Plastics Chemistry and
tnaineerina 7
I
RAYMOND
he multibillion-dollar polymer industry continues to be the most T explosive segment of the entire peacetime economy of every developed nation. For example, the annual growth rate of the synthetic polymer industry in the USA is almost three times that of the average for all other industries. Thus, simple extrapolation suggests that the volume of synthetic polymer production will exceed that of all other nonpolymeric materials before the 1980’s. Leaders in the field recognize that this industry has already come of age and is now a commodity-type rather than a specialty-type industry (3A). The qualifications that are essential to the solution of many social and economic problems in our society, uiz., automation, computerization, and unlimited potential for expansion are inherent in the modern polymer industry. I n addition, the versatility of synthetic macromolecules fosters a variety of chemical and physical modifications which facilitate the solution of these and many other problems. For example, the employment of polymers as functional materials of construction in over a million mobile homes may serve as a precursor to the solution of instant habilitation problems. Likewise, the wide acceptance of expanded polymers for packaging eggs and other fragile products should suggest a host of related applications for cushioning and packaging. Those who are unable to visualize the myriad potential uses of polymers should observe how synthetic polymers have displaced classical materials in brushes and carpeting and are now replacing grass, classical flooring, and paving materials. Similar comments could be made for many experimental polymer applications which will be extrapolated to the solution of problems which will affect many facets of our economy during the next decade. Polymer reaction kinetics ( 2 A ) and polymer progress have been reviewed ( 7 4 7 4 8 A ) . These reviews summarize new processes, new polymers, and new applications which are already affecting many areas of today’s economy. The interest manifested by over 40,000 industrialists who viewed exhibits of plastics applications by over 350 firms a t the 12th National Plastics Exposition reinforces the thesis of the importance of polymer power a t the beginning of the second century of the plastics industry. The annual disposal of multimillion pounds of plastics continues to merit attention. The Department of Health, Education, and Welfare has granted $100,000 to TRW, Inc., for a study of this problem a t Redondo Beach, Calif. The magnitude of this technological progress problem will increase with population growth and prosperity and as more institutions adopt techniques dependent on the use of disposable plastics. I t is anticipated that over 300 million pounds of disposable plastics will be used in the USA in 1970. Engineers a t the Bureau of Mines have demonstrated that 140 gallons of combustible oil and 1500 fta of fuel gas can be obtained 28
INDUSTRIAL A N D ENGINEERING CHEMISTRY
I
B. SEYMOUR
by the pyrolysis of one ton of discarded pneumatic tires. Comparable results would be anticipated from the pyrolysis of other polymeric hydrocarbons. Water-soluble polymers continue to be used as coagulants in the production of potable water and in waste effluent treatment. Polymers are also effective in reducing the damage from oil spills. Silica-coated expanded perlite has been used for the preferential absorption of oil from oil-water mixtures. This composite absorbs over 50070 of its weight in oil. Other preventives used aeration from perforated plastic pipe and cellular plastic barriers to prevent the spread of oil. Almost 16 billion pounds of crude plastics worth over $4 billion were produced in the USA in 1768. It is anticipated that the 1769 production will exceed 17.5 billion pounds and that over 100 lb of finished plastic will be used by each American citizen in 1973. A comparable rate of growth is anticipated for Canada, Western Europe, Australia, and Japan. Over 15 billion pounds of plastics were produced in Western Europe in 1968 and it is anticipated that the per capita use in that area will increase from 40 to 100 pounds by 1980. I t has been stated frequently by polymer technologists that the volume of polymers will exceed all other nonpolymer products in the 1980’s. The volume of steel now produced annually in the USA is less than that of synthetic polymers and that even the volume of synthetic fibers exceeds that of all nonferrous metals (Table I). I n 1963 the volume of synthetic polymers will exceed the entire volume of the American production of steel and nonferrous metals. Seven commodity-type polymers accounted for 75% of the entire USA plastics production in 1968. Eight of the raw materials for polymer production are produced a t an annual rate in excess of a billion pounds. Thus, production for the polymer industry is the major effort of the gigantic petrochemical industry. Almost 50% of the capital expenditure in the entire chemical industry is associated with the production of polymers. Over 10 billion pounds of polyolefins were produced in the free world in 1968. The American polymer industry produced about half of this material and over 60y0 of this production was lowdensity polyethylene. The production of high-density polyethylene was slightly greater than that of polypropylene which was slightly less than 1 billion pounds. Approximately 8 billion pounds of poly(viny1 chloride) and 3.5 billion pounds of polystyrene were produced worldwide in 1968. The American production of these polymers was 3 and 2.6 billion pounds, respectively, The production of phenolic resins exceeded 1 billion pounds and accounted for more than one-third of the entire American production of thermosetting resins in 1968. Almost 3.5 billion pounds of synthetic fibers were produced in
The explosive growth of the polymer industry plays a large role in the economy of most countries. Uses for synthetic polymers are being found that over-ride classical materials in packaging, housing materials, automobiles, aircraft, and road paving. Industrial technology continues to explore new pathways for expansion
the USA in 1968 ( 5 A ) . The principal products were Nylon-66, polyacrylonitrile, and poly(ethy1ene terephthalate). Several other varieties of nylon are being produced throughout the world ( 4 A ) . The crude plastics, paints, and synthetic fibers produced in the US.4 in 1968 were valued a t over $10 billion. Over 4 billion pounds of synthetic elastomers were also produced but the average selling price of less than 20.j a pound resulted in a dollar volume of less than $1 billion. The selling price for end products from the rubber and plastics industries was at least five times greater than the cost of crude polymers. Approximately 13 billion pounds of natural and synthetic elastomers were produced worldwide In 1968 ( 6 A ) . Synthetic rubber accounted for almost 607, of this volume. S-type elastomer (SBR) accounted for over 60% of the 4.5 billion pounds of synthetic rubber produced in the USA last year. Stereospecific elastomers accounted for about 2070 of the entire synthetic elastomer production.
Education in Polymer Science and Technology
The phenomenal growth of all segments of the polymer industry has focused attention on existing deficiencies in polymer education. This unprccedentcd growth may be retardcd in the early 1970’sbecause of the dearth of polymer-oriented technicians, engineers, and scientists. The projected demand for polymers in the penultimate decade of this century will require more technicians, scientists, and engineers than are now being trained by our educational institutions. At present, over 100 times as many advanced degrees are being granted in obsolescent subjects than in polymer science which now offers over 50Y0 of the job opportunities for recipients of degrees in science and technology. Leaders both within and outside of the scientific community are attempting to help the educators prepare students to meet the challenge of the polymer age. X committee called Industrial Interface has been established to acquaint chemical faculty members with modern industrial chemistry (79B). The serious lack of communication between colleges and industry has been noted (8B), and several channels for interaction between the polymer industry and education institutions have been proposed ( 3 B ) . According to one education leader, a dichotomy prevails between the practice of chemistry inside and outside American institutions of higher learning (72B). Apparently, the antipathy to this important branch of science is an intrinsic quality observed by Baskel in the previous century and by the Nobel laureate Staudinger in the 1920’s. That this aversion still exists is suggested by anonymous practices such as the provision of very few funds for polymer research (4B). VOL. 6 1
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Simple extrapolation of past growth suggests that the volume
of synthetic polymer production will exceed that of all other nonpolymeric materials before the 1980’s
TABLE 1.
PRODUCTION OF PRINCIPAL POLYMERS AND METALS I N T H E USA
Synthetic polymers Plastics Elastomers Fibers Steel and nonferrous metals Steel Aluminum Zinc Copper Magnesium Lead
1968 (Cu F t 107) 400 260 80 60 424 370 40 6 4.5 2 1.5
1973 (Cu F t 107, Estimate) 710 500 110 100 574 500 50 7 4.7 3 1.6
Opportunities in the field of plastics present a point of entry into practically any industry and hence even in the absence of known and projected opportunities, polymer education should be initiated and expanded a t all levels (22B). A nationwide survey by the joint SPE-SPI Plastics Education Foundation has revealed a serious shortage of trained personnel which is becoming more critical as a result of continued industrial growth (5B, 77B). A Plastics Education Guide has been prepared (ZOB), a list of colleges and universities offering courses in this field has been provided (27B), and the place for polymer science in materials education has been discussed (76B). Over 100 colleges, hundreds of trade and high schools, and a multitude of continuing education seminars and workshops offer opportunities in polymer education. Thirty-nine institutions with formal plastics education programs are listed in “The Modern Plastics Encyclopedia” (9B). The task force of the SPE-SPI Plastic Education Foundation termed “Call to Action” has compiled and released a brochure on “The Need for Plastics Education.” Opportunities for careers in polymer chemistry are increasing at a rapid rate (IOB), and it has been estimated that in spite of educational deficiencies, two thirds of all recent chemistry graduates will accept positions related to this branch of science (2B). A specially designed plastics shop was incorporated in the new Susan E. Wagner High School in Staten Island, N. Y. The Orange County (Calif.) Plastic Industries Apprentice and Training Committee has endorsed requests by educational institutions for assistance (73B). As a result of information available on needs for education in plastics processing (7B), equipment manufacturers have donated almost 300 extruders and molding presses to high and trade schools. I t is anticipated that many other high schools will introduce plastics technology as part of their classical industrial arts training. Garfield High School (East Los Angeles) has already enrolled 140 students in 5 classes in plastics technology. A manual for plastics education in secondary schools is being used in New York City (7B). The Plastics Education Foundation maintains that the graduate education and research programs a t the Plastic Institute of America must be expanded 10-fold to meet the needs of this industry (78B). However, other segments of the academic community have failed to recognize the importance of undergraduate and graduate courses in macromolecular chemistry ( 7 4 B ) . A column on plastics education is now a regular monthly feature of Western Plastics (73B). Two-year plastics technician programs are being offered a t Bronx (New York) Community College and eight evening courses are being taught at Los Angeles Trade Tech College. New courses in this field have been instituted at Laney 30
INDUSTRIAL A N D ENGINEERING CHEMISTRY
College (Oakland, Calif.), Orange Coast College (Calif.), California State College at Long Beach, San Diego State College, the University of Southern California, and at Brigham Young University. A new macromolecular Research Center has been established at the University of Michigan. Comparable interest in polymer education is also being demonstrated on several other campuses. The phenomenal growth of the plastics industry is demonstrated by a 5000% increase in the production of polystyrene during the past 3 decades ( 6 B ) . Die Angewandte Makromolekulare Chemie, The Journal of Elastoplastics, The Journal of Adhesion, and Journals of Macromolecular Science-Chemistry and Physics have been originated to describe progress in this field. Over 200 terms relating to plastics have been approved and will be submitted to the International Standards Organization for possible adoption. At a recent meeting of the Technical Committee on Plastics of the International Standardization Organization (ISO/TC61), the following abbreviations for plastics were adopted and recommended for international use ( 7 I B ) : ABS CA CAB EP MF PA PC PE PETP
= poly(acrylonitri1e-co-butadiene-co-styrene) = cellulose acetate
SAN UF
= poly(styrene-co-acrylonitrile)
= cellulose acetate butyrate = epoxyresin = melamine-formaldehyde resins = polyamide (nylon) = polycarbonate = polyethylene = poly(ethy1ene terephthalate) PF = phenol-formaldehyde resin PMMA = poly(methy1 methacrylate) P O M = polyoxymethylene (polyformaldehyde, acetals) PP = polypropylene = polystyrene PS PTFE = polytetrafluoroethylene PUR = polyurethane PVAC = poly(viny1 acetate) PVAL = poly(viny1 alcohol) PVPC = poly(viny1idene chloride) (saran) = urea-formaldehyde resin
Over 250 polymer journals and papers presented a t more than 50 technical conferences are abstracted monthly by Engineering Index ( 7 5 B ) . Many new volumes are being issued periodically in a series of reviews and encyclopedias (23B-36B). Many new books have also been published to meet the needs of the polymer scientist and technologist (37B-84B). Plastic Structures
The use of plastics as structural materials now,accounts for 25% of the annual production and this use is growing at a n annual rate in excess of 12.5’%, The end uses range from aircraft to furniture. Other unique applications include water-filled poly(viny1 chloride) automobile bumpers, temporary buildings, and domed structures. Over 400 Ib of plastics is used on the Havilland Twin Otter Commuter Plane. A four-seat airplane with glass fabric-reinforced epoxy wings, fusilage, and tailpiece has been designed in Midland, Tex. (29C). Fibrous glass-reinforced plastic sandwich structures with aluminum ribs are being used for the construction of 77-ft fairings for the Lockheed 1011 Tristar. The use of reinforced plastics for aircraft (77C),submarines ( 7 IC), and marine applications (5C, 36C) has been reviewed. Structural shapes such as I-beams are being constructed from reinforced polyesters. Cellular polyurethane ceiling beams are available in 26-ft lengths. Propellers for outboard motors are
being injection-molded from polycarbonates and centrifugal pumps are being fabricated from polytetrafluoroethylene. Considerable equipment for the themical (70C,73C,32C,47C),steel (7C), and textile industries (78C) are being constructed from reinforced plastics. A 100-ft reinforced polyester stack is being used to vent corrosive gases in a Florida fertilizer plant. New information on PVC stacks and exhaust systems has been provided (42C). Extruded high-impact PVC profiles are being used as key-way Test data on forms for the construction of concrete highways. portland cement-poly(viny1 acetate) composites are available (40C). The use of epoxy resins in highway construction has been discussed (8C). Epoxy resins have been used to stabilize sandy road beds in the Netherlands (22C). Epoxy resin has also been used to join transverse bridge sections (9C). A continuous ribbon of resin-saturated glass mat has been used for road and airstrip surfacing (20C). Foamed-in-place urea-formaldehyde resin was used to stabilize sandy soil at Antwerp, Belgium. An iron-filled epoxy resin has been used to produce jaws for holding precision metal parts during assembly. The performance of furfural-acetone resin concrete has been reviewed (30C). The third rail in the new San Francis0 Bay Area Rapid Transit System (BARTS) is protected by almost one million feet of a plastic composite structure. The Fitch inertia barrier consisting of sand-filled polyethylene containers has been recommended for use as a nonlethal highway barrier system. A 4500-lb car traveling a t a rate of 50 mph was stopped within a distance of 21 ft by this type barrier. Applications of polymers in the biomedical field have been reviewed (6C). Progress continues in the design and application of plastic valves (3C) and hearts (35C). Polyethylene sheet with symmetrical perforations has been produced by exposure to a 100W carbon dioxide laser. Linked, tufted, molded polyethylene rings are being used for skiing surfaces. Polyolefin balls are being molded in Switzerland and used throughout the world for insulating water reservoirs. Allplastic structures that can be erected as gasoline fdling stations are available in the United Kingdom (34C). Modules consisting of polyurethane foamwood veneer panels may be mounted on perimeter foundations to produce prefabricated motel units. The “Hunter Structural System,” consisting of poured lightweight concrete within two vacuum-formed rigid PVC sheets is being used for building in the United Kingdom (26C). Several different plastic bungalows have been designed by Royal Shell in Delft, Netherlands (23C). Over 100 uses for plastics in a traditionally built bungalow were demonstrated at Breda, Netherlands (24C). The use of polyurethane in housing has been reviewed
(ZC,37c,39C). Disposable igloo-shaped “geo-huts” have been produced by spraying polyurethane foam over inflated balloons. Comparable structures produced by spraying a mixture of polyurethane resin and chopped fibrous glass on paperboard forms have been used to house migrant workers in California. These structures have provided each of 1000 families with 360 fta of usable living space during the past 4 years (4C). Swedish ceilings are being constructed from stretched PVC film (44C). The successful use of glass-reinforced PVC (46‘2)and PC window panes has been described (25C). Seamless P U R (37C, 38C) and acrylic flooring (28C)have also been discussed. The acoustical properties of plastics (7C,76C)and their use as roofing materials have been reviewed (33C). New information has also been published on the use of plastics as adhesives (72C)and sealants (74C) in building construction. One-piece packaged bathrooms comparable to those used at Expo ’67 are also being used in rehabilitation projects. These units are delivered on the job site complete with wiring and plumbing and thus provide instant toilet facilities (79C). Wash basins, shower stalls, and bath tubs of poly(methy1 methacrylate) were displayed a t an exposition in London (43C). Self-contained toilets for camping and boating are being rotomolded from powdered polyethylene. Guidelines for the quality control of plastic bathtubs and other plumbing components have been developed
(45C). Many types of extruded profiles for semifabricated building products are now available (27C). The use of long-term or secant modulus tests for plastics design data has been described (47C). I n addition to their use in residential construction (75C),plastics were used to construct a 60-ft diameter radome in Australia
(27C). Other large installations of plastics include a cast acrylic sheet dome a t Summerland in Tokyo, a n 8000-ft2planetarium constructed
from triangular acrylic panels in Portland, Ore., and a 96-ft diameter reinforced polyester roof in the market place at Argenteuil, France. The acoustics in the Royal Hall in London were improved by the installation of reinforced plastic saucers below the ceiling. Over 200,000 recreational vehicles such as golf carts, snowmobiles, and land vehicles were constructed with plastic bodies. A 96-in. X 74-in. ABS sheet was thermoformed to produce the body of a new terrain mobile. Over 80 Ib of plastic was used on each American car produced in 1968. I t is anticipated that over 1 billion pounds of plastics will be used annually by the American automotive industry in the early 1970’s. Plastic Containers and Vessels Over 3 billion pounds of plastics were consumed by the American container industry in 1968. Almost 1.570 of this volume was used for blow-molding bottles. Most of these were blow-molded from HDPE. The perfection of techniques for the production of clear bottles from PVC and PP assures a rapid growth of this segment of the packaging industry. Over 650 million milk bottles were blow-molded from HDPE last year but these accounted for less than 5% of all dairy product packages. Yet it has been predicted that 90% of all milk containers will be plastic or plastic-coated paperboard by 1973. New information on the design of blow-molded bottles (40)and the production of large PVC containers (220)is available. The Food and Drug Administration has approved the use of gallon-size HDPE bottles as containers for potable water. Other regulatory procedures of FDA and their counterparts in West European countries have been reviewed (370). The use of blown PVC bottles was restricted to nonfood uses prior to 1968, but propylene-modified vinyl polymer has been approved for this use
(801*
The announcement of a Swedish plastic beer bottle that disintegrated by oxidative photolysis when empty was presumably premature (270). However, thin-wall, blow-molded, unstabilized PVC bottles are being used in France as containers for mineral water, wine, olive oil, and vinegar; and molded PVC beer bottles are in use in Germany (780). Some of the hazards associated with automation and transportation have been overcome by the use of 1/2-gal plastic bottles for bottling Bourbon Supreme in the USA. A completely integrated production line in which plastic bottles are produced, filled, and capped has been described ( 9 0 ) . Plastic syringes are also being made on automated equipment (5D). Many different types of closures have been investigated for use with plastic bottles (350). Containers are being blow-molded from P O M (730). Two-quart capacity collapsible canteens are being blow-molded from copolymers of ethylene and vinyl acetate. A PVC-Saran paperboard beer container is being tested in Karlstad, Sweden (200). The use of PVC films for packaging bread and PE films for packaging vegetables (250) and poultry (260) has been discussed. The advantages and disadvantages of plastic containers of various shapes and sizes have been reviewed (ID), and a survey of tests for flexible packaging materials has been presented (20,290). Techniques for protecting light-sensitive products (340)and for estimating the shelf life of packaging films (300)have been described. Many difficult packaging problems have been solved by the use of laminated plastic film (230,330). Integrated lines have been described for the processing and heat sealing of PP (320)and PVC bags (30) and for encapsulation by low-pressure transfer molding techniques (380). Plastic pouches for ground coffee (790,390), blister pack packages (70),skin packaging (77D), shrink-film-packaged coal briquets (37D),thermoformed butter packages (76D), frozen food packages (280), and Nylon-6-laminated food packs (270) have been discussed. Approximately 5 million pounds of polymers were used for the production of laboratoryware in 1968, and it is expected that this use will double in the early 1970’s. Polyolefins account for almost 500/, of this application. The advantages of producing equipment from transparent heat-resistant stereoregular poly(4-methyl pentene-1 ) have been discussed (240). Flame-resistant S-shaped strands of polystyrene and polystyrene foam in the shape of cogwheels are available as loose fill packaging materials. Expanded polystyrene which has a low specific gravity, good cushioning qualities, low thermal conductivity, and low water absorption is also used for packaging (700). VOL. 6 1
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The unprecedented growth of the American polymer industry may be retarded early in the 1970’s because of the dearth of polymer oriented technicians, engineers, and scientists
Egg cartons molded from this cellular product represent one of the largest-volume, single-packaged products (400). The use of transparent plastic bags in place of opaque sacks has reduced pilferage in self-service stores. I t has been predicted that many products will be packaged in plastic bags with integral handles in the future ( 6 D ) . The use of polyethylene refuse bags has reduced the cost of solid waste collection. The Society of the Plastics Industries has formed a special committee to study this end use which is in conflict with some ordinances specifying the use of metal trash cans. However, 400,000 plastic bags donated by nine plastic companies will be used experimentally in a test in New York City during the summer of 1969. PE refuse bags were the subject of a sizable research project at Massachusetts Institute of Technology. They have already proved satisfactory in Kansas City and Toronto, Canada. T h e adoption of the recommendations of the M I T report for the use of plastic bags for disposal of household, industrial, and institutional waste would require a billion pounds of plastics annually. The advantages of PE bags have been discussed ( 3 6 0 ) . A new pasted-valve plastic bag is available ( 1 5 0 ) . Over 70 million pounds of PP was used to construct sand bags in 1968. Nitrile rubber-coated nylon collapsible fuel tanks for boats are available. Two 100,000-gal tanks of this type are being used as temporary storage for sewage overflow in the Anacostia River near Washington, D. C. Transparent propylene modified PVC battery cases weighing Commodity-type, over 17 lb are being injection-molded. filament-wound reinforced tanks 15 ft in diameter which can be used to fabricate long tanks are available in 10-ft sections. Reinforced plastic tanks for gasoline storage are available with a capacity range of 4000 to 10,000 gal. More than 2500 of these tanks are now in service. The use of reinforced polyester resins has simplified containerizing for air, marine, and land shipments of various commodities. Economies in transportation have also been realized by protecting pallets with a prefabricated PE film which is heat-shrunk to form a tight-fitting protective cover (740). Shrink-film systems are also used for cans (720). Aircraft food carriers weighing almost 50 Ib but less than metal carriers of comparable size have been vacuum-formed from PC sheet. Plastic crates and cases are also being used for the storage and transportation of almost every type of salable product (7 I D ) . Small pressure tanks in 14 different sizes are being produced by placing a filament-wound E P resin casing outside a blow-molded ABS container.
Plastics Composites
Over 1 billion pounds of asbestos and fibrous glass were used for the production of composites in 1968. One of the fastest growing segments of this phase of the plastics industry is that of reinforced thermoplastic composites. Over 50 million pounds of reinforced thermoplastics were produced last year (16E). Fibrous glass is still the most widely used reinforcement for all types of plastics (EE, 40E). The use of fillers and reinforcements in the polymer industry has been reviewed (45E, 54E, 57E). New nomenclature has been proposed to depict the use of additives as fillers, reinforcements, and carriers (23E, 32E). The minimum critical length for glass fibers for reinforcing nylon is 0.25 mm (15E). The longitudinal modulus of composites of this type has been estimated by extrapolation (29E,44E). I n addition to their use with PA, short glass fibers have been used to reinforce ABS, PAN, PC, PE, PETP, POM, PP, PPO, PS, PUR, and PVC (77E, 22E, 25E, 51E, 52E, 62E, 65E, 69E, 71E). The addition of milled-glass fibers reduces the coefficient of expansion of chlorinated polyether resins (53E). Fibrous glass has also been used to increase the heat stability of PF (50E),resorcinolfurfural (27E),and epoxy-acrylic resins (43E). Attempts have been made to improve the interfacial bonding between the resin and glass surface by the addition of silane coupling agents (46.23) or 32
INDUSTRIAL A N D ENGINEERING CHEMISTRY
tribromofluoromethane (20E) and by grafting styrene to the glass surface (26E). The addition of solid glass spheres to fibrous glass reinforced nylon has improved the quality of molded parts (49E). Recent reports on other fillers and reinforcements include the use of the following: PS (47E),PE (37E), Coir pitch ( 9 E ) , pyrolyzed lignin (70E), PF (37E), powdered aluminum ( 6 E ) ,molybdenum disulfide (59E), kaolin (72E), and PETP fibers (42E). The addition of zinc oxide has improved the weatherability of P P (7OE). Kaolin has been added to cellulose acetate to decrease the creep of films in the reverse osmosis process (17E). Finally, divided fillers have been used to control the viscosity of PVC solutions (55E). Finely divided calcium carbonate and quartz have been used to reduce the coefficient of expansion of EP (ZlE, 57E). Pyrogenic silica has been used to decrease resin stresses in composites (63E) and to reduce plate out during the processing of PVC (47E). New information has been published on interfacial stresses (34E), fatigue properties (56E), the evaluation of microvoids (4E, 28E), creep (72E),tensile strength (57E), and load transfer from resin to fiber (36E) and to broken fibers (66E). Other test data include nondestructive tests (73E),thermal tests (5E, 67E), and accelerated alternating pressure tests (18E). The thermal stability of fibrous glass-reinforced plastics has been improved by preliminary pyrolysis followed by reimpregnation with a furfural solution of a phenolic resole resin (64E). Preparatory techniques and the physical properties of asbestos reinforced polyesters have been reported (73E). Carbon filaments with a uniform cross section and a modulus of more than 50 million psi were obtained by pyrolysis of polyacrylonitrile filaments (33E, 60E). New information on filament winding techniques has been published ( ? E , 7E, 79E, 24E, 68E). Feasibility evaluations of fibrous glass-reinforced (48E) and boron filament wound pressure vessels have been reported (35E). The properties of concrete have been improved by the production of composites from furfural resins and PMMA ( 3 E ) . Products with superior physical properties have also been produced by the polymerization of vinyl monomers after impregnation of wood ( 7 4 3 ) . I n spite of a cost of over $300 a pound, exotic fibers are being used to extend the useful range of many composites (39E). The term “whiskers” may be used to describe naturally occurring fibers, such as asbestos, the crude alumina crystals that grow on aluminum after it has been immersed in hot mercury, and many single crystal reinforcements (38E). Single crystals of alumina have been obtained by heating the oxide at 1400°C (ZE). Continuous boron filaments produced by the hydrogen reduction of boron trichloride on a tungsten filament have been used to fabricate polyimide composite I beams for SST Aircraft (30E,67E). Metal fibers called filamets have also been used experimentally for the reinforcement of polymers.
Polymer Sheet and Film
Approximately 2 billion pounds of transparent film was produced in the USA in 1968. Less than 60Oj, of the 1.4 billion pounds of polyethylene film produced was used for packaging. Other applications included mulching and soil stabilization, protective covers, greenhouse construction, and pond or ditch liners. The production of blown PE film (24F),blown composite film (7F), extruded P P film (26F), and PVC film (75F) has been described. New information is also available on PP ( 5 F )and poly(ethy1ene-covinyl acetate) films (9F). Isotactic polybutylene films which are competitive with medium density PE films are available: Films that shrink to predesigned dimensions which have been used for novelty toys, have been produced by heating PP films that were stretched while being cross-linked by irradiation (ZF,20F): The adhesion of cellophane or printing inks to extruded PE film has been attributed to the presence of oxygen containing functional groups on the film surface ( 6 F ) . New techniques have been described for the removal of electrostatic charges from film surfaces (76F). The properties of PVDC (25F) and PC films ( 4 F ) have been modified by treatment with amines.
Other recent developments include synthetic paper based on PS, PVC, and PE, water-soluble poly(ethy1ene oxide) seed tape, and methanol-soluble hydroxypropyl cellulose. A matrix consisting of a polysulfone sheet overlay on hot, extruded P P film has been used for printing plates in place of papier-mache. A recent study showed that biaxial orientation develops when PE f i l m are joined by thermal techniques ( 7 IF). Excellent adhesion has been noted when Nylon-6 film is bonded by heating solvent-softened surfaces (74F). PTFE sleeves are now available for use with tapered glass joints. Handling techniques and the design of extruded PVC strip siding have been improved. Over 50 million ft2 of this product was used in 1968. Techniques for assembling thermoplastic sheet by ultrasonics (73F)and forming by heat (77F)have been reviewed. Over 20 million pounds of each of the major thermoplastic sheets, uiz., ABS, PP, and PVC, were used in the production of luggage last year. Superior weathering resistance is claimed for acrylic modified ABS sheet. Symposia on thermoplastic sheet processing and poromeric sheet technology were held in Quebec, Canada, and London, respectively. A poromeric leather-like product is being produced in Japan by the polymerization of methyl-l-glutamate-n-carboxyanhydride. New developments in sheet calendering have been surveyed ( I F ) . A polypropylene carpet was installed in a barn housing 400 cows i n Vidalia, Ga. The Drake (Iowa) Relays were run in the rain on a polymer composite track in 1969. All-weather polymeric surface tennis courts are planned for Forrest Hills (N. Y.). Sixteen major stadiums in the USA now use synthetic polymeric surfaces for their football fields. Equipment is now available for thermoforming polymer sheet as large as 74 in. X 50 in. with a maximum draw of 14 in. The body of the Mehair is manufactured by Citroen by thermoforming ABS sheets. The body of the Amphicat is made by ultrasonically welding two thermoformed sections of ABS sheet. The body of the Altex all-terrain vehicle consists of the same polymer. An alloy of ABS and P C is used for the chassis and body of the Formacar. PVC sheets 62 ft in width were welded together to form a 9acre salmon fish bowl a t Azwell, Wash. Four million ftaof solventwelded PVC film was used as the lining for a solar evaporation pond containing liquid effluent from a synthetic rubber plant at Odessa, Tex. Commercial reverse osmosis systems consisting of a cellulose acetate membrane have been used to produce potable water from the Hudson River a t an estimated cost of 1# for 20 gal. A 10,000-gal reverse osmosis system is being used to supply potable water to the entire community a t Bessie, Okla. U p to 60,000 gal of dilute waste water is being concentrated daily by a reverse osmosis process at Appleton, Wis. A unit with a daily capacity of 80,000 gal is being built for the U. S. Navy. Household reverse osmosis units capable of providing 3 gal a day and small commercial units with a capacity of 1000 gal of potable water are available. These units have replaceable membranes inserted in reinforced plastic tubes. The reverse osmosis process is being used for concentrating maple syrup and for the separation of urea from aqueous solutions (ZIF). Recent reports in this field include information on the design of a stepwise process (72F), p!ocess cost data (79F),and a series of reports by the American Institute of Chemical Engineers (IOF). Cellulose acetate reverse osmosis membranes are available in 1000-ft lengths and in widths u p to 2 ft. This highly porous film is cold-water quenched and solvent beached after casting. Several sheets are then cemented together to secure a final thickness of 4 mil after the laminate is immersed in hot water. An ultrathin (500-A thick) cellulose acetate film supported on a porous 2-mil thick polysulfone film has shown promise for rapid desalination processing (3F). Ultrathin cellulose films (5000- to 2000-A thick) useful in dialysis processes such as artificial kidneys have been produced by casting cellulose nitrate films on water and using ammonium hydrosulfide to regenerate the cellulose (23F). The use of electrodialysis fqr
water purification has been described (22F, 27F). An electrodialysis plant with a daily capacity of over 1 million gallons is being constructed at Sarasota, Fla. The use of membranes for the separation of binary liquids has also been investigated (BF). A silicone-polycarbonate copolymer membrane has been used for the separation of gases in a blood oxygenator. Hollow fibers of cellulose acetate and polyamide have been used as molecular sieves for ultrafiltration of solutions (78F).
Cellular Polymers
Almost a billion pounds of cellular polymers were produced in the USA last year and it is anticipated that the volume of this type plastic will exceed 1.5 billion pounds in 1970. Flexible PUR foam and PS foam account for 40 and 25y0 of the entire market, respectively. Polymer foam is now being produced from ABS (75G, 34F, 47F, 48G), PUR (6G, BG, 33G, 38G, 44G, 49G), U F (39G),PF (37G), PS (5G, 27G), PVC plastisols (73G), polyimides (77G),and 1-butene-sulfur dioxide copolymers (7OG). Progress in this field has been reviewed (32G, 36G), and new information has been supplied on syntactic foams (2G). As much as 18 lb of flexible PUR foam was used in each of the 1969 model cars. This volume may be increased considerably if foam is used in place of air in pneumatic tires in the future. Almost 5 million pounds of cellular plastics were used last year for insulation of shelters and storage areas on farms. Over 3 million pounds were used for shipping celery and lettuce produce. King Harbor a t Redondo Beach, Calif., was protected from damage by the Santa Barbara floating oil slick by the use of a 2000ft floating barrier constructed from cellular PS billets. Foamed in place, P U R was used to float the S. S. Wahine which sank off the coast of New Zealand. Twenty thousand pounds of PP foam was used on the ocean floor to reduce shore erosion at Wallop’s Island, Va. Equipment is available for the continuous extrusion of 9-ft wide rigid PUR core panels (42G). A disposable paint brush consisting of reticulated P U R foam has been designed. A high-temperature resistant pyranyl foam has been produced from acrolein dimer. Structural shapes are being produced by the Celka process in which the skin thickness is controlled by reinjection cycles. The thermoforming of this type product has been described (28G). PS beads have been expanded by heating in a rotary pan to produce pre-expanded beads which may be heated to obtain products with bulk densities ranging from 0.85 to 7.5 Ib ft3 (37G). Expanded polymers have also been produced by the nucleation of gas injected directly into the polymer mass (79G). Economies have been achieved by use of steam or vacuum blowing processes (35G). The relationships of properties of foams to nucleation, growth, and bubble stability have been investigated ( 7 F ) . Strong reticulated structures have been obtained by cross-linking foams of poly(viny1 chloride-co-maleic anhydride) with isocyanates. New information has been provided on network PVC foams (26G) and expanded PVC textiles (29G). Porous beads of poly(styrene-co-divinyl benzene) have been prepared by copolymerization in the presence of gasoline or PS (25G). Foamable poly(viny1idene-co-acrylonitrile) microspheres containing liquefied isobutane are now available for the production of syntactic foams. PE foam has been cross-linked by electron bombardment. The flame resistance of SBR foams has been improved by increasing the styrene content of the copolymer (27G). Phenolic nylon syntactic foams are now being used for ablative heat shields (24G). The quality of PUR foams has improved by the use of sucrose-based polyols in place of other glycols. The ability of silicone surfactants to increase the number of bubbles in P U R has been investigated (23G). The relationship of cell structure of PE foams to their dynamic cushioning effects has been studied (4G) and these relationships to other properties has been considered (7G). The geometry of PVAL foams (30G) and the mathematical analysis of the effects of high temperature on P U R foams have been studied (7G). VOL. 6 1
NO. 8
AUGUST 1969
33
Cross-linked cellular plastics were used in the construction of a 4.5-acre underground parking deck at Western Reserve Medical Center in Cleveland, Ohio. General information has been published on the use of cellular polymers for structures (40G, 43G), packaging ( 74G, 78G, 20G), floating devices (ZZG), sandwich-type panels (77G), void fillers (44G), furniture (47G), automobile applications (45G, 46G), and insulation (3G, QG, 76G). Cellular plastic construction has been used to improve gun-firing accuracy ( 7ZF). Plastic Pipe
Over 350 million pounds of plastic pipe valued at almost $200 million was used in the USA in 1968 (73H). This volume included over 325,000 PVC drain, waste, and vent (DWV j systems. Such application has been approved by major regional codes in 13 states and many communities but are prohibited by more than 609;b of all towns and cities with populations greater than 5000. The International Association of Plumbing and Mechanical Officials has approved PVC pipe for DWV systems in accordance with ASTM standard D-2665-68 but the Cast Iron Soil Pipe Institute has challenged code approvals of nonferrous pipe. The Federal Housing Administration (FHA) has approved PVC for DWV and chlorinated PVC for distribution piping systems in rehabilitation projects in five states. Over 200,000 PVC cold-water distribution and DWV pipe system was installed in a new community at Allamuchy, N. J. Over 3000 ft of 18-in PVC pipe was installed in water mains at Shawinigan, Canada. The Almaden Vineyards in San Benito County, Calif., is irrigated by water from 2000 miles of PVC pipe. A DWV plastic pipe system was installed in a 19-story apartment house in Europe but the use of such systems above three stories is prohibited by the New York City code. ASTM standard D2672-68 has been established for solvent-welded PVC pipe (SWP), and one major firm is guaranteeing its ABS DWV pipe for 50 years. The use of lead-stabilized PVC pipe for transporting mineral waters has been discussed ( 6 H ) . The production and use of pipe extruded from PVC ( I H , ZH, 74H, 75H), poly(viny1 dichloride) (3H, 4H, 76H), and P P ( 8 H ) have been described, and the economics of PVC pipe use has been discussed ( 7 H ) . Rigid PVC and LDPE pipe have been used successfully for 10 years in sulfuric acid service (78H). Poly(ethy1ene-co-vinyl acetate) pipe is being used for blending Gilbey’s Gin in Essex, England. Perforated PVC pipe is being used to create underwater turbulence in an effort to protect beaches from oil slicks and sewage. Over 30 million pounds of plastic pipe was used for agricultural applications in 1968. The use of plastic pipe in gas distribution lines is growing a t an annual rate in excess of 25Yc. Over 90% of the pipe used for this service was PE and PVC pipe. Plastic pipe installed by the Michigan Consolidated Gas Corp. was found to be in excellent condition after 26 years of underground service. The creep resistance of PVC pipe was improved by irradiation with gamma rays (77H). A high-pressure (2500 psi) polymer pipe is now available. Over 1 million feet of extruded high-impact well casings, guaranteed for 5 years, have been installed. Most automotive radiator and heater hose is being made from ethylene-propylene copolymer (EPDM). “Instant pipe,” consisting of flat-rolled uncured reinforced plastic tubing, may be inflated and cured at the job site (7QH). The production and use of fibrous glass-reinforced polyester pipe have been reviewed (5H, QH). Reinforced plastic pipe has been produced from EP and PF reinforced with asbestos of fibrous glass (7ZH). Large-diameter reinforced plastic pipe has been produced by the filament winding process (IOH, 7 7H).
Synthetic Fibers
If its birthdate is considered as the time when Count de Chardonnet extruded xyloidin, 1969 would be the centennial for the synthetic fiber industry. T h e worldwide production of synthetic fibers exceeded 8 billion pounds last year but almost three times as much cotton was produced during the same period. The USA, Western Europe, and the United Kingdom produced 3, 2, and 1 billion pounds of synthetic fibers, respectively. The American production of nylon exceeded 1 billion pounds and that of polyester fibers was almost 750 million pounds. The dollar value for all synthetic fibers produced in the USA was almost $4 billion. Over a billion pounds of resins and finishes are consumed by the textile industry annually. More than 600 million pounds of polymers were used as stretched tapes, split yarns, and spun-bonded textiles ( 7 7 K ) . Equipment is now available for slitting and fibrillating PP film for the fabrication of carpet and twine at a rate of 650 Ib per hr. Sweaters are being made in Japan by this technique. The copolymer of butadiene and acrylonitrile has been used as a binder in the production of nonwoven textiles ( 7 3 K ) . The cost of articles from these and spun-bonded polyolefin fabrics are competitive with linen service. These products are being used for industrial garments, graduation gowns, and hospital sheets. New information on generic names and definitions of man-made fibers has been developed by ASTM and meaningful tests have been proposed (32K). New data have been provided on the production and drawing of polyester fibers (27K, 3 8 K ) . The structures of twisted PETP and Nylon-6 filaments have been investigated ( 9 K ) ,and new information on the chemical modification of fibers has been published (30K, 34K). New information has also been provided on the production of acrylic fibers (79K, 22K, 25K, 43K), their morphology (40K), blends of these fibers, and PVAL fibers ( 7 K ) , and chemical modifications (8K, 28K). Over one half of all wigs sold are fashioned from modacrylic and polyester fibers (39K). The structural changes occurring during the spinning, drawing, and heat-setting of PP (77K, 3 7 K ) have been investigated. Graft copolymers of PP fibers and methyl methacrylate have been described ( 3 6 K ) . The dyeability of these fibers has been improved by copolymerization with amino-alkyl acrylates. The melt extrusion process has been modified by the addition of small amounts of volatile plasticizers (20K). The spinning of Nylon-6 fibers (7K, 24K), their modification by diisocyanates (3K, 78K), and simultaneous polymerization and extrusion of these filaments ( 7 5 K ) have been described. Fibers have also been prepared from polysulfonamide (33K), poly-trans-p-(4aminocyclohexy1)propionicacid, Nylon-4, Nylon-1 2, poly-p-ethylene oxybenzazole, and the condensation product of (bis-p-aminocyclohexy1)methane and dodecandioic acid. Biconstituent polyester-polyamide fibers (29K) and casein PVAL fibers (47K) are now available. Nylon fabric has been joined by use of capacitance welding techniques ( 7ZK). Over 25,000 yards of temperature-resistant polyamide fibers are being used for upholstering the Boeing 747 superjet aircraft. This fiber is also being used for filter bags which operate continuously at temperatures as high as 450°C. PVAL fibers have been modified by phosphorylation of formalized fibers ( 7 6 K ) , by the addition of inorganic reactants ( 6 K ) , and by copolymerization with methylol crotonamide (23K). A new elastic fiber has been obtained by grafting acrylonitrile on crosslinked poly(buty1 acrylate). The role of fiber optics in analytical chemistry has been reviewed ( I O K ) . Fibers that are resistant to flame and moisture have been produced by grafting acrylonitrile on cellulose fibers (ZK,4K, 74K, 27K, 42K). Other cellulose modifications include graft copolymers with vinyl acetate (37K), methyl methacrylate ( 5 K ) , and silicones (35K), and reaction products with chloroacetamide ( 2 6 K ) . Polymers vs. Weather
AUTHOR Raymond B . Seymour. Prior to joining the University of Houston where he is coordinator of polymer science, D r . Seymour served as head of the department of chemistry at Sul Ross State College and director of research at the University of Chattanooga. He has held industrial positions ranging from bench chemistry to chairman of the board for severalJirms in thepolymerJield. This is the 20th Annual Review written for INDUSTRIAL AND ENGINEERING CHEMISTRY by this author. Arrangements have been made with the editor of I@EC to permit translation and reproduction of this review in several foreign journals. 34
INDUSTRIAL
AND ENGINEERING CHEMISTRY
The unprecedented growth of the billion-pound plastics has been dependent upon the weatherability or aging characteristics of these materials. These properties which are inherent in PF had to be developed through the use of additives in the large-volume thermoplastics. Several new reviews on this general subject ( Q M ,ZOM) and degradative mechanisms (73M, 2 Q M )have been published. Trends in the stabilization of low-density polyethylene ( IOM), HDPE ( 2 8 M ) , and PVC (27M) have been reported. The results of several investigations on the resistance of polymers to radiation have also been published ( I M , 37M, 3 3 M ) . The effect of ultra-
violet light on PS block copolymers ( I I M ) and stabilization of polymers by the use ofnickel oxime chelates ( 7 M )and 2-(2-hydroxy phenyl) benzothiazole derivatives ( 2 5 M )have been studied. Other weatherability-related reports include : the surface degradation of polyethylene ( 3 2 M ) , the kinetics of crack development ( 7 7 M ) , and accelerated testing procedures ( 2 2 M ) . PP has been stabilized by the addition of zinc oxide ( 8 M ) and organic pigments ( 1 2 M ) . Degradative studies of PVC include: the effect of plasticizers ( 4 M ) , metallic soaps ( 3 0 M ) , and tributyl tin compounds ( 2 6 M ) . The presence of calcium citrate accelerates degradation, whereas the stearate serves as a stabilizer for PVC (IQM). The stabilization of Nylon-6 ( 2 3 M ) and ABS copolymers ( 2 M ) has been investigated. The deterioration of the latter is related to the butadiene content ( 7 4 M ) . The degradation of stereoregular polymers ( 1 6 M )and the aging of reinforced polyesters ( 2 4 M ) have been investigated. The use of alkyl derivatives of xylenols as stabilizers has been reviewed ( 1 5 M ) . The use of stressed specimens in ultraviolet exposure tests has been recommended ( 6 M ) . Gamma-ray spectroscopy has been used to study the role of tin stabilizers ( 3 M ) . Derivatives of polymers of formaldehyde have been prepared in order to study the heat stability of POM ( 5 M ) . Molecular weight determinations were used lo measure the effect of stabilizers on PETP ( 2 7 M ) . The change in stiffness and the angle of break of an exposed cantilever beam have also been used to measure the aging of polymers (78M). Polymer VI. Flame
The increased use of polymers as materials of construction on land, sea, air, and outer space has focused attention on the need h r flame-resistant products in many applications. Organic phosphates accounted for more than 60% of the 85 million pounds of additives used to improve the flame resistance of plastics in 1968. I n addition, over 50 million pounds of flame-resistant reactants such as tetrachlorophthalic anhydride were used to produce flameresistant plastics last year ( 3 7 N ) . The flame resistance of organic pdymers has been improved by the addition of chlorinated compounds ( 1 8 N )such as chlorinated PE ( 7 N ) and fillers ( 2 7 N ) . Flame-resistant polymers have also been produced by the chlorination of polyesters ( 2 7 N ) , by copolymerization with abromoacrylates ( 2 6 N ) , by the synthesis of oligoestermaleinates with isocyanuric rings (ZN), by the reaction of diisocyanates with phosphorylated alcohols (33N), or with adducts from the reaction of castor oil and hexachloropentadiene (23N), and by the addition of tetrabromo phthalic anhydride to thc reactants in the production of P U R foams ( 2 8 N ) . The flame resistance of cellulose has been improved by the formation of flame-resistant polyesters in situ (39N). Fortunately, when one excludes cellulose nitrate and shellac, plastics may be classified as ranging from slow burning to inert. Also unlike many nonsynthetic materials of construction, the composition of synthetic polymers may be modified to meet significant specifications ( 5 N , 3 5 N ) . The problems associated with the flame resistance of plastics (75N, 30N, 37N, 34N), fibers ( I N , I IN, 2 2 N ) , and polymeric foams (SN, 74N, 77N, IQN, ZON, 2 9 N ) have been reviewed. The fire hazards associated with the procession of polymers ( 8 N ) and the use of plastics for duct work construction ( 2 4 N ) have been described. Modern construction procedures which provide large areas without fire walls under a single roof, efficiency storage systems, and possible progressive deterioration of fire-resistant materials also contribute to fire hazards ( 3 2 N ) . Since 430/, of businesses are discontinued after a major fire, flame resistance is an important factor and the need for significant tests for flame resistance is obvious. SPI has supported a research project at Illinois Institute of Technology to ascertain the effect of fire environment on plastics. Polyester panels prepared from chlorendic anhydride are acceptable for use in high-rise buildings ( 4 N ) ,and also a PUR foam sandwich with an inert center has potential use as a fire barrier ( 3 N ) . T h e recently amended Flammability Fabrics Act applies to home furnishings as well as to the interiors of motor vehicles, boats, and aircraft. The criterion for flame resistance used by this act is a flame-spread rating of less than 25 on the ASTM E84-61 tunnel test. However, the relationship of this test to actual fire conditions is questionable, and the extent of generation of smoke and toxic fumes must also be considered when materials of construction are approved (ION, 25N, 3 8 N ) . There is also a definite need 36N). for large-scale tests for determining flame resistance (76N,
Model tests have been suggested for the study of the flame resistance of plastics ( 7 3 N ) . Most materials that fail to pass the ASTM E84 test may be eliminated by use of a series of simple tests ( 9 N ) . The excellent interlaboratory agreement obtained in the first roundrobin oxygen index test suggests that this type of test may be useful in rating the relative flame resistance of plastics (7ZN). Polymers VI. Heat
Among the new temperature-resistant polymers introduced recently was a low-priced cross-linked flame-resistant phenolic-type fiber which was demonstrated at the 39th Annual Meeting of the Textile Research Institute. This polymer is resistant to the heat of an oxyacetylene flame (2500'C) and is unaffected by nonoxidizing acids and most solvents. Several new reviews on heat-resistant polymers have been published (5P, 73P, 23P, 30P, 32P, 34P). New information has also been supplied on the heat aging of reinforced polyimides (72P, 29P), the pyrolysis of polymellitimides (18P), the hydrolytic stability of poly(organoborosi1oxanes) ( IP), the oxidation of polyamides and polyimides (39P), and the ablative qualities of PF composites (24P, 4ZP). The relationship of heat resistance to the structure of polymers has been investigated (2P, 27P, 45P). Among the many heat-resistant polymers described are polyanhydrides ( 8 P ) , polyimides (6P, 7P, QP, 15P, 79P, 28P, 36P, 38P, 40P, 43P), polybenzimidazoles ( IOP, 26P, 31P), polyoxamides (44P), polyquinoxalines (ZOP, 46P), polyoxadiazoles (25P, 32P, 37P), polybenzothiazoles (21P, 38P), polytetrazoles (16P), polybithiazoles (35P), polyxanthones (33P), polyhydrazides (41P), polyketones (22P), polyphenylene oxide ( 4 P ) , poly(perimidine tetrayls) ( 3 P ) , polybenzophenanthrolenes (32P),oxabicyclononane ring polymers (17P), boron-containing phosphonitrile polymers (74P), and poly(si1oxane-s-triazinyl ethers) ( 7 IP). Polymers vs. Corrosives
Corrosion continues to plague the chemical and metal-working industries. The annual cost is approximately $10 billion. However, in spite of unprecedented inflation and industrial growth, the corrosion losses are being controlled by the use of more resistant materials of construction. The corrosion of boilers and condensate systems has been lessened by the use of floating hollow P P balls. For example, the dissolved oxygen in a machine hot well at Renfrew, Scotland, was reduced by 9601, through the use of over 13,000 plastic balls with a diameter of 1.75 in. The use of reinforced plastics for construction in the chemical (54)and textile industries (734)and other corrosive environments (ZQ) has been reviewed. The properties and uses of this type construction have been tabulated (14Q), the relationship of the environment to these properties (ISQ), and the effect of composition on chemical resistance ( 7 2 4 ) have been considered. I n one series of environmental tests, a catalytic acceleration of the degradation of aromatic polyesters in the presence of hydrochloric acid was noted ( 2 7 4 ) . The exposure of reinforced polyesters to boiling water for 3 hr has been correlated with long-time exposures in seawater (44). The use of chlorine containing polyesters by chemical industry has been cited ( 7 9 4 ) . A comprehensive review of testing procedures for the chemical resistance of plastics has been published (64). The time for failure by repeated deflection of rigid PVC in aqueous solvents has been studied ( 1 7 4 ) . Other test information includes soil burial tests on PVC ( 3 4 ) ,the effect of water and solvents on Nylon-6 (78Q), the effect of acids on elastomers (7141,the swelling of elastomers by wine ( 2 2 Q ) ,the ozonolysis of elastomers (75Q), and the effect of humidity on this ozonolysis ( 704). Composites applied as dispersions of fibrous glass-reinforced Nylon-6 phenolic resins in furfuryl alcohol have been proposed as protective barriers for corrosives ( 7 4 ) . New information has been published on the use of modified epoxy resin coatings ( Q Q ) and the selection of coatings for the detergent industry ( I Q ) . The use of emulsions as protective coatings for metals (84) and the general problem of protecting metals by coatings have been reviewed ( 2 0 4 ) . Characterization and Testing of Polymers
The characterization of polymers has become the principal interest of a majority of modern analysts as evidenced by over 60 pages being devoted to this subject in the Annual Reviews of Analytical Chemistu (57R, 88R, QQR). Many other technicians are VOL. 6 1
NO. 8
AUGUST 1 9 6 9
35
concerned with the development and use of new testing procedures. For example, six new test methods for EP molding compounds were issued by SPI last year. The need for testing under end-use conditions (43R) and the effect of variables such as anisotropy on physical tests (24R, 67R) have been discussed. New information on nondestructive testing includes the use of fluorescent probes and microscopy (23R,85R),microwaves ( 74R), ultrasonics (42R),convergent polarized optics (34R), light scattering (9R,83R), krypton absorption of films (75R), the use of gammarays for evaluating bonding in composites (707R), and the measurement of bond strength by acoustic spectroscopy (54R)and by infrared spectroscopy (5R). Other investigations reported include the micro-optical swelling of elastomers (25R),rheometric studies with a plastometer (45R) and with a n inexpensive instrument (77R), radioisotope studies (78R), and the peel strength of laminates (59R). The internal motion of polymers which may be detected by electrical, electromagnetic, and dynamic mechanical measurements can provide an insight into the behavior of polymers over a wide range of temperature and frequency (76A) and the relationships of properties to molecular motion (7R) and molecular structure (707R). The need for better understanding of polymer fundamentals has been emphasized for the interpretation of brittle rupture during prestressing (35R),low-temperature impact failure of PVC (37R), plastic deformation (Q8R),and creep (6ZR, 6 4 R ) . New data are available on plastic creep (65R) and the relationship of stress and failure time for plastic bottles (30R). A laboratory extruder has been used to study the susceptibility of PVC to die swelling (75R). The toughness of reinforced polymers has been attributed to the energy absorbed during the cold drawing of the filaments and the free volume of the polymer (84R). A sclerometric pendulum hardness test has been used to study paint films (706R) and the effect of aging on reinforced plastics (95R). New information is available on stress cracking (70R) and the relationship of accelerated tests to outdoor exposure tests (68R). The intensification of solvent stress cracking at 20' to 30°C below the glass transition temperature has been noted (53R). The melt viscosity of polyolefins has been related to temperature and shear (56R). The morphology of crystalline polymers (58R) and the relationship of composition to thermal expansion (46R) have been investigated. Dilatometry and torsion pendulum techniques have been used to measure the glass transition temperature of poly(viny1 cyclohexane) (94R). Pressure-volume relationships and differential scanning calorimetry have been used to measure the glass-transition temperature of E P (27R) and PA (36R). Infrared spectroscopy has also been used to measure this important parameter (4R). New information has also been supplied on the X-ray diffraction patterns of fibers (82R),foam fractionation of polymer solutions (37R), and the electrical properties of polymers (29R, 47R). Lacquers and polyurethanes have been identified by thin-layer chromatography (77R, 49R). Gel permeation chromatograms have been calibrated by computers (8R). Molecular weight data have been obtained by osmometry (33R) and ultracentrifugation (57R, 60R, 77R). Mass spectrometry has been used to study the permeability of films (26R). Polarography has been used to study Schiff bases formed by the condensation of nylon hydrolyzates and formaldehyde (78R). Solubility parameters have been determined by turbidimetric titrations (86R). The use of spectroscopic techniques for the investigation of polymeric structures has been reviewed (32R, 76R). The potential uses of N M R and other spectroscopic techniques in the paint ( I R , 72R) and fiber (80R) industries have been discussed. This type spectroscopy has been used to study deuterated polystyrene ( 7 3 R ) for the C13 analysis of copolymers of ethylene oxide and maleic anhydride (70R), for the detection of end groups in telomers (77R), and the run numbers in copolymers (48R). The applications of spin-resonance spectroscopy to polymer science have been described (28R). EPR techniques have been used to study the pyrolysis of polyacrylonitrile (44R), the irradiation of nylon (93R), and the irradiation of rubber in the presence of halogenated compounds (50R). Internal reflectance spectroscopy has been used to monitor the increase in carbonyl content during the weathering of films. The use of this technique on the coatings field has been reviewed (IoOR). Infrared spectroscopy has been used to characterize fibers (79R, 87R) to study the curing and to detect allophanate groups in PUR (704l2,705R), to differentiate between fumaric and maleic esters in copoIymers chains (67R),to relate carbonyl content to the 36
INDUSTRIAL A N D ENGINEERING CHEMISTRY
hydrolytic stability of polyesters (72R), and to study chain folding and orientation (ZR,3R). Near infrared spectroscopy has been used to characterize pyrolytic products from nylon (96R) and neoprene (27R), to differentiate between random and block copolymers of ethylene and propylene (97R),and to study poly(styrene-coacrylonitrile) (92R). Raman spectroscopy has been used to study the pyrolysis products from polymers of acetylene (102R). New information has been published on the pyrolysis of PF laminates (63R), silicone lacquers (5ZR), polyolefin mixtures (39R), and the presence of PS in acrylates (87R). Reviews have been published on the use of mass spectrometry for thermal analysis (79R) and pyrolytic gas chromatography (73K,20R, 38R, 90R). The latter technique has been used to study the chlorination of PE (97R), the saponification of alkyd resins (4OR, 47R), PUR foams (8QR),and elastomeric membranes (66R). Cross-linked PS has been used as a column packing in gas chromatography (74R). Differential thermal analysis has been used to determine the fine structure of PETP (703R), to characterize elastomers ( 6 4 ZZR, 55R),and to study polymer degradation (5ZR, 69R).
Progress in Polymer Science
Those who have studied growth trends in this dynamic industry believe that much of the future expansion of the poIymer industry will be related to the replacement of other materials including polymers by more functional polymers, to improvements and modifications of production techniques, fabrication, and processing methods, and to utilization of the polymers which are now being produced a t an annual rate of at least 1 billion pounds, Contribution to polymer progress in the last decades of this century will also be made by new materials with functional properties not characteristic of classical polymeric materials. An example of advantageous replacement is the use of ABS for telephone handles and housings in place of CAB which resulted in an annual savings of $1.4 for Western Electric. Among the many other noteworthy replacements are PP sand bags and PE refuse containers. Notable modifications of existing processes are the production of low-density polyethylene at relatively low pressures (500 psi) in contrast to the classical high-pressure process (30,000 psi) (83, 77S), the use of isopropyl peroxydicarbonate for forming a n initiator in situ for the two-phase polymerization of vinyl chloride, a two-step bulk polymerization process for styrene (67S), new oxidative processes for the production of butadiene (74S), vinyl acetate (46S), and terephthalic acid (35S, 70s). New economical processes are also available for the production of resorcinol and melamine (78s). The problems associated with monomer storage have been described (57s). Epoxy resins have been produced from chloro and cyano compounds (67S),phenyleneoxide (40S), and from dinaphthols (6s). Among the new resins are a polyarylether (45S), polystannol elastomers (56S),polysulfones ( 70S, 52S, 65S), phosphonitrilic fluoroeIastomers (.53S), polyacetal elastomers (66S), poly(methy1 pentene) (73S), ionomers (.36S), fluorinated polymers (27S, 69S), modified nylons (ZS, 47S, 6ZS), aliphatic polyesters (5S), functionally terminated polybutadienes (23S), bisphenate silicone oligomers (64S),copolymers of ethylene and hexene (30s) and vinyl epoxy undecanoates (SS), block copolymers of polyalkylene oxides and polyterephthalates ( 7 7S, 49S), and copolymers produced from dimeric dianions (48s). Block copolymers have been prepared by the mechanical cleavage of polymer bonds in the presence of monomers (75S, 765'). New information has been supplied on cross-linked PE (39s)and crosslinked PS (34s). Simple models have been provided for stereopolymers (50s). New information has been published on telomerizations (4S, Z S ) , charge transfer polymerization (59S), gamma-ray polymerization techniques (60S), the surface aspects of emulsion polymerization (57S),photopolymerization (25S, 42S), photocuring (38S),and suspension polymerization (43s). A symposium on polyolefins was sponsored by the ACS (27s)and a review of the growth potentials ofHDPE hasbeen published (32s). New hardeners for EP have been described (3S, 7QS,28S, 58s). A new classification has been proposed for EP molding compounds (ZOS), and progress in the development of epoxy elastomers has been reviewed (24s). Symposia on radiation curing ( 2 9 s ) and epoxy resins were sponsored by the Division of Organic Coatings and Plastics Chemistry (475'). Factors affecting the cure of E P have been studied (72s) and new encapsulation techniques with liquid resins have been described (77s).
The chemical reactions of polymers have been reviewed (5557, and new information has been published on the chlorination of polyisobutylene (3757, polyethylene (7S), and polystyrene (31s). New reviews on phosphorus (54s)and sulfur-containing polymers (26s) are available. The use of trimellitic esters as plasticizers is increasing (IS). Extrusion temperatures have been controlled through changes of temperature of the polymer melt instead of cylinder temperatures (44s). High-molecular-weight PE has been processed by forging techniques (68s). PF molding compounds are being extruded and injection molded by classical techniques (63s). The properties of PF moldings have been improved by postbaking (33s). Comparable progress is being made in almost every facet of this technically oriented industry. REFERENCES General I n f o r m a t i o n
(1A) Kline, G. M., Mod. Plast., 46 (2), 58 (1969). (2A) Lenz, R. W., IND.ENO.CHEM.,61 (3), 67 (1969). (3A) Meyer, A. W., and Kaufman, H. S., Pl&. World, 26 (E), 47 (1968). (4A) Mod. Plastics, 45 (12), 88 (1968). (5A) Roth, D. W. A., Twilley, I. C., and Harvre, L. K., Chem. Eng., 7 5 (27), 86 (1968). (6:d6b(ybber Industry Facts,” Rubber Manufacturers Assoc., New York, (7A) Seymour, R. B., Plustiques, 5 (6), 349 (1968). (EA) Seymour, R. B., Plust,inAustralia, 19 (7), 11 (1968), Education i n Polymer Science and Technology
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(42B) Bruins, P. F., “Epoxy Resin Technology,” Interscience, New York, 1968. (43B) Bruins, P. F., “Plastics for Electrical Insulation,” Interscience, New York, 1968. (44B) Bruins, P. F., “Polyurethane Technology,” Interscience, New York, 1968. (45B) Buist, J. M., and Gudgear, H., “Advances in Polyurethane Technology,” Interscience, New York, 1969. (46B) Couzens, E. G., and Yarsley, V. E., “Plastics in the Modern World,” Pelican Press, New York, 1968. (47B) Doyle, E. N., “The Development and Use of Polyester Products,” McGrawHill, New York, 1968. (48B) Frank, H. P., “Polypropylene,” Gordon and Breach, New York, 1968. (49B) Frazer, A. H., “High Temperature Resistant Polymers,” Plenum Press, New York, 1968. (50B) Gould, R. F., “Stabilization of Polymers and Stabilizer Processes,” American Chemical Society, Washington, D. C., 1968. (51B) Griff, A. L., “Plastics Extrusions Technology,” 2nd ed., Reinhold, New York, 1968. (52B) Hildago, C. J. “Flammability Handbook for Plastics,” Technomic Pub. GO., Stamford, Conn., lb68. (53B) Kamal, M . R., “Weatherability of Plastic Materials,” Wiley, New Yo&, 1968. (54B) Katon, J. E., “Organic Semiconducting Polymers,” Marcel Dekker, New York, 1968. (55B) Kaufman M., “Giant Molecules ” and “The Technology of Plastics, Fibers and Rubber,”’Doubleday & Co., N e d York, 1968. (56B) Kenne! J. P and Toin uist, E. “The Polymer Chemistry of Synthetic Elastomers, ‘inters?ience, New%ork, 1668. (57B) Keskkula, H., “Polymer Modifications of Rubbers and Plastics,” Interscience, New York, 1969. (58B) Koleski, J. V., and Wartman, L. H., “Poly(viny1 chloride) ,” Gordon-Beach, New York, 1969. (59B) Lenk, R. S. “Plastics Rheology,” Maclaren, London, 1968. (60B) Lever, A. E., and Rhys, J. A., “Properties and Testing of Plastics,” CRLPress, Cleveland, Ohio, 1968. (61B) Lewis, 0. G., “Physical Properties of Linear Homopolymers,” SpringerVerlag, New York, 1968. (62B) Lubin, G., “Reinforced Plastics,” Reinhold, New York, 1969. (63B) Mallinson J H “Chemical Plant Design with Reinforced Plastics,”McGrawHill, New Yord, i96;. (64B) McCreight, L. R., Rauch H. W and Sutton W. H . “Ceramics and Graphite Fibers and Whiskers,” GeLeral Eikctric Co., King of Prussia, Pa, 1968. (65B) McIntyre, D., “Characterization of Macromolecular Structure,” National Academy of Science, Washington, 1968. (66B) Middtpman, S., “The Flow of Hi h Polymers Continuum and Molecular Rheology, Interscience, New York, 1 9 b . (67B) Miller, E., “Textiles: Properties and Behavior,” Batsford, London, 1968. (68B) Moacanin, J., Holden, G., and Tschoegl, N . W., “Block Copolymers,” Interscience, New York, 1968. (69B) Raff, R. A. V., “The Graftin of Organic Pol mers onto Inorganic Substances,” U . S . Dept. of Commerce,%pringfleld, Va., r968. (70B) Reich, L., and Stivala, S. S., “Autoxidation of Hydrocarbons and Polyolefins, Kinetics and Mechanisms,” Marcel Dekker, New York, 1969. (71B) Rosato, D. K., Fallow, W. K., and Rosato, D. V., “Market for Plastics,” Van Nostrand-Reinhold, Princeton, N. J., 1968. (72B) Rubin, I. D., “Poly(1-butene),” Gordon-Breach, New York, 1968. (73B) Sarvetnick, H. A,, “Polyvinylchloride,” Van Nostrand-Reinhold, Princeton, N. J., 1968. (74B) Schwartz, R. T., and Schwartz H. S “Fundamental Aspects of Fiber Reinforced Plastic Materials,” Interscience, N& York, 1968. (75B) Serafini, T. T., and Koenig, J. L., “Aryogenic Properties of Polymers,” Marcel Dekker, New York, 1968. (76B) Seymour, R. B., “Polymer Chemistry,” McGraw-Hill, New York, 1969. (77B) Sitti M., “Synthetic Leather from Petroleum,” Noyes Development, Park Ridge, $J., 1969. (78B) Smith, D. A., “Addition Polymers, Formation and Characterization,” Plenum Press, New York, 1968. (79B) Sonneborn, R. H., and Rue, C. C “Reinforced Plastics,” International Correspondence Schools, Scranton, Pa., 1d68. @OB) Sorenson W R. and Campbell R W., “Pre arative Methods of Polymer Chemistry,” i n d ’ed.,’Interscience, N‘ew‘York, 196f. (81B) Szwarc, M., “Carbanions, Living Polymers and Electron Transfer Processes,” Interscience, New York, 1968. (82B) Tsurata, T., and O’Driscoll, K. F., “Structure and Mechanism in Vinyl Polymerization,” Marcel Dekker, New York, 1969. (83B) Wendland R. T “Petrochemicals, The New World of Synthetics,” Doubleday, GardcnC:ty,N.%,, 1969. (84B) Whitehouse, A. A. K., Pritchett, E. G. K., and Barnet, G., “Phenolic Resins,” American Elsevier, New York, 1968. Plastic Structures
(1’2) Appl. Plast., 11 (lo), 18 (1968). (2C) Becker, W. E., SPE-26th Ann. Tech. Conf., 14 354(1968). (3C) Carmen, R., and Kahn, P., Biornec. M a t e r . Res., 2 (4), 457 (1968). (4C) Chem. Eng., 76 (7), 86 (1969). (5C) Cheetham, M . A., Plast. Poly., 36 ( Z ) , 15 (1968). (6C) Dallaire, E. E., Chem. Eng., 7 6 (7), 80 (1969). (7C) Darrington, P., Plast. Poly., 36 (121), 53 (1968). (8C) Dussek, I. J., Inst. Highway Eng., 15 (4),7 (1968). (9C) DuPuy, L. E. R., Plsstica, 21 (lo), 419 (1968). (1OC) Fenner, 0. H., Mater.Protection, 7 (5), 19 (1968). (11C) Fried, N., Plast. Poly., 36 (6), 261 (1968). (12C) Howe, H. E., and Radtla, S . F., AdhesiwesAge, 11 (9), 22 (1968). (13C) Izat, G., Plurt. Poly., 7 (5), 19 (1968). (14C) Jackson, B., and Welch, M., Rubber J . , 150 (3), 12; (4), 46; ( 5 ) , 65 (1968). (15C) Johnson, R. J., S P E J.,24 (lo), 98 (1968). (16C) Laeis, W., Kuwtstofe, 5 8 (4), 305 (1968). (17C) Lin, H., Plast. Poly., 36 (6), 249 (1968).
VOL. 6 1
NO. 8
AUGUST 1969
37
Mallinson, J. H., Mater. Protection, 7 ( 5 ) , 19 (1968). Mod. Plast., 45 ( 8 ) , 84 (1968). Ibid., p 108. Murphy, J., Kunststoffe-Plastics, 15 ( S ) , 173 (1968). Neith, W. N., ibid., p 166. Plastica, 21 (2),67 (1968). Ibid., (3), p 96. Ibid., (15), p207. Ibid.,(11),p554. Plast. in Australia, 19 (31, 29 (1968). Ibid., (7), 18 (1968). Prod. Eng., 39, 156 (1968). Rechner, L., Maieriuux et Constructions-Muter. Slruclures, 1 (3), 227 (1968). Rees, K., Plnrt. in Australia, 19 (7), 16 (1968). Reid, A.,ibid., (3), 31 (1968). RubberPlust.Ape,49 (1),56 (1968). Ibid., (7), 638 (1968). Russo, M., Mater. Plost. Elastomeri, 34 (3), 293 (1968). Simpson, J. H., Plast.Poly., 36 (2), 7 (1968). Sleddon, G. J., Chem. Ind., 1968, 907. Srnejkal, V., PlnstickeHmoty Kaucuk, 5 (2), 44 (1968). Stahl, J. S., and McKee, J. R., SPE26thAnn.Tech. Conf., 14, 369 (1968). Stibrany, P., PlustickeHmoly Kaucuk, 5 ( Z ) , 39 (1968). Strzelbicki-Sas, G., Kunrtrtofe-Rundschnu, 15 (9), 485 (1968). Van Laere, R. J., Plastica, 21 (2), 60 (1968). Van Zetten, L., ibid., ( l ) , 12 (1968). Visser, C. A., ibid.,( l l ) , 521, 536, 542 (1968). Wilson, E. L., and Gelin, R. J., P h i . Technol., 15 (2), 61 (1969). Wolff, G., Bouzeitung, 22 (l), 25 (1968). Zonneveld, R., Plartica, 21 (G), 236 (1968). Plastic Containers a n d Vessels
(1D) Bailey,F. Z., andBailey, M . E., Plnst. Elost., 20 ( 7 ) , 125 (1968). (2D) Berger, W., Kuflststofe, 58, 186 (1968). (3D) Bippus, W . , and Akermann, H., ibid., p. 197. (4D) Borsian, W., Plustnrbeiter, 1 9 (4), 293 (1968). (5D) Bruhn, R., V~rpnckungs-Rundschau,19 (5), 524 (1968). (6D) Coward, C . T., and Nash, M . H., Rubber Plnst. Age, 49 (4), 329 (1968). (7D) Dooley, D. D., Package Eng., 1 3 (11), 76 (1968). (8D) Hannigan, K . U., FoodEng., 40 (3),70 (1968). (9D) Hansen, G., Kunrtrtofe, 58, 217 (1968). (10D) Harding, J.S.,Plart.Poly.,36 (124), 317 (1968). (11D) Hertsch, H., Verpackungs-Rundschau, 19 (6), 672 (1968). (12D) Holder, R . G., and Copping, B. G., Mod. Packaging, 41 ( 9 ) , 143 (1968). (13D) Holzmann, R., and Kluescner, P., Veerpackungs-Rundschatr, 1 9 (lo), 1228 (1968). (14D) Kaliwoda, K., Kunststaffe, 58, 216 (1968). (15D) Kelley, D. S., Puckage Eng., 13 (4), 68 (1968). (16D) Kuehne, G., Verpackirngs-Rlindschou, 19 (41, 411 (1968). (17D) McLauglin,T,F.,PnckageEng.,13(11),76 (1968). (l8D) Mod. Packaging, 41 (lo), 106 (1968). (19D) Mueller, B., Suchan, D . F., and Overhoff, H., Verpnckungs-Rundschnu, 19 (4), 400 (1968). (20D) Mueller, D . E.,ibid., 19 (6), 669 (1968). (21D) Ninneman, K . W., and Pechenski, L., Package Eng., 1 3 (3), 66 (1968). (22D) Peach, A . F., Rubber ?last. Age, 49 ( 9 ) , 847 (1968). (23D) Pelzer, H., and Hinsken, H., Verpockungs-Rundschou, 1 9 (3), 222 (1968). (24D) Pluslica, 21 (91, 394 (1968). (25D) Pratella, G . C., MateriePlasticheedElastomer, 33 (lo), 1039 (1967). (26D) Ranken, M. D., Plurt. Poly., 36 (124), 325 (1968). (27D) Rubber Plart. Age, 49 (6), 538 (1968). (28D) Sacharow, S., Kunstofe-Rundschuu, 15 (4), 171 (1968). ( 2 9 0 ) Sacharow, S., Verpackungs-Rundschau, 19 (31, 230 (1968). (30D) Sacharow,S.,Plast.inAustralia,19 (l), 11 (1968). (31D) Sacharow, S.,Plart.Des. Process., 8 (7), 14 (1968). (32D) Schoenbach, G., Kunststofe, 58,188 (1968). (33D) Schvtte, K., Verpuckungs-Rundschau, 19 (3), 214 (1968). (34D) Signore, A. C., Mod. Packaging, 41 (6), 143 (1968). (35D) Takouchi, T., Jup. Plast. (Tokyo), 2 (21, 5 5 (31, 21 (1968). (36D) Van Himbeeck, J., Rev. Belle des M a l i e r e s Plasfiques, 9 (3), 175 (1968). (37D) Verpnckungs-Rundschau, 19 (lo), 1226 (1968). (38D) Walker, K . G., Plnst. Poly., 36 (125), 479 (1968). (39D) Wallenber, K . E. S., Mod. Packaging, 4 1 (6), 146 (1968). (40D) Weber, W. O.,SPEJ., 25 (2), 70 (1969).
Plastic Composites
(1E) Algra, E.A.H., andVanderBeek, M.H.B.,Plorlica, 2 1 (7), 282 (1968). (2E) Armbruster, F., Kunststofe u Gummi, 7 (5), 151 (1968). (3E) Bares, R., Navratil, J., et ai., Colloid J.of USSR, 3, 239 (1967). (4E) Bascom, W. D., and Romans, I. B., IND.ENC.CHEM.,PROD.RES.DEVELOP., 7 (3),179 (1968). (5E) Bil, V. S., and Autokratova, N . D., Plasticheskie Mussy, (2), 35 (1968). (6E) Boehm, R.D.,J.A@l. Poly.Sci., 12 (5), 1097 (1968). (7E) Braun, G., Plast. Poly., 36 (4), 135 (1968). (8E) Caroselli, R. F., Man, Made FibersSci. Technol., 3, 425 (1968). (9E) Chatgc, N. D., and Mahajan, S. S., Rubber World, 159 ( 2 ) , 61 (1968). (10E) Deanin, R. D., ‘Margosiak, S. A , , and Llompart, A , , Mod. Plast., 46 (I), 114 (1969).
38
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
(11E) Deanin, R. D., Baum, B., et al., Division of Organic Coatings and Plastics Chemistry, ACS Preprints, 29, (1) 105 (1969). (12E) desilva, A. K . T . , J . M e c h . Phys.So/ids, 16 (6), 169 (1968). (13E) Dvoretskaya, R. M., Ivnitskaya, R. B., et o l . Plnsticheskie iMossy, (6), 65 (1968). (14E) Ekstrome, W. B.,and Rosen, S. L . , S P E J . , 24 (9), 53 (1968). (15E) Filbert, W. C., ibid., 25 (l), 65 (1969). (16E) Fletcher, J. A,, ReinforcedPlast. Composites World, 8 (l), 5 3 (1969). (17E) Germelis, A , , Latishenko, V. A,, and Likovskil, V. Y., Mekh. Polim.,4 (5), 853 (1 968). (18E) Gleich, D., Plastnrbeiter, 19 (9), 679 (1968). (19E) Goldsworthy, W. B., ReinforcedPlust. Composites World, 39 (5), 645 (1968). (20E) Golugenkova, L. D., Nikonova, S. N., et al., Plarticheskie Mossy (5), 36 (1968). (21E) Hamilton, K. W. O., Greeve, D. B., and Davidson, D . E., Reu. Sci.Inrtr., 39 (5), 645 (1968). (22E) Hauck, J. E., Mod. Plast., 45 (11) 80 (1968). (23E) Jones, R. F., S P E A n n . Tech.Conf., 14,533 (1968). (24E) Jube, G., Plnst. Poly.,36 (61,221 (1968). (25E) Kercha, Y. Y., Lipatov, Y. S., and Ryaibokon, L . I., Sin.Fiz-Khim. Polim., ( 5 ) , 193 (1968). (26E) Klimanova, R . S., Sergecva, V. K., and Serenkov, V. L., Plasticheskie Massy, (5),33 (1968). (27E) Kochnov, I. M., Lutsenko, L. M., e t a l . , ibid., (2), 28 (1968). PROD.RES. Kohn, E. J., Sands, A . G., and Clark, R . C., IND.ENG.CHEM. DEVELOP., 7 (3), 179 (1 9 6 8 ) . (29E) Lees, J. K., Poly. Eng.Sci., 8 (31,186,195 (1968). (30E) Luben, G., Plart. Technol., 1 4 (lo), 59 (1968). (31E) htackay, H. A., and Courtney, R. L. Mod. Plast., 45 (12), 147 (1968). (32E) hlandler, H., Plasterarbeiter, 19 (3), 185 (1968). (33E) Maki, R., Kobunshi Kagaku, 17 (1981, 857 (1968). (34E) Matonis, V. A , , Poly. Eng. Sci., 9 (21, 100 (1969). (35E) Mattavi, J. L., and Seibert, A. G . , ASME Papcr 69-PVP-21, Sept, 22, 1968. (36E) McGarry, F. J., and Fujiwara, M., Mod. Plat., 45 ( l l ) , 143 (1968). (37E) McSharry, J. J., and Cook, K . L., ibid., 45 (12), 137 (1968). (38E) Milewski, J. V., ReinforcedPlast. Composites World, 8 ( l ) , 24 (1969). (39E) Mod. Plast., 46 (4), 102 (1969). (40E) Mohr, J. B., Reinforced Plast. Composites World, 8 (I), 13 (1969). (41E) Morton, M., Austrul. Rubber, 1 (12), 5 (1968). (42E) Mueller, H. D., Kumtsfofe, 58,777 (1968). (43E) Newey, H . A , , Plast. Resinar, 10 (53), 28 (1968). (44E) Nielson, L. E., and Chen, P. E., J.Muter., 3 (2), 352 (1968). (45E) Ogden, G., and Morant, D., Appl. Plnst., 11 ( l l ) , 40 (1968). (46E) Pakhomov, V. I., Serdynk, N . I., et al., Plusticheskie Marry, ( 5 ) , 48 (1968). (47E) Pearlman, D. V., and Tully, P. R., Plost. Technol., 14 (13), 50 (1968). (48E) Pearson, L. E., Isham, A. B., and Cargnel, S., Poliplnst. Plast. Rinforz., 16 (129), 18 (1968). (49E) Plast. World, 26 (12), 20 (1968). (50E) Poimanov, A . M., Belnik, A . R., et al., Mekh. Polim., 4 (41, 677 (1968). (51E) Riley, V. R., and Reddaway, J. L., J.Muter. Sci.,3 ( l ) , 41 (1968). (52E) Sagalaev, G. V., and Ismailov, T. M., Plarticheskie Massy, (2), 59 (1968). (53E) Sanzhatonskii, A . T., and Sankov, V. M., ibid. (l), 12 (1968). W E ) Seymour, R . B., Mod. Plast., 45 (14A), 570 (1968). (55E) Shapiro, T. M., and Gorshkov, V. S., Plasticheskie M a s s y , (111, 10 (1968). (56E) Smith, T. R . , and Owen, hf. J., Mod. Plnst., 46 ( 5 ) , 128 (1969). (57E) Spiegel, M. J., ReinforcrdPlnst. Composites World., 8 ( l ) , 56 (1969). W E ) Sprietsma, H. B., Kunrtstofe, 58, 777 (1968). (59E) Stern, H . J., Maunder-Foster R.,and Mead, S. F., Inst. Rubber Imd. J . , 1 ( G ) , 336 (1967). (60E) Sugio, O.,.Sen-ItoKogyo, 1(4),201 (1968). (61E) Takenaka, Y., Ogawa, K., and Nogushi, Y., Kyoka Purasuchikkuso, 1 4 (9,282 (1968). (62E) Theberge, J. E., Mod. Plast., 45 (lo), 155 (1968). (63E) Trostyankaya, E. B., and Gunyaev, G. M., Soviet Plast., ( S ) , 28 (1967). (64E) Vinogradov, V. M., Plasticheskie Massy, (9), 32 (1968). (65E) Viventi, R. V., Plant, H. T., and Maker, R . T., Mod. Plast., 45 (l5), 289 (1968). (66E) Wadsworth, N. J., and Spilling, I., Brit.J . Appl. Phys., 1 ( 8 ) , 1049 (1968). (67E) Warner, F. E., Mod. CompositeMater., 1967,244. (68E) Wesh, L., Plast. Poly., 36 (6), 24 (1968). (69E) Wilmes, K., Plastverarbeiter, 19 (71, 511 (1968). ( 7 0 E ) Yakohson, B. Y . , Sokolov, A. D., el a!., PlastickeskierMassy, (21, 32 ( 1 9 6 8 ) . (71E) Yanovskii, Y. B., Frenkine, I,, and Vinogradov, G. V., Rheol. Acta, 7 (3), 277 (1968). (72E) Young, P. R., ReinforcedPlnsl. Composites World, 8 (l), 277 (1968). (73E) Zurbrick, H. R . , S P E J.,24 (91, 56 (1968). P o l y m e r Sheet a n d Film
(1F) Ancker, F. H., Plast. Technol., 14 (12), 50 (1968). (2F) Braslinsh, U. E., Kalis, V. Y., et al., Plasticheskie Massy, (4), 39 (1968). (3F) Cadvtre, J., Division of Cellulose, Wood, and Fiber Chemistry, 157th Meeting, ACS, Minneapolis, hlinn., April 1969. (4F) Caldwell, J. R., and Jackson, W. J., J.Poly. Sci., 24,15 (1968). (5F) Fadeeva, A. V., Kurzhenkova, et a/., Plasticheskie Massy, (4), 50 (1968). (6F) Fomina, L. L., and Gul, V. E., Ibid., ( 6 ) , 52 (1968). (7F) Guillotte, J. E., Mod. Plart., 46 (11, 128 (1969). (8F) Huang, R . Y. M., and Lin, V. J. C., J.Appi. Poly. Sci.,12, 2615 (1968). (9F) Jacobs, P. E., and Rizos J. A , , Package Eng., 13 (lo), 84 (1968). (10F) Johnson, J . S., Gouveia, .4.et , nl. Water Chem. Eng. Progr. Ser., 64, 90 (1968), Am. Inst. Chem. Eng., New York. (11F) Kimura, H., EhimeDaigaku Kiyo, 6 ( l ) , 35 (1968). (12F) Kimura s. Sourirajan, s., and Ohya, H., I N n . ENC.CHEhl. PROCESS DES. DEVELOP., 8’(1),’79 (1969).
(13F) Kolb, D. J., Plast. in Airstruliu, 19 (lo), 29 (1968). (14F) Komarov, G. V., Tostyanskaya, E. B., and Pavlova, A. P., Plusticheskie Massy, (9), 52 (1968). (15F) Kozlowski, R. R., and Ratchford, J. J., Plust. Technol., 14 (9), 31; (12), 43 (1968). (16F) Kramer, H., and Messner, D., Kunststofe, 58 (lo), 673 (1968). (17F) Limbert, F. J., S P E J . , 24 (41, 91 (1969). (18F) Michaels, A. S . , Chem. Eng. Progr., 64 (12), 31 (1968). (19F) Miller, E. F., Chem. Eng., 75 (25), 153 (1968). (20F) Newey, A. B., Muter. Protection, 7 (E), 35 (1968). (21F) Ohya, H., and Sourirajan, S.,IND. END.CHEM.,PROCESS DES. DEVELOP.,8 (I), 131 (1969). (22F) Pnttison, D. E., Chem. E w . , 7 5 (12). 38 (1968) (23F) peterson, A., Division of Polymer Chemistry, 157th Meeting, ACS, Minneaoolls. Minn.. Ami1 1969. (24F) Prall, G. M., Plust. Technol., 14 (E), 43 (1968). ( 2 9 ) Tsutomu, N., Kogyo Kagaki Zusshi, 71 (E), 1272 (1968). (26F) Vlasov, S . V., Segalaev, G. V., and Belov, E. P., Plasticheskie Mussy, (4), 40; (6),50 (1968). (27F) Yamane, R., Ichikawa, M., et ul., IND. END.CHEM.,PROCESS DES. DEVELOP. 5, 159 (1969).
,.
C e l l u l a r Polymers
(1G) Armstrong, A., and Traeger, R. K., J.Cell. Plast., 4 (lo), 329 (1968). (2G) Beck, W. R., O'Brien, D. L., and Davies, E. P., SPE J.,25 (4), 83 (1969). (3G) Benford, A. E., J . Cell. Plast., 5 (l), 51 (1969). (4G) Benning, C . J., ibid., p. 40. (5G) Bjornsson, B. A., Plustuurlden, 18 (2), 34 (1968). (6G) Blaich, C. F., Plast. Technol., 14 (12), 55 (1968). (7G) Briscoll, H., and Thomas, C. R., Brit. Plart., 41 (7), 79 (1968). (8G) Brit. Plust., 41 (lo), 84 (1968). (9G) Brown, W. B., Rubber Plast. Age, 49 (91, 829 (1968). (10G) Chatelain, J., Ledoux, C., e t a l . , Ind. Chem. Belge, 32, 423 (1967). (1lG) Delmonte, J., Adhesiues Age, 11 (4), 27 (1968). (12G) Dickinson, L. A., and McLennan, D. E., J.Cell. Plast., 4 (4), 149 (1968). (13G) Dietz, G. R. SPEJ., 24 (9), 49 (1968). (14G) Dunaetz, R. A,, and Budna, J. J., J.Cell. Plast., 4 (6), 229 (1968). (15G) Ebneth, H., Kunststoffe, 58,598 (1968). (16G) Faddoul, J. R., and Lindquist, C. R., J.Cell. Plust., 4 (3), 113 (1969). (17G) Fincke, J. K., and Wilson, G. R., Mod. Plust., 46 (4), 108 (1969). (18G) Gordon, J. B., Immel, R. H., and Slaprich, J., SPE J.,24 (E), 51 (1968). (19G) Hansen, R . H., and Martino, W. M., Poliplnst. Plust. Rinforz., 16 (127), 19 (1968). (20G) Harding, J. S . , RubberPlost. Age, 49 (8), 317 (1968). (21G) Hecker, K. C., Rubber World, 159 (3), 59 (1968). (22G) Hobaica, E. C., and Cook, S . D., J.Cell. Plust., 4 (41,143 (1968). (23G) Kanner, B., and Decker, T. G., ibid., 5 ( l ) , 32 (1969). (24G) Keller, L. B., ibid., 4 (111, 418 (1968). (25G) Knall, H., and Gros, I., Mater. Plust., 5 (4), 182 (1968). (26G) Lebel, P., RubberPlast. Age, 49 (6), 522 (1968). (27G) Leese, L., Plus!. Poly., 36 (6), 189 (1968). (28G) Lensing, R., and Fleming, P. J., Rubber Plust. Age, 49 (4), 327 (1968). (29G) Meazly, A. T., Brit. Plast., 41 (9), 133 (1968). (30G) Mihira, K., Ohsana, T., and Nakayama, A., Kolloid-Zeit Zeit Fuer Polymere, 222 (21,135 (1968). (31G) Muroshov, Y. S . , and Valgin, V. D., Plusticheskie Massy, (Z), 49; (3), 22 (1968). (32G) Nadeau, H. G., Plast. Techno!., 14 (lo), 65 (1968). (33G) Naturman, L., ibid., 15 (l), 44 (1969). (34G) Plustvarlden, 18 (7-8), 44 (1968). (35G) Porteou, A., and Waller, G . B., J . Cell. Plast., 4 ( l l ) , 431 (1968). (36G) Progr. Plust., 10 (lo), 27 (1968). (37G) Raff, R. A. F., and Adams, M . F., SPE J.,24 ( l l ) , 23 (1968). (38G) Scheiner, L. L., PIust. Technol., 14 (13), 135 (1968). (39G) Schutz, C. A,, J . Cell. Plast., 4 (4), 32 (1968). (40G) Smith, C . H., and De Gisi, S. L., ibid., 4 (lo), 386 (1968). (41G) Smith, H. A,, Plust. Technol., 14 (9), 38 (1968). (42G) Stewart, S . A., Plus!. World, 26 (7), 46 (1968). (43G) Sivenson, S.B., J.Cell. Plust., 4 (51,178 (1968). (44G) Waite, W. A., Waldron, M. L., and Habedean, A., Undersea Technol., 9 (6), 33 (1968). (45G) Williams, J. L., Bell Lnb. Record, 46 (lo), 305 (1968). (46G) Wolf, G. M., and Marinette, M. A,, SPEJ., 24 (7), 42 (1968). (47G) Woolard, D. C., J.Cell. Plast., 4 (l), 16 (1968). (48G) Wollard, D. C., Poliplast. Plast. Rinforz., 16 (127), 19 (1968). (49G) Wright, J. M., P l a t . in Australia, 19 (lo), 15 (1968). Plastic Plpe
(1H) Arp, J., Plastuarlden, 18 (6), 5 5 , 62 (1968). (2H) Binder, G., Kunstofe Plast., 15 (51, 152 (1968). (3H) De Croly, P., Rev. Belgc des Mutieres Plus!., 9 (31, 153 (1968). (4H) Derveaux, M., ibid., p. 159. (5H) Faust-Kuebler, E., Kunststoff-Rundschau, 15 (9), 488 (1968). (6H) Hobincu, A,, Crainic, C., et ul., Muter. Plusl., 5 (3),, 145 (1968). (7H) Keggs, F., MuunyagesGumi, 5 (4), 141 (1968). (8H) Kulicek, V., Plastickc Hmoty Kaucuk, 5 (9), 266 (1968). (9H) Lauffenberg, F., Kunslstoffe-Rundschau, 15 (E), 429 (1968). (10H) Neitzel, M., V D I Z e i t , 110 (153,618 (1968). (11H) Poole, H. V., Plast. Poly., 36 (41, 155 (1968). (12H) Schweitzer, P. A., Air Cond., Heut. Vent, 65 (9), 45 (1968).
(13H) Signorini, P. P., PI&. World, 27 (4), 20 (1969). (14H) Strese, H., V D I Z e i t , 110 (15), 609 (1968). (15H) Werblinski, W., Polimery, 13 (l), 5 (1368). (16H) Wijbrans, F. W. R., Plusticu, 21 ( 9 ,287 (1968). (17H) Wilski, H., Gaube, E., and Roesinger, S . , Kerntechnik, 10 (3), 142 (1968). (18H) Witteveen, F., Plusticu, 21 (9), 380 (1968). (19H) Wright, C. W., Chem. Eng., 75 (13), 230 (1968).
Synthetic Flbers
(1K) Legk. Antoshkina Pron., (6),'45'(1%8). T F Shevchenko, A. S . , et al., Izu Vyssh. Ucheb Zuued., Technol. (2K) Avny, Y., and Rebenfeld, L., Tex. Res. J . , 38 (7), 684 (1968). (3K) Bezhusashvili, T . ,et ai., Khim. Voloknu, ( 5 ) , 74 (1968). (4K) Blouin, F. A., Morris, N. J., and Arthur, J. C., Tex. Res. J., 38 (7), 710 (1968). (5K) Blouin, F. A,, Arthur, J. C., et al., ibid., 38 ( 8 ) , 811 (1968). (6K) Bochkov, G., Volf, L. A., and Meos, 0.I., Legkuyu Prom., (4), 52 (1968). (7K) Bulik, S . , Kielbasinski, W., eta!., Polimery, 13 (E), 367 (1968). (8K) Choinski, Z.,ibid., 13 (5), 185 (1968). (9K) Coo er S.L., McKinnon, A. J., and Prevorsek, D. C., r e x . Res. J . , 38 (E), 803 (1983) (1OK) Crum, J. K., Anal. Chem., 41 (2), 26A (1969). (11K) Ford. J. E., Chem. Ind., 1968,1417. (12K) Gorchakova V M Ustinova E. T and Voyutskii, S . S . , Izu. Vyssh. ucheb. Zeued., Tekhnol. L$k.'Pro'k, (5), 20 '(1968j: (13K) Grebowski, J., and Nowakowski, J., Pr.Inst. W o k , 17, 271 (1967). (14K) Hebeisch, A,, and Mehta, P. C., Text. Res. J., 38 (lo), 1070 (1968). (15K) Illing, G., Kunststoftecknik, 7 (lo), 351 (1968). (16K) Katayama, K., Amano, T., and Nakamura, N., Kolloid-Zeit Zeit fuer Poly., 226 (21,125 (1968). (17K) Katsuura, K., and Yamane, T., S e n 4 Gukhaishi, 24 (E), 378 (1968). (18K) Kercha, Y. Y., Zubovich, e t u l . , Khim. Volknu, (5), 71 (1968). (19K) Klos, S . , Chemik (Gliwice), 21 (e), 285 (1968). (20K) Maslowski, E., ibid., 21 (E), 289 (1968). (21K) McCaffery, E. L., J. Chem. E d . , 46 ( l ) , 59 (1968). (22K) Mezhirov, M . S . , and Ovsynnikova, V. A,, Khim. Voloknn, (6), 20 (1968). (238) Miroschnichenko, I. I., Samsonova, T . I., et a!., ibid., (51, 75 (1968). (24K) Muromova, R. S., Demidova, T. V., et al., ibid., (51, 70 (1968). (25K) Paul, D. R., J . Appl. Poly. Sci., 12, 2273 (1968). (26K) Pierce, A. G., and Reinhardt, R. M., J . Poly. Sci.-Poly.Symp., (24), 725 (1968). (27K) Rogovin, 2.A., Chemiefusern text Aniuendungstech., 1 8 (lo), 738 (1 968). (28K) Romamova, T. A., Zharkova, M. A., et ul., Khim. Voloknu, (5), 23 (1968). (29K) RubberPlast. Age, 49 (91,795 (1968). (30K) Sagaguchi, Y., Sen-i To Kogyo, 1 (I)', 4 (1968). (31K) Samuels, R. J., J. Poly. Sci., A-2, 6 , 2021 (1968). (32K) Schulman, S . , Poly. Eng.Sci., 8 (l), 32 (1968). (33K) Shchetinin, A. N., Khim. Voloknu, (5), 50 (1968). (34K) Shimeha, J., and Koyana, K., Kngaku, (Kyoto), 23 ( l l ) , 1014 (1968). (35K) Shimizu, A., Shinozaki, Y.,et ul., Sen4 Gakkaishi, 24 (8), 361 (1968). (36K) Skwarski, T., and Mikolajczyk, W., Polimsry, 13 (51,197 (1968). (37K) Skwarski, T., Mikolajcyk, T., and Krasinska, A., ibid., 13 (7), 301 (1968). (38K) Stalevich, A. N., Tiranov, V. G., and Malentov, P. V., Legkuyu Prom. (5), 17 (1968). (39K) Laboratory, 37 (1969). (40K) Van Veld, R. D., Morris, G., and Billica, H. K., J . Appl. Poly. Sci., 12, 2709 (1968). (41K) Wlochowicz, A., Polimery, 13 (6), 256 (1968). (42K) Za alova, 2. A., Petrova, L. U., and Pakshvet, E. A., Khim. Volokna, ( 9 , 20 (1963. (43K) Zrerov, M. P., Barash, J. V., and Kostrova, K . A., ibid., (6) 48 (1968).
Polymers US. W e a t h e r
(1M) Adolf, F., V D I (VerDeut. Ins.) Z . , 110 (251,1105 (1968). (2M) Akijama, M., Shimada, J., et ut., Denki Tsushin Kenkyusho Kenkyu Jttsuyoka Hokoku, 17 (9), 1961 (1968). (3M) Aleksandrov, A. Y., Baldokhim, Y. V., et ul., Khim. Vys. Energy, 2 (4), 331 (1968). (4M) Barshstein, R. S . , Plnsticheskie Massy, (12), 13 (1968). (5M) Baudisch, V., and Zimmerman, H., Pluste Kuutschuk, 15 (8), 549 (1968). (6M) Boboev, T. B., Regel, V. R., et ul., Mekh. Polim., 4 (4), 661 (1968). (7M) Briggs, P. J., and McKellar, J. F., J . Appl. Poly. Sci., 12 1825 (1968). (8M) Deanin, R. D., Mod. Plust., 46 ( l ) , 114 (1969). (9M) Deanin, R. D., Rev. Gen. Caoutchouc Plust., ed. Plust., 5 (3), 155 (1968). (1OM) Dodson, U.M., and Sharma, V. R., Rubber PI&. Age, 49 (6), (1968). (11M) Dolezel, B., Adamirova, L., and Akimova, G . L., Plasticke Hmoty Kuucuk., 5 (9), 260 (1968). (12M) Geleji, F., and Holly, S . , Mugy. Kern. Lapi., 23 ( 9 ) , 477 (1968). (13M) Geuskens, G., F.A.T.I.P.E.C., 9, 20 (1968). (14M) Gesner, B.D., S P E J . , 25 (l), 73 (1969). (15M) Glushkova, L. V., and Starkov, S . P., Khim. Prom., 44 (E), 571 (1968). (16M) Jellinek, H. H. G.,Strcochem. Macromol., 3,371 (1967). (17M) Kaminskii, A. A,, Dopouidi Akud. Nauk. Ukr Ser A , 30 (7), 660 (1968). (18M) Kelleher, P. G., Miner, R . J., and Boyle, D. J., S P E J . , 25 (2), 53 (1969). (19M) Kimura, T., Kagakr, To Kogyo (Osaka), 42 (3), 127 (1968). (20M) King, A,, Plast. Poly., 36 (123), 195 (1968). (21M) Klaponskaya, 0. A., Korvarskaya B., et a[., Plasticheskid Mussy, ( 7 ) , 41 (1968). (22M) Moore, R. A., Kund, H. L., and Gower, B . G., Rubber World, 159 (5), 55 (1969).
VOL. 6 1
NO. 8
AUGUST 1 9 6 9
39
( 2 3 ~ Morrell, ) S.H., and Mosely, R. J., Rubber J.,150 (lo), 75 (1968). (24M) Mullins, L., Kuuch. Rezeua, 27 (7), 10 (1968). A., Chem. Tech. (Amsferdum),23 (13), 373 (1968). ( 2 5 ~ Nauck, ) (26M) Penczek, P., Przem. Chem., 47 (lo), 602 (1968). (27M) Rose, S.H., J.Poly. Sci.,B 6,837 (1968). (28M) Seidov, V. M., Dolin, M . A,, and Kyazimov, S. M., Azerb. Khim. Zh., (l), 68 (1968). ( 2 9 ~ Sekhar, ) B. C., Ind. Gamma, 12 (5), 30 (1968). (30M) Schmidt, Y. A,, Keltseva, 0. B., and Semonova, N. I., Sin. Fir-Khim. Polim. (5),5 (1968). ( 3 1 ~ Steihler, ) R . D., Parks, E. J., and Lining, F. J., Appl. Poly. Symp., (7), 143 (1968). ( 3 2 ~ )Stoica,M. Reu.Fiz.Chim.SerA., 5 (4), 132 (1968). (33M) Toernquist, E., High Poly., 23 (l), 21 (1968). (34M) Tucker, H . A , , and Jorgensen, A. H., ibid., p. 253. (35M) Werner, H., ibid., p. 185. (36M) Van der Hoff, B.M.E., Appl. Poly. Symp., (7), 143 (1968). (37M) Younger, J . D., Ind. Rubber Bull., (236), 18 (1968). polymers VS. F l a m e
(IN) Aenishaenslin, R., Meliand Textilber, 49 (lo), 1210 (1968). (2N) Alaminov, H., Michailov, M., and Damianova, I., J . Poly. Sci., C22 (l),419
(1968). (3N) Andrews, W. R., J.Cell. Plast.,4 (3), 102 (1968). (4N) Appl. Plust., 11 (81, 38 (1968).
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Polymers vs. H e a t
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40
JNDUSTRIAL A N D ENGINEERING CHEMISTRY
(21P) Hergenrother, P. M., and Levine, H. H., ibid., p 2939. (22P) Iwakina, Y.,Uno, K., and Tagiguchi, T., ibid., p 3345. (23P) Jones, J. I., J. Mucromol. Sci.,C2, 303 (1968). (24P) Keller, L.B., J.Cell. Plast., 4 (111, 418 (1968). (25P) Klein, D. A,, and Fouty, R. A,, Macromolecules, I, 318 (1968). (26P) Korshak, V. V., and Tseillin, G. M., et al., Izv. Akad. Nauk SSSR, Ser. Khim, (91,2143 (1968). (27P) Korshak, V. V., and Vinogradova, S. V., Us$ Khim., 37, 2024 (1968). (28P) Korshak, V. V., and Rusanov, A. L., Izu. Akad. Nauk SSSR, Scr. Khim, (lo), 2418 (1968). (29P) Kudishina, V. A., Vestn. Mashinostr., 48 (7), 44 (1968). Kurihara, M., and Yoda, N., J.Poly. Sci., B6, 875 (1968). (31P) Kurosaki, T., and Young, P. R., J.Poly. Sci., C23 ( l ) , 57 (1968). (32P) Mortillaro, L., Materie Plastiche ed Elastomeri, 34 (6), 614 (1968). (33P) Mozgova, K. K., Korshak, V. V., and Levitshaya, S. G., Plasticheskie Marry, (101, 14 (1968). (34P) Patnaik, B. K., J.Sci. Ind. Res., 27 ( I l ) , 417 (1968). (35P) Preston, J., and Black, W. B., J. Poly. Sci., C23-1 441 (1968). (36P)Reimschuessel, H. K., ibid., A-2 (6) 559 (1968). (37P) Rode, V. V., el nl., ibid., A-1 (61, 1351 (1968). (38P) Russo, M., Materie PlasticheedElastomeri, 34 (7), 739; (8) 876 (1968). )% 3’( Scala, I,. C., Hickam, W. M., and Marschika, I., J . Apfil. Poly. Sci., 12, 2339 (1968). (40P) Slominski, G. L., Korshak, V. V., et al., Dokl. Akad. Nouk SSSR,182 (4), 851 (1968). J . Poly. Sci.,AI (6), 1449 (1968). (41P) Takahaski, H., and Hosegawa, M., (42P) Vinitskii A . M . Demidov V I., and Chudetskaya, E. A , , Izv. Vysshikh Uchabn. Zavedenii, Ma;hinortr.’, (5), 78 (i968). (43P) Vlasova, K. N., Chernova, A. C., et nl., Plasticheskie Massy, (5), 15 (1968). (44P) Vogl, O., and Knight, A. C., Macromolecules,1, 311 (1968). (45P) Wallach, M.L., J. Poly. Sci., AZ, 6, 953 (1968). (46P) Wolf, R., Okada, M., and Marvel, C. S., ibid., A-1, 6, 1503 (1968). Polymers
VI.
Corrosives
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o),
Characterization and Testlng of Polymers
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NO. 8
AUGUST 1969
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