panels and building insulation. A product with improved cell size and strength is obtained when isopentane is used as the expanding agent (5G). Over two thousand diamond shaped preforms of flame resistant polyurethane were used to erect 18 twentyseven foot diameter radomes in Canada and the U. S. A. This type of foam (3G, 7G) has been proposed as a substitute for casting compositions (8G). According to the Urethane Institute of the Society of the Plastics Industry, the total annual production of polyurethane exceeds 225 million pounds. Readily moldable one-shot urethane foams (2G) can be made flame resistant without reducing strength and other desirable physical properties ( I G ) . A relationship between water vapor permeability and structure has been demonstrated (4G). Foams with improved quality have been produced from toluene diisocyanate and glycosides (6G)* Plastic Pipe
Considerable publicity was given to the repair of a corroded metal pipeline by the insertion of plastic pipe surrounded by epoxy resin since the line was under 33 feet of water in the Houston Ship Channel. However, many of the applications of the 125 million pounds of plastic pipe produced this year are equally newsworthy from a n engineering viewpoint ( 4 H ) . It is anticipated that over 300 million pounds of plastic pipe will be produced in 1969. Other interesting innovations were the use of 700 feet of continuous 3-inch polyethylene pipe for conveying diesel oil from ship to shore in the Bahamas, the suspension of polyacetal natural gas pipelines on existing telephone poles in rural communities, and the laying of 45 miles of ABS water pipe 42 inches below the frost line in Colorado. Much of the phenomenal economic and technical success of this industry may be attributed to investment in technology and the establishment of significant commercial standards such as CS 254-5,6 (1963) which describe quality, dimensional tolerance, and minimum bursting pressure for over 75y0 of available plastic pipe. Additional technical information for thermoplastic pipe 3H, 5 H ) . is also available (ZH,
of polymers suitable for use in severe environments
Class I and I1 polyvinyl chloride pipe is now available in 20-foot lengths in diameters up to 16 inches. Polyethylene has been extruded over steel pipe as large as 8 inches in diameter and has been reinforced with carbon black and chemically cross-linked to provide exceptional resistance to temperature and weather. Greater resistance to the effects of elevated temperature has been secured by lining metal, asbestos, or reinforced plastic pipe with polypropylene, polyester resin, or reinforced thermoplastics ( 7 2 3 ) . Glass and asbestos reinforced epoxy and polyester pipe continue to provide excellent service in chemical process plants and sewer lines. Progress in Polymer Science
A continuation of the investigation of the science of high polymers has resulted in the development of new materials and in the improvement of the quality of standard plastics (25J). Double polymer chains or ladder-like structures have been obtained by the free radical polymerization of thiocarbonyl fluoride, cyclization of poly 3,4-isoprene, and polymerization of vinyl isocyanate. The flexibility of polycarbonates has been reduced by the addition of anti-plasticizers such as chlorinated biphenyl, terphenyl, polystyrene glycol, or abietic acid derivatives. New information on plastic materials is as follows : Polyolefins. Over 2 billion pounds of general purpose and 400 million pounds of high density polyethylene and 250 million pounds of polypropylene will be produced in the U. S. A. this year. Flexible copolymers of ethylene with vinyl acetate, ethyl acrylate, or propylene will contribute to the 3 billion pound production anticipated for 1965 ( 2 J ) . Copolymerization of ethylene with propylene in the presence of non-conjugated dienes produces stereoregular, flexible, oil extendable products which may be cured with sulfur or phenolic resins (74J). Products with similar properties are also obtained when propylene oxide is polymerized by coordination compounds. Irradiation of polyolefins (35J) or heating of mixtures containing carbon black and organic peroxides yields cross-linked products ( 7 J ) . New design data for polypropylene are available (76J). Polychlorocarbons. Rigid polyvinyl chloride structures have not been used as widely in the U. S. A. as in other countries, almost 2 billion pounds of vinyl chloride polymers will be produced this year. The availability of powder blends should increase the use of such products (6J, 3 6 4 . Considerable new information on plasticizers and other additives for polyvinyl chloride is available (3J, 5J, 23J, 28J, 30J, 37J). Plasticizers with free carboxyl groups are advantageous ( 7 7 4 . Bisphenol-A is an
effective stabilizer (4J). Impact strength can be increased without decreasing stiffness by the addition of chlorinated polyethylene (26J). Styrene Polymers. The fast growing engineering plastics ABS and SAN will account for 7.5 and 2.5 percent of the 1.6 billion pounds of styrene plastics produced in the U. S. A. this year. The use of expanded ABS plastics for the production of large structures assures continued growth of this type of product (77J). Polyfluorocarbons. Four different types of fluorocarbon polymers contributed to the 20 million pound production of this type plastic. Large parts have been produced by compressing a naphtha slurry of finely divided polymer, sintering and recompressing the molding. Precision woven monofilament polyfluorocarbon cloth has been produced (73J). Polyester Plastics. Flexible copolymers of ethyl acrylate and chloroethyl vinyl ether are being used for oil resistant products (24J). Thermosetting acrylic enamels are used for coating home appliances. About 10 million pounds of polycarbonate plastics will be produced in the U. S. A. this year (75J, 78J). Crystallization of plasticized films has been reduced by quenching a t low temperatures (29J). Ultraviolet stabilized sheet and film are available. Improved polyester plastics have been obtained from anthracene-maleic anhydride adducts, from reaction products of anhydrides and epoxides (37J),and by tailoring the structure so that the unsaturation is predominantly near chain ends (27J). Polyaldehydes. Copolymers of formaldehyde and acetaldehyde are more elastic than those containing acrolein (27J) or polyacrolein plastics with free aldehyde groups ( 7 J ). Aging of acetal resins has been improved by the addition of carbon black (34J). New technical information for these resins has been published (201, 33J ). Epoxy Resins, Improved products have been obtained by modifying epoxy resins with furans (22J),use of tetrabromobisphenol-A (IOJ), epoxidation of cyclic olefins by peracetic acid and by curing with dimerized C-18 fatty acids, styrene-maleic anhydride resins and polyazelaic polyanhydride (84. The effect of other variables ( 9 J )and the changes in infrared spectra during curing (72J, 79J) have been investigated. Miscellaneous, Phenoxy resins with both thermosetting and thermoplastic properties are now classified as engineering plastics (32J). Dust-free phenolic molding powders may be molded by a modified injection molding process. Nylon with hydrophyllic properties has been obtained by radiation grafting of appropriate monomers. Flexible transparent room-temperature curing silicones, silicon-nitrogen polymers and phospene oxide polymers are available. VOL. 5 6
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LITERATURE CITED Plastic Structures
(1.4) Brock, F. H., J.Appl. PolymerSci. 7, No. 5, 1613 (1963). (2A) Hitt, W. C . , Ramsey, J. B., Rubber Plastics Age 44, 411 (1963). (3A) Hofeditz, J. T., Mod. Plastics 41, No. 8 , 127 (1964). (4A) Millane, J. J., Plastics 28, N‘o. 34, 101 (1963). (5A) Reich, L., Levi, D . LV., Makromo!. Chem. 6 6 , 102 (1963).
(21D) Preston, H. M.. M’ahl, K. E., Inst. Environ., Science Tech. Meeting Proc., Chicago, 1960, p 349. (22D) Seymour, R. B., Plastics World 22, No. 4, 50 (1964). (23D) Stepanek, J., Dolezel, B., Chem. Listy 57, No. 8, 818 (1963). (24D) Stepek, J., Vymazal, Z., Modern Plastics 40,No. 10, 146 (1763). (25D) Szymanski, W. A,, Talbot, R. C., Ind. Eng. Chem. 5 6 , No. 4, 39 (1964) (26D) Todd, G., Weld, G . A., Nature 199, KO. 4889, 172 (1963). (27D) Van Delinder, L. S., M o t e r . Protect. 2, No. 5, 30 (1963). Sheet a n d Film
Composites ( l a ) Ballo, R., Hajdoczky, G., Acta. Chim. Acad. Sci. Hung. 39, No. 1, 129 (1963). (2B) Boenig, H . V., “Unsaturated Polyesters,” .4merican Elsevier Publishing Go., New York, 1964. (3B) Carter, H . A,, Moorefield, S.A , , Plastics Technol. 9, KO. 9, 42 (1963). (4B) Chadbourne, M’. B., Murphy, T. P., Reinforced Plastics 2, No. 4, 18; No. 5. 8 (1963). (5B) Clark, H . A,, Plueddemann, E. P., Mod. Plastics 40, No. 10, 133 (1963). (6B) Davis, R . L., Plastics World 21, No. 11, GO (1963). (7B) Feuer, S. S., Torres, A . F., Chem. Eng. 70, KO.15, 168 (1963). (8B) Fraussen, H., Metall 17, 600 (1963). (9B) Furse, C., Corrosion Prevent. Control 10, No. 7, 24 (1963). (10B) Gassinger, H . A,, 20th Annual Tech. Conf. S.P.E., Atlantic Cit)-, N. J., Jan. 27, 1964. (11B) Klema, F., Kunststoffe-Plastics 10, 35 (1963). Przemsyl Chem. 42, 73 (1963) (12B) Klosowska, Z., (1313) Kubisiak, D. F., Eash, R . P., 20th Annual Conf. S.P.E., Atlantic Clty, K. J., Jan. 27, 1964. (14B) Lukovenko, T . M., Li, P. Z., P/asticheskie Massy No. 4, 10 (1959). (l5B) Mark, H. F., Intern. Sci. Techno!. 27, No. 3, 72 (1964). (16B) Mumby, K., Kunstrtoffe-Plastics 10, 25 (1963). (17B) Pebly, H. E., Chem. Eng. 71, No. 1, 75 (1964). (18B) Ramsey, J. B., Western Plastics 10, KO. 9, 33 (1963). (19B) Rosato, D. V., Reinforced Plastics 3, No. 3, 14 (1964). (20B) Sterman, S., Marsden, J. G., Mod. Plastics 40, N-0. 11, 125; 41, So. 2, 254 (1963). (21B) U’underlich, B., Ind. Eng. Chem. 56, KO.2, 19 (1964).
Plastics vs. Temperature (1C) Amborski, L. E., Ind. Eng. Chem. Prod. Res. Develop. 2, No. 3, 189 (1963). (2C) Bower, G. M., Frost, L. M’., J.Polymer Sci.,Pt. A . 1, No. 10, 3135 (1963). (3C) Denney, M . A.: Martindale, J. C., Aircraft Eng. 35, 10 (1963). (4C) Garvan, G. S., Western Plasfics 10, No. 7, 27 (1963). (512) Gimblett, F. G., “Inorganic Polymer Chemistry,” Butterworth’s, London, 1963. (6C) Green, J., Mayes, N.. J.Polymer Sci., Pt. B. 2, KO.1, 109 (1964) ( 7 C ) Hammer], A. J., Reinforced Plastics 2, No. 5 , 22 (1963). (8C) Isenberg, L., Chem. Eng. Prog. 60, No. 2, 63 (I964). (9C) Klema, F., Chemiker Ztg. 87, KO.13, 472 (1963). (1OC) Johnson, R. L., Buckley, D. H., 20th Annual Conf. S.P.E., Atlantic City, N . J., Jan. 27, 1964. (11C) Long, J. T., Hoover, L. P., S P E J . 19, 1090 (1963). (12‘2) Lurie, R., Georgiev, S . , Chem. Eng. Progr. 60, No. 2, 62 (1964). (13C) Marcel, C. S., SPE J. 20, 220 (1964). (14C) Medvedeva, P. A,, Rybkina, 0 . Y . , Plasticheskie Massy No. 9, 17 (1963). (15C) Mileweski, J. V., Shine, J. J., Reinforced Plastics 3, No. 2, 10 (1964). (16C) Ostwald, J., Kubin, E. T., S P E Trans. 3, No. 3, 168 (1963). (17C) Parvin, K . , Plastics Inst. Trans. 31, No. 10, 132 (1963). (18C) Popoff, I. C., U.S. Dept. Comm. OBce Tech. Sew. AD 276, 924 (1962). (19C) Rahn, C.L., Edgerton,N-. \ V . , S P E J . 18, 1503 (1963). (ZOC) Rosenweig, R . E., Beecher, N., A I A A J. 1, S o . 8, 1802 (1963). (21C) Schmidt, D. L., Jones, TV. C., S P E J . 20, 162 (1964). (22C) Sheppard, H . R., Sampson, R. N., S P E J. 20, 347 (1964). (23C) Smith, H. A,, Rubber Plastics Age 44, No. 9, 1048 (1963). Series 59, h‘0.~40, 1 (1963), (24C) Strauss, E. L., Chem. Eng. Pmgr.-Symporium (25C) Techel, J., Plastic Kautschuk 10, No. 3, 137 (1963).
Plastics vs. Environment (1D) A d a m , C. H., Chem. Eng. 71, No. 1, 83 (1964). (ZD) Antoni, C. M,Verna, J. R., Chem. Eng. P r o g r . S j m p o s i u m Series 59, KO. 40, 51 (1963). (3D) Baseman, .4. L., Plasfics Techno!. 10, No. 4, 30 (1964). (4D) Connally, R . A,, Mafer. Res. Std. 3, No. 3, 193 (1963). (5D) Cooke, H . G., McWhorten, W.F., Ind. Eng. Chem. 5 6 , S o . 5, 38 (1964). (6D) Dolezel, B.:Chem. Prumsy! 13, No. 7, 388 (1963). (7D) Dominghaus, H., Plastics 28, No. 3, 14, 47 (1963). (8D) Edwards, J. P., Chem. Eng. 70, No. 25, 206 (1963). (9D) Gackenbach, R . E., Chem. Eng. Prog. 59, No. 10, 9 6 (1963). (10D) Green, J., Levine, N. B.: Ind. Eng. Chem. Prod. Res. Develop. 2, No. 2, 127 (1963). (11D) Hansen, R. H., 20th Annual Conf. S.P.E., Atlantic City, N. J., Jan. 27, 1964. (12D) Holtman, R., Kunrtstofe 53, 22 (1963). (13D) Joffe, L. D., C h m . Eng. Progr.-Symposium Series 59, No. 40, 81 (1963). (14D) Keelman, E., Werkstoffe Korrosion 14, 161 (1963). (15D) Kerle, E.J., Plastics Ii’orld 21, No. 12, 22 (1963). (16D) Lamm, A,, Reignot, J., Ind. Plastique Mod. (Paris) 15, No. 3, 15 (1963). (17D) Le Clerc, P., Rappl Tech. 1161-6 (1962). (18D) Lee, H., Watson, F. T., 20th Annual Conf. S.P.E., Atlantic City, Jan. 30, 1964. (19D) Little, J. W., Stroehlein, F. C., S P E J . 20, 366 (1964). (20D) Mueller, U’,, Werkstoffe Korrosion 14, No. 11, 925 (1963).
48
INDUSTRIAL A N D ENGINEERING CHEMISTRY
(1E) (2E) (3E) (4E) (5E) (6E)
Black, P. B., SPE J. 19, 1146 (1963). Bowers, R. C., Zisman, W. A,, Mod. Plartics41, No. 4, 139 (1963) Castagna, E. G., Plastics Tech. 10, No. 3, 32 (1964). Korolov, A. Y., Bek, V. I., Vysokomolekul. Soedin. 4, 1411 (1962). Schmidt, J. E., Mathews, A . L., Prod. Eng. 34, N-0. 11, 43 (1963). S P E J . 19, 1142 (1963).
Coatings a n d Linings
(1F) Bureau of Reclamation, ”Lining for Irrigation Canals,” U. S. Gov. Print. Off., Washington 25, D . C. Lorant: M., Kunststofje Plastics 10, S o . 2 , 147 (1963). Marshall, D. I., Chem. Eng. Prog. 59, No. 9, 39 (1963). Pailas, V. R., Johnson, R . E,, Western Plastics 10, No. 10, 33 (1963). Renkis, A. I,, Weill, P. S., S P E Tech. Papers 1963,p. 52. Severance, W. A.,Chern. Erg. 70, No. 12, 248 (1963). Suba, M . hl., Tomfohrde, R., Rubber Age 90, 941 (1962).
(2F) (3F) (4F) (5F) (6F) (7F)
Cellular Plastics (1G) Anderson, J. J., Ind. Eng. Chem. Prod. Res. Demlop. 2, No. 4, 261 (1963). (2G) Deckert, E. A,, Himmler, W.A , , Chern. En!. Prog. 59, No. 9, 33 (1963). (3G) Ferrigno, T. H . , “Rigid Plastic Foams,” Reinhold, New York, 1963. (4G) Helado, C. J., Harding, R . H., J . Appl. PoljmriSci. 7, No. 5, 1775 (1963). (5G) Ingram, A. R., Wright, H . A,,Mod. Plastics 41, No. 3, 152 (1963). (6G) Otey, F. H., Zagoren, B. L., Ind. Eng. Chem. Prod, Res. Develop. 2, No.14, 2-51. (1963). (7G) Resnick, I., P. B . Report 762,367 U. S. Depr. Com. Office Tech. Service, 1963. (8G) Woodland, J. H., 20th Annual Conf. S.P.E., Atlantic City, S. J., Jan. 30, 1964. Plastic Pipe
(1H) (2H) (3H) (4H) (5H)
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