5
an l ~]Blaterials of Construction Review by Raymond B. Seymour, Sul Ross State College, Alpine, Tex. Plastics industry growth continues, despite business recession Functional uses and unique properties continue to be emphasized Sizable quantities of engineering plastics are being produced TL BUSINESS RECESSIO~ which oc- curred during the past year affected the plastics industry in many ways. However, in spite of low prices and low profit margins, the growth of the plastics industry continued. While “engineering plastics” were emphasized, the growth of the billion pound plastics (olefin, vinyl chloride, and styrene polymers) continued. It has been predicted that these three plastic types will account for about 607, of the 8 billion pounds of plastics produced in 1965. The total use of “engineering plastics” [acrylonitrile-butadiene-styrene (ABS), polyacetals, polycarbonates, poly- oxetane, and nylon] should be about one half billion pounds in 1965. It is significant that the growth of these tough materials is independent of the general purpose plastics The engineer- ing plastics are replacing other accepted functional materials of construction. World-wide production of plastics paralleled growth in the U.S.A. This nation produced about 507, of the 15- billion-pound total. West Germany, the United Kingdom, and Japan ranked second, third. and fourth. Significant advances were made in plastics education. technical publica- tions, technical expositions, and large scale uses of plastics in structural ap- plications. Los Angeles Trade Technical College and New York State University started two- and four-year courses in plastics technology. A traveling ex- hibit of plastics in building was sponsored by the Society of Plastics Engineers. New plastic journals were introduced in several countries. Made of Plastxr, a three-language publication (English, French, and German), was announced. Over 100,000 feet of plastic pipe and 10 acres of cellular plastic sheet were used in the construction of the United Kingdom’s largest office building. The pipe was in sizes up to 6 inches in di- ameter and included poly(viny1 chlo- ride), high and low density polyethylene, and nylon. This review includes significant de- velopments in the plastics industry during the 12-month period ending June 1, 1961. Design and Engineering Plastics, like all other materials of construction, creep when subjected to stress. Many past failures of plastic structures resulted from a lack of knoivl- edge of stress, strain, temperature, and time relationships for specific plastic materials. Fortunately, sufficient de- sign data are now available to minimize the chance of underdesign and to re- duce the need for overdesigned structures. In addition to case history data cover- ing periods as long as 20 years (22), the design engineer now can benefit from many new tests and standards which assure uniformity (29) and aid in predicting performance (66). In addi- tion to tests comparable to those used for other structural materials, a method based on the evolution of heat during swelling in solvents was proposed (39). In the past, some engineers have criticized the industry because of lack of design data. ’Today, the industry questions why more engineers have not recognized the design possibilities in- herent in plastics materials (87). Thus. the need for classical mortar joints and other accepted methods of construction are being scrutinized. In contrast, helically wound fuel tanks holding 3100 gallons at a pressure of 665 p.s.i. are now specified for rocket fuel tanks. Comparable modern functional design has created many other structures es- sential for the space age (52). Other new developments in design may result from a study of nature’s approach to reinforcements (53). Fortunately, new materials as well as structures may be designed. It is now possible to graft new groups on natural polymers as well as synthetic plastics. For example, amine and carboxyi groups can be built on the polymer molecule. These can then be reacted further undei controlled conditions. Strucfural Application of Plesfics New applications of plastics as struc- tural materials range from standard molded plastic tanks to the aquarium at the Brookfield Zoo: Chicago, Ill. Tanks range in size from polyolefin detergent dispensers IO 100,000-gallon dracories The latter are forerunners of tanks at least 10 times this size. This type of tank has already been used for storage as well as transportation. A report on many phases of structural plastics has been published (64). Tanks up to 12 feet in diameter have been con- structed by filament winding. However. a stainless steel helical winding has been proposed as an external reinforcemenr for all large plastic tanks. The use of vinyl liners for reinforced plastic struc- tures has been proposed. The size of plastic stacks continues to make news. Yet, vinyl and rein- forced plastic stacks up to 40 inches in diameter and 200 feet in height have been in service for over 10 years. Re- inforced plastic stacks 72 inches in diameter were installed in 25-foot sec- tions last year. The tallest reported was 150 feet high. Regardlesq of originality these stacks are now commonplace and perform as expected. Plastic lined pipe which has been used successfully for over 25 yeari continues to be rediscovered. Newer linings of polyfluorocarbon and polyoxe- tane are more resistant than saran Large molded scrubbers arc common- place. Plastic grids, molded oxetanc pumps, and metering devices are standard equipment. Acrylic structures have low absorption for TV beams and ara ideal for broadcasting. Sand has been stabilized by the addi- tion of plastics (26). Modern iron casting technology has been improved by add- ing epoxy resin to surfactant-treated sand (64). A new roof design has been devised through the use of sectional cellular plastic paraboloids Reinforced Plastics The design of an all plastic rocket has been studied. Obviously, most of the material considered from the solid propellant to the phenolic nose cone is classified as reinforced plastic. One of the more important problems, ad- hesion of filler and resin, is still being studied, and progress is being made. The necessity of control of variables 848 INDUSTRIAL AND ENGINEERING CHEMETRY

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Page 1: Plastics. Materials of Construction Review

an l ~ ] B l a t e r i a l s of Construction Review

by Raymond B. Seymour, Sul Ross State College, Alpine, Tex.

Plastics industry growth continues, despite business recession Functional uses and unique properties continue to be emphasized Sizable quantities of engineering plastics are being produced

TL BUSINESS R E C E S S I O ~ which oc- curred during the past year affected the plastics industry in many ways. However, in spite of low prices and low profit margins, the growth of the plastics industry continued.

While “engineering plastics” were emphasized, the growth of the billion pound plastics (olefin, vinyl chloride, and styrene polymers) continued. I t has been predicted that these three plastic types will account for about 607, of the 8 billion pounds of plastics produced in 1965. The total use of “engineering plastics” [acrylonitrile-butadiene-styrene (ABS), polyacetals, polycarbonates, poly- oxetane, and nylon] should be about one half billion pounds in 1965. I t is significant that the growth of these tough materials is independent of the general purpose plastics The engineer- ing plastics are replacing other accepted functional materials of construction.

World-wide production of plastics paralleled growth in the U.S.A. This nation produced about 507, of the 15- billion-pound total. West Germany, the United Kingdom, and Japan ranked second, third. and fourth.

Significant advances were made in plastics education. technical publica- tions, technical expositions, and large scale uses of plastics in structural ap- plications. Los Angeles Trade Technical College and New York State University started two- and four-year courses in plastics technology. A traveling ex- hibit of plastics in building was sponsored by the Society of Plastics Engineers. New plastic journals were introduced in several countries. M a d e of Plastxr, a three-language publication (English, French, and German), was announced.

Over 100,000 feet of plastic pipe and 10 acres of cellular plastic sheet were used in the construction of the United Kingdom’s largest office building. The pipe was in sizes up to 6 inches in di- ameter and included poly(viny1 chlo- ride), high and low density polyethylene, and nylon.

This review includes significant de- velopments in the plastics industry during the 12-month period ending June 1, 1961.

Design and Engineering

Plastics, like all other materials of construction, creep when subjected to stress. Many past failures of plastic structures resulted from a lack of knoivl- edge of stress, strain, temperature, and time relationships for specific plastic materials. Fortunately, sufficient de- sign data are now available to minimize the chance of underdesign and to re- duce the need for overdesigned structures.

I n addition to case history data cover- ing periods as long as 20 years (22), the design engineer now can benefit from many new tests and standards which assure uniformity (29) and aid in predicting performance (66). In addi- tion to tests comparable to those used for other structural materials, a method based on the evolution of heat during swelling in solvents was proposed (39).

I n the past, some engineers have criticized the industry because of lack of design data. ’Today, the industry questions why more engineers have not recognized the design possibilities in- herent in plastics materials (87). Thus. the need for classical mortar joints and other accepted methods of construction are being scrutinized. In contrast, helically wound fuel tanks holding 3100 gallons a t a pressure of 665 p.s.i. are now specified for rocket fuel tanks. Comparable modern functional design has created many other structures es- sential for the space age (52). Other new developments in design may result from a study of nature’s approach to reinforcements (53).

Fortunately, new materials as well as structures may be designed. I t is now possible to graft new groups on natural polymers as well as synthetic plastics. For example, amine and carboxyi groups can be built on the polymer molecule. These can then be reacted further undei controlled conditions.

Strucfural Application of Plesfics New applications of plastics as struc-

tural materials range from standard molded plastic tanks to the aquarium a t the Brookfield Zoo: Chicago, Ill. Tanks range in size from polyolefin detergent

dispensers IO 100,000-gallon dracories The latter are forerunners of tanks at least 10 times this size. This type of tank has already been used for storage as well as transportation.

A report on many phases of structural plastics has been published (64). Tanks u p to 12 feet in diameter have been con- structed by filament winding. However. a stainless steel helical winding has been proposed as an external reinforcemenr for all large plastic tanks. The use of vinyl liners for reinforced plastic struc- tures has been proposed.

The size of plastic stacks continues to make news. Yet, vinyl and rein- forced plastic stacks up to 40 inches in diameter and 200 feet in height have been in service for over 10 years. Re- inforced plastic stacks 72 inches in diameter were installed in 25-foot sec- tions last year. The tallest reported was 150 feet high. Regardlesq of originality these stacks are now commonplace and perform as expected.

Plastic lined pipe which has been used successfully for over 25 yeari continues to be rediscovered. Newer linings of polyfluorocarbon and polyoxe- tane are more resistant than saran

Large molded scrubbers arc common- place. Plastic grids, molded oxetanc pumps, and metering devices are standard equipment. Acrylic structures have low absorption for T V beams and ara ideal for broadcasting.

Sand has been stabilized by the addi- tion of plastics (26). Modern iron casting technology has been improved by add- ing epoxy resin to surfactant-treated sand (64). A new roof design has been devised through the use of sectional cellular plastic paraboloids

Reinforced Plastics

The design of an all plastic rocket has been studied. Obviously, most of the material considered from the solid propellant to the phenolic nose cone is classified as reinforced plastic. One of the more important problems, ad- hesion of filler and resin, is still being studied, and progress is being made. The necessity of control of variables

848 INDUSTRIAL AND ENGINEERING CHEMETRY

Page 2: Plastics. Materials of Construction Review

a n m d Materials of Construction Review

has been recognized and is not being overlooked.

The need for reinforcing fiber un- affected by moisture and high tempera- ture has also been recognized. A new organic fiber (Pluton) which does not melt a t 18,000' F. has been announced. Tensile strength in excess of 120,000 p.s.i. has been observed with quartz fiber-reinforced plastics. A more crit- ical look a t standard tests for reinforced plastics has been recommended (73).

The state of the art in filament wind- ing has been reported (96). Actually, the space age is the reinforced plastic age. This type of plastic is used for rotor blades, jet engine parts, compressor housing, radomes, radar reflectors, and nose cones.

The total production of reinforced plastics in this country was less than 250 million pounds last year. Yet, con- servative estimates predict that the use will double by 1965. Over 60% of the present production is used in construc- tion of buildings, boats, and vehicles.

Interest in polyester-methyl meth- acrylate reinforced plastics (5) and finishes for the glass reinforcement con- tinues (78). However, recent develop- ments with high-modulus glass fiber indicate that such reinforcements can be independent of finish. Hollow glass fibers have been proposed as fillers for light weight plastics. Levy (60) has championed reinforced plastic pipe and compared anticipated performance with nonreinforced pipe. Additional data on the effect of water on long term strength have been published (65).

Heat Resistant Applications The many successful space age ac-

complishments are monuments to ad- vances in the technology of heat-resist- ant plastics. New developments have been reported in both resins and their reinforcements. The results of studies on the relationship of molecular struc- ture to heat resistance were reported

Additional information on heat-resist- ant epoxy and phenolic resins has been published. Inorganic modifica- tions of phenolic resins continue to be of interest (55). Marvel (63) has pre- pared heat-resistant resins by solid state polymerization of diaminobenzene and diphenyl isophthalate. These poly- imidazoles are soluble in dimethyl sulfoxide, exhibit high strength a t 400' F., and lose hydrogen and cross link a t 800' F. A polycaprolactam film with ablative properties has been reported (36).

Plastic Film and Sheet The use of plastic film continues to

increase. I t is estimated that almost one half billion pounds of transparent

(86).

plastic film will be consumed in 1965. Considerable water is being saved through the use of film as liners for irri- gation ditches. Reservoirs and lagoons with capacities up to 6 million gallons of water have been lined with film at Lancaster, Calif., Edmonton, Alberta, and in Australia (84.

Vinyl-coated nylon fabric continues to be used for air-supported structures and inflatable dams. Air-supported structures 50 feet in diameter have been constructed. The capacity of a reservoir in Hawaii was increased by 500 million gallons through the use of an inflatable plastic dam.

Polyethylene sheet can be adhered to copper plated steel (7). Microporous sheet has been produced by molding mixtures of low melting solids and phenolic resins (57).

The use of vinyl-clad steel is now well established. Poly(viny1 fluoride) as well as poly(viny1 chloride) is being used in this application. Polyester film is now being laminated to plywood and other surfaces. A strong polyester film, poly( 1,4-cyclohexylenedimethylene tere- phthalate), is now available (93).

Cellular Plastics The use of cellular plastics has created

a revolution in boat building. For ex- ample, the total weight of the nuclear powered submarine SS Skipjack was reduced by almost 10 tons. This was accomplished through the use of eight tons of polyurethane foam as insulation on the reactor core of the power plant.

Extruded paperlike polystyrene foam is now available. A comparable tech- nique has been applied to coated fabrics. Cellular polystyrene roof structures which require very little support are of con- siderable interest to architects. Steel sheet with a backing of polystyrene foam and sandwiches of foam glass and cel- lular polyurethane are available.

Cellular products based on almost every available plastic have been de- scribed. Flame-proof properties have been incorporated by the addition of fillers (74) or by the reaction with halo- gens. Rubber latex foams have been improved by irradiation of the latex.

Potential creativity with plastic foams was demonstrated by the construction of a 15-foot cellular plastic statue for the American Bowling Congress. Poly- styrene foam of controlled density is now being extruded (23). The use of foamed adhesives has reduced costs in plywood manufacture (34). The insulation of a 10,000-gallon wine tank with a 2-inch-thick sprayed polyurethane foam has been described (75). It has been estimated that 300 million pounds of this type of cellular product will be produced in 1965.

Plastic Pipe Because plastic pipe is now an ac-

cepted type of construction, large in- stallations are no longer newsworthy A 53-mile length of reinforced submarine pipe with an inside diameter of 4.85 inches is conveying gas from Vancouver, British Columbia, to Vancouver Island; 300 tons of poly(viny1 chloride) was used for the inner liner. Polyethylene pipe was wrapped with strips of lead so that it rested on the bottom of a lakr at Milton, Vt.

Twenty three miles of plastic pipe and 50 miles of nylon tubing was used in the construction of a new office build- ing in London. Two miles of vinyl pipe up to 4 inches in diameter was in- stalled in a dairy in Illinois. Four miles of vinyl pipe has given satisfactory service for three years while conveying uranium concentrates in New Mexico.

Four miles of ABS plastic pipe in 40- foot lengths was installed in Orange County, Calif. Metal pipe is now being lined and clad with plastics. A pipe lined with polyethylene tubing measuring 42,000 feet was installed in Warren, Pa.

The trend toward longer lengths of rigid pipe continues. A joining method which consists of shrink fitting by heating over a flexible ring insert has been described.

Work on establishing pipe standards continues. There are now over 25 standards in the U.S.A. Some firms are giving a five year warranty with their pipe.

Expansion and stretching during the extrusion process can increase strengths

AVAILABLE FOR ONE DOLLAR I I I I I I I I copies. I I I I I I I

The complete annotated bibliography of the 1960 Materials of Construe- tion Review of Plastics by Seymour.

After one year this material can be obtained from the AD1 Auxiliary Publica- t ions Project, Library of Congress, Washington 25, D. C., as Document No. 6835. The price will then be $1.75 for microf i lm and $2.50 for photostat

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VOL. 53, NO. 10 OCTOBER 1961 849

Page 3: Plastics. Materials of Construction Review

anI-4 Materials of Construction Review

by 100% (43, 74). Reinforced pipe can be made in continuous lengths (49, 83). While water has an effect on lubricants, stabilizers, emulsifying agents, and other components of pipe, moisture absorption should not be considered as a criterion of bursting strength (97). Van der Wal (92) believes that the heat distortion temperature is more important than water absorption.

Plastics vs. Corrosion

The obvious functional use of plastics in corrosive atmospheres is now being accepted as engineers become acquainted with essential information now avail- able. Recent graduates, of course, possess this knowledge, but too few en- gineers recognize the need of continued study. The knowledge of heat resistant plastics has been accumulated a t a rapid rate because of the space age emergency. A similar situation exists in industry, which is wasting a billion dollars annually in corrosion losses. Fortunately, more engineers are recogniz- ing that the use of plastics can reduce this loss by many millions of dollars.

Case histories of the use of reinforced plastics in corrosive environments have been reviewed (4) . Arndt has empha- sized the need for evaluation under actual conditions of exposure. Bell (70) has recognized the obvious relationship of chemical resistance and molecular con- stitution. This relationship has been emphasized further by Feuer (37) in his studies of polyesters. He compared three different polyesters and observed a wide variation in resistance to chem- icals.

A summary of the chemical resistance of plastics has been published (80). Those who recognized the relationship of chemical structure and corrosive resistance have already designed nu- merous hoods, ducts, and stacks which have stood the test of time in corrosive atmospherm

Coatings and linings

In spite of past mistakes caused by lack of knowledge and overemphasis on this

phase of plastics utilization, coatings and linings are now accepted as standard materials of construction.

The advent of fluidized coatings has created considerable interest in even the most insoluble plastics. This tech- nique and water suspensions have been used for the fabrication of unusually successful linings. The use of poly- oxetane and polyfluorocarbon coatings and linings is now commonplace (70). Automatic coating installations are now in operation with almost every type of chemical resistant plastics (57, 82). The specific advantage of each type is dis- cussed under subsequent headings.

Plastic Materials

Polyolefins. Because of the utility of the end products, the availability of the starting materials, and the ability to regulate molecular structure during polymerization, polyolefins have at- tracted world-wide attention. The pro- duction of linear polyolefins increased by over 100% during the past year. This rate will continue; yet, it will not detract from the growth of the general purpose olefin polymers. It has been predicted that linear polymers will account for 2570 of the 3 billion pounds of polyolefins produced in the U.S.A. in 1965.

Comparable advances have been made with diolefins. I t is now possible to produce either elastic &-polymers or hard trans-polymers by appropriate selec- tion of catalyst (68).

Copolymers of ethylene with ethyl acrylate, vinyl acetate, and styrene are available. The stability of polypro- pylene fiber has been increased by the addition of appropriate inhibitors. All polyolefins can be cross linked if com- pounded with organic peroxides (79). Chlorinated polyethylene is more stable than chlorinated rubber. Blends with poly(viny1 chloride) have improved heat distortion points.

Copolymers of ethylene and propylene exhibit elastic properties (2). Leather can be improved by impregnation with a hot melt of polybutene ( 6 ) . The ad-

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850 INDUSTRIAL AND ENGINEERING CHEMISTRY

verse effect of ultraviolet light on poly- olefins has been minimized (41). The permeability of polyethylene has been decreased by surface fluorination (72). The effects of irradiation on polyole- fins has been reviewed (94).

Vinyl ChIoride Polymers. In spite of low prices and low profit margins, the growth of vinyl plastics continues. Over 1 billion pounds were produced in 1960. I t has been predicted that almost 2 billion pounds will be produced in 1966. Rigid poly(viny1 chloride) (PVC) should account for over 5Y0 of this volume. At least 25% of the total production will be used as materials of construction. Over 250 million pounds of vinyl plastics were used in construc- tion in 1960.

The thermoplastic structure division of the Society of the Plastics Industry has published a manual on the use of PVC in construction. New information has been supplied on fabrication and welding (44, 48, 54, 97).

Large structures fabricated from rigid poly(viny1 chloride) are now common- place. Blends of poly(viny1 chloride) with chlorinated polyethylene, halo- genated butyl rubber, polymethyl acry- late, and a blend of copolymers of styrene-acrylonitrile and butadiene- methyl isopropenyl ketone have been investigated. These products, like the so-called poly(viny1 dichloride) (78), have superior heat resistance and ease of fabrication.

Since it serves both as a heat stabilizer and a light stabilizer, di(isodecy1)-4,5- epoxytetrahydrophthalate has been pro- posed as the ultimate plasticizer for poly(viny1 chloride). Studies on the relationship of solvating power and structure of plasticizers have been made (33). Users have been cautioned about the acute toxicity of triaryl phosphate plasticizers (73) . However, conclusions should be based on end use rather than composition of the ingredients (20).

Polyfluorocarbons. Because of their characteristic resistance to chemicals and heat, polyfluorocarbons continue to be selected for unique and critical applications. Polytetrafluorocarbon re- inforced by ceramic fibers served as the beacon antennae on Diszoverer XI[. Glass fiber-reinforced polyfluorocarbons have proved superior when used as piston rings in jet engines. Self-lubricating retainer rings are fabricated from similar compositions compounded with MoS2. Asbestos saturated with polyfluorocarbons continues to be used for high tempera- ture gaskets.

Thin films of poly(viny1 fluoride) pass 95% of the sun’s energy yet re- flect heat. Thus 2-mil films have been proposed as a cladding for roofs. Mono- filament polyfluorocarbon fibers are also available. Improved flexible hose is

Page 4: Plastics. Materials of Construction Review

an= Materials of Construction Revlew

now produced continuously by simul- taneously winding polyfluorocarbon im- pregnated tape and stainless steel tape around a mandrel.

Copolymers of trifluoronitrosometh- ane and tetrafluoroethylene are flex- ible a t low temperatures and possess the characteristic chemical resistance of this type product (67). A change in volume in excess of 1% has been noted when polytetrafluoroethylene is heated a t 394.2’ F. (59).

Case history data have been provided showing excellent performance of fluoro- carbon-lined pipe (88). Additional in- formation on old and new fluorinated polymers has been published (8, 77, 76). Less than 15 million pounds of polyfluorocarbons was produced by three different firms last year. However, it has been predicted that more than 40 million pounds will be consumed in 1965.

Styrene Polymers. As a result of over 10 years of successful performance as a structural plastic, the blend of co- polymers of styrene, acrylonitrile, and butadiene (ABS) has been classified as an “engineering plastic.” This type of product is now being produced by four firms, and production capacity is being increased. I t has been predicted that this product will be produced at a rate of 100 million pounds in 1965. New copolymers of styrene with butadiene and methyl methacrylate are also avail- able.

I n spite of its shortcomings, poly- styrene continues to be produced at annual rates in excess of a billion pounds. Among the many new uses of styrene plastics (72), probably the most signifi- cant is a simple polystyrene clip for holding six beer cans.

The ability of polystyrene to react with a wide variety of reagents has at- tracted considerable attention (75). The sulfonated product is used in water softening. Pdystyrene has been cross linked with formaldehyde and chloro- sulfuric acid (69). A polymer containing lithium has been described (5G).

Polyacetals. A commercial polymer of formaldehyde introduced less than 2 years ago is already being accepted widely as an “engineering plastic.” Approximately 10 million pounds will be used in 1961. Production is ex- pected to exceed 100 million pounds annually by 1964.

A new copolymer acetal (90) has been announced, and a third firm is considering the production of these interesting tough products. The strength properties of acetals approach those of nonferrous metals.

Properties of acetal resins have been described (9 ) , and crystalline polymers have been obtained from other aldehydes including chloral (35, 37). Lee (58)

has discussed a more efficient gear pump molded from acetal polymer.

Polycarbonates. Polycarbonates can be made by the condensation of phosgene with polyhydric compounds such as bisphenol A (27). Because of its ex- cellent impact resistance, this type of product is also classed as an “engineer- ing plastic.” Approximately 1 million pounds were produced by two firms in the U.S.A. last year. Another firm has announced interest in the production of “phenoxy materials.” Predictions for the sale of 50 million pounds in 1965 and 100 million pounds in 1970 appear to be conservative.

This type of plastic is resistant to aliphatic hydrocarbons, salt solutions, and dilute acids. I t is soluble in chlo- rinated hydrocarbons and slightly soluble in aromatic hydrocarbons (47). Gruen- wald (45) has described cold stamping of this type plastic.

Polyesters. Polyesters have been pro- duced by the reaction of epoxides and anhydrides in the presence of tertiary amines (32). Phosphorous-containing polyesters have superior resistance to flame and heat (38).

The significance of acid number in evaluation of long-term wet strength of glass reinforced polyesters has been discussed (67). Scheimer has empha- sized the importance of variables in- cluding curing time (79). Hazards as- sociated with the use of isopolyesters as maintenance coatings have been dis- cussed (85).

Epoxy Resins. Progress in epoxy resin applications continued during the past year. Over 60 million pounds of base resin was produced by five different firms. Since, in its final application, most of the product was reinforced or filled, the end point weighed about 200 million pounds. The base epoxy resin used in 1966 should approach the present volume of filled resin.

In addition to satellite and missile applications, epoxy resins were used widely for repair of equipment and as jointing materials. A special valve- equipped wrapping for pipe repair is now available. Economies have been claimed when thin metal pipe has been joined with epoxy resins.

High impact sheet has been produced by reinforcing combinations of epoxy resins and thermoplastic materials (30). Epoxy resins have also been used as sprayed coatings (95), trowelling ce- ments (27), adhesives, and foams. Flex- ible products have been obtained by using tin(I1) octoate as the hardener. Self-extinguishing formulations are avail- able. Several new base resins have been introduced commercially (46, 50).

Crystallinity of epoxy resins is reduced by atomic irradiation ( 7 ) . Ehlers (28) has investigated the relationship of

structure and heat resistance. Michaels (64) has suggested use of highly filled products as low cost materials of con- struction. Recommended procedures for safe use of formulated epoxy com- pounds have been compiled by SPI’s Epoxy Resin Formulators Division.

Silicones. New developments in silicone technology included polyphenyl- silsesquioxanes with a double chain formula, transparent potting compounds (76), filled silicone moldings, cyanoethyl- substituted dimethyl siloxanes, organo- silicon esters of acrylic acid (25), and fluorosilicone rubbers (77). All possessed excellent high temperature properties. The cyanoethyl derivative has unusual electrical properties.

Miscellaneous. Polyspiroacetals made by the condensation of penta- erythritol and glutaraldehyde are being investigated. Polyoxetane is produced by chlorination of pentaerythritol (87). This product which is being used for pipe, linings, and molded products is classified as an engineering plastic. High melting polyspiroxetanes are also being investigated.

Building codes have been modified to permit the use of transparent sheets of poly(methy1 methacrylate). Reac- tive esters such as diaminoethyl and hydroxyethyl methacrylate are avail- able. Transparent copolymers have been obtained from tin derivatives of methacrylic acid. Plastics with better resistance to temperature were obtained by adding bentonite derivatives before polymerization. Several reports have been presented on thermosetting meth- acrylate compositions (40).

New water-soluble oxazolidinones are available. Several new copolymers of maleic anhydride have also been an- nounced. Crystalline polymers of pro- pylene oxide have been described. Condensation anhydride polymers have been produced from dibasic aromatic acids (62).

Nylon-7 has been obtained by heating esters of aminoheptanoic acid in water. Colorless resins have also been obtained when e-caprolactam was heated with ammonium thiocyanate (3). Over 30 million pounds of nylon was molded last year. I t is anticipated that the use of these engineering plastics will double during the next five years. Filled nylon is used for floor tile and piston rings.

In addition to their use as cellular plastics, polyurethanes are finding ap- plication as adhesives, coatings, castings, and moldings.

Liquid polysulfide manufacture has been discussed by Bertozzi ( 7 7 ) . This type of polymer is being used as a binder for NH&lOd in solid propellants; a butadiene-acrylic acid copolymer has also been investigated.

Flexible phenolic resins have been

VOL. 53, NO. 10 OCTOBER 1961 851

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a n m d Materials of Construction Review

prepared by chlorination or alkyla- tion of the phenolic grouping. Fur- furyl alcohol has been cross linked with polyamines. Furfural has been con- densed with epichlorohydrin to produce a thermosetting plastic. Flame resist- ant products have been obtained from chloromethyl derivations of diphenyl ether (24).

Polytetracyanoethylene has been de- scribed. Copolymers of acrylonitrile and nitroethylene have been reduced to yield amine-containing polymers. Uranek (89) has cross linked blends of butadiene copolymers of acrylic acid and vinylpyridine. Interest in con- ductive polymers continues (77). Ad- ditional information on chelate polymers and polyphosphonitrilo chloride (42) has been published. Three dozen dif- ferent plastics are being consumed with satisfaction at the rate of almost 7- billion pounds a year in the U.S.A. Obviously, the newer polymers must possess unique and desirable properties to justify future commercialization.

Acknowledgment

preparatian of this report is appreciated.

Literature Cited (1) Aitken, I. D., Ralph: K . ; At. Encrgy

Research Establ. (Gt. Brit.) R30, p. 85. 1960.

(2) Amberg, I,. O., Robinson, A. E.? IND. ENG. CHEM. 53, 368 (1961).

(3) Antykov, A. P., Zhur. Priklad. Khini. 33, 2371 (1960).

(4) Arndt! F. W., Corrosion 16, No. 11, 14 (1961).

(5) Xvrasin, Y . D., Prigoreva, A. 1.; Plasticheskie Massy 1960, No. 1, p. 13.

(6) Bailey, M. (to U. S. Government), U. S. Patent 2,967,165 (Jan. 3,1961).

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(23) Collins, F. H., SPB Journal 16, 705 (1 960).

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( '5) Dolgov, B. N., Kukhaiskaia, E. V., Andreev, D. IN , Vysokomolekulyarnye Soedineniya 2, 1463 (1960).

(26) Dorian, G. H., Burkhard, H., Llihite, M. L., ASTM Bull. No. 250, 34 (1960).

(17) Dunn, P. A,, Rubber t3 Plastics Age 42, 200 (1961).

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(31) Feuer, S. S., Plastics World 18, No. 9, 7n (ioc,n\

\ - ' - " / ' -" '32) Fischer, R. F., J . Polymer Scz. 44,

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134'1 Freeman, H. 6.. Sorsa, B.. Valtzon T e k

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?utkeniusZait& 1, No. 16 (1960). (35) Fujii, H.. Makromol. Chem. 40, 226

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(37) Furukawa, J., others, Makromol. Chem. 37, 149 (1960).

(38) Gefter, E. L.: Rubtsova, I. K., Russ. Patent 132,404 (Oct. 5, 1960).

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78 (1960).

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119 (1960). 150) Johnston, C. W., Greenspan, F. P.,

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Ann. Mtg., SOC. Plastics Engrs., Wash- ington. D. C.. Januarv 1961.

(53)"Knoppel, C. A., Ibid. (54) Kohler, R., Kunstof-Rundschau 5,

No. 9. 385 11958). (55) Landry, 'R. J , , Bartel, E. H., 17th

Ann. Conf., Soc. Plastics Engrs.. Wash- i-ngton D. C., January 1961.

(56) Leavitt, F. C., Mattervas. L. V., J . Poljrner Soc. 31, 249 (1960).

(57) Lee, M. M.: Electro Tech. 66 , No. 10, 149 (1960).

(58) Lee, P. A,, Materiais in Design Eng. 53, No. 5, 138 (1961).

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(60) Levy, R. M.. Corrosion 16, No. 11, 33 (1960).

(61) Loetel. C. E., Fordyce, H. E., SPE Journal 16,1137 (1960).

(62) McIntyre, J. E., Pugh, S. C., Brit. Patent 838,986 (June 22, 1960).

(63) Marvel, C. S., 139th Meeting, ACS, St. Louis, Mo., March 1961.

(64) Michaels, A. S., IND. ENG. &EM. 52, 785 (1960).

(65) Millane, J. J. ; Brit. Plastics 33, No. 5, 194 (1960).

(66) Molt, R. P., 17th Ann. Mtg., SOC. Plastics Engrs.: Washington, D. C January 1961.

(67) Montermoso, J., Division of Rubber Chemistry. ACS, New York, September i 9150.

(68) Gatta, G., Crespi, G., Rubber G"

(69) Patterson, J. A., Abrams, I. M., U. S .

(70) Pavne, C. R., Central Regional Conf.,

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(71) Pierce, 0. R., Holbrook, G. W., others, IND. ENG. CHEM. 52, 753 (1960).

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(73) Raech, H., Materials in Design En,?. 53, No. 5, 121 (1961).

(74) Reed, G. H.; S P E Journal 16, 1101 (1 960).

(75) Riley, N. W., Materials in Desi,yn Eng. 53, No. 3, 119 (1961).

(76) Robb, L. E., Western Plastics 7, No. 12, 23 (19601.

(77) Roubhe, K. L., Wasserman, A,,

(78) Rubber C8 Plastzcs Age 42, No. 5, 53 Proc. Chem. SOC. (London) 1960, p. 248.

(19611 (7j) Scfieimer. H., Kunststofle 50, 388

(1961). (80) Seymour, R. B., "Modern Plastics

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(81) Seymour, R. B., 17th Ann. Conf., Natl. Assoc. Corrosion Engrs., Buffalo, N. Y., March 1961.

(82) Sherwood, P. W., Plastics 25, 495 (1 960).

(83) Smoluk, G. R., Modern Plasticz 38, No. 1, 119 (1960).

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Am. Ind. Hjg. Assoc. J . 6 , 522 (1960). (86) Streble, E., 17th Ann. Conf., Soc..

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(88) Thierry, T. R., Corrosion 16, No. 11, 9 (1 960).

(89) Uranek, C. A, Sonnenfeld, R. F., IND. EKG. CHEM. 52, 790 (1960).

(90) VBn Boskirk, R. L.; Modern Plastics 38, ho . 8, 41 (1961).

(91) Van der Vegt, .4. K., KunstJtofe 50, 537 (1960).

(92) Van der Wal. A. A , , Plastics 25, 361 (1961).

(93) Watson, M. T., 17th Ann. Conf., Soc. Plastics Engrs., Washington. D. C., .January 1961.

(1 05R\ (94) Weiss, J., J . Polyniet .Sei. 29, 425

\-.--,. (95) LVittcoff, H., Floyd, D. E., others,

17th Ann. Mtg., Natl. Assoc. Corrosion Engrs., Buffalo, N. Y., March 1961.

(96) Young, R. E., SOC. Aerospace Ma- terial & Process Engrs., Filament Wind- ing Symposium, Pasadena. Calif., March 1961.

(97) Zade, H. P., ''Heat Sealing of Plas- tics," Temple Press Books, London, 1960.

After October 1962 the complete bibliog- raphy can be obtained from the AD1 Auxiliary Publications Project, Library of Congress, Washington 25, D. C . , as Docu- ment No. 6835, at $1.75 for microfilm and $2.50 for photostat copies,

852 INDUSTRIAL AND ENOINEERING CHEMISTRY