un
I I / E C l M a t e r i a l s of Construction Review
Fibers by C. S. Grove, Jr., Syracuse University, Syracuse, N . Y., Joseph 1. Vodonik, Minnesota Mining & Manufacturing Co., St. Paul, Minn., and Robert S. Casey, W . A . Sheaffer Pen Co., Ft. Madison, Iowa Fibers and fiber aggregates help meet demands for enduring materials in the most severe environments missiles and space exploration
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THE
industrial market now accounts for more than one third of total fiber production. New fibers, especially modifications of existing ones, continue to find expanding applications in engineering and industry. Over-all economy is one factor. For an increasing number of applications the higher initial cost of many man-made fibers is more than compensated by their longer service life. Another factor is the available combinations of specific properties required for specialized applications. Most of the new fibers brought out in recent years have been superior to the natural fibers in strength and other mechanical properties and in chemical, physical, and biological stability. However, current emphasis is on tailoring fibers for specific end uses, such as fiberreactive dyeing and finishing, modifying elasticity and hydrophobic or hydrophylic character, through special modifications such as graft copolymerization. Also treatments, blending, and combinations of fibers with other materials have resulted in structures and devices having specialized properties for specific end uses. Research on fibers of graphite, metals, ceramics, and inorganic polymers has been intensified by the requirements of missiles and space vehicles for fibers having high thermal stability. New fibers and modifications are entering the unabating competition for the tire cord market. Nonwoven fabrics have been the subject of intensive research and development, but it is not clear yet just how much technology can do to remove their present limitations and what the ultimate market potential will be. Some man-made fibers are beginning to replace metals-Teflon fibers in bearings, and nylon, polyethylene, and other fabrics in air-supported structures.
Economics Although consumption of all fibers increased during the past decade, manmade fibers, especially the newer noncellulosics, continued to take an in-
creasing proportion of the total fibers market :
% of Total Fibers Market Cotton Wool Cellulosics Noncellulosics
1949
1959
70.6 9.4 18.3 1.6
65.7 6.7 18.6
9.0
The annual per capita consumption of fibers varies little. For several decades it has fluctuated between 30 and 36 pounds. I t stood at 30.8 in 1949, a poor year, and at 31.1 in 1958, also a poor year. In 1959, a good year (Table I), it was 35.8. The Textile Fiber Products Identification Act, effective March 3, 1960, requires that textile products be labeled with the appropriate generic names which have been set up to cover the various types and classes of fibers. A significant trend in the textile industry has been toward consolidation and integration of manufacturers.
Industrial Uses Man-made fibers and new modifications continue to displace natural fibers in industrial applications with severe service conditions, especially in marine and industrial cordage. It is estimated that 12 million pounds of fibers per year are required for mooring lines (7A). I n 1956, 10% of the filter cloth market was man-made fibers. Now the figure is 20y0. Among the man-made fibers used in cordage are the polyolefins, Dacron, nylon, and a new cordage yarn, Type 707 nylon, said to produce rope
Table I.
1959 U. S. Man-Made Fiber Production ( 6 A )
Total Acetate Rayon Noncellulosics Textile glass
% Change
Millions of Pounds
from 1958
1961.7 300.6 867.2 646.5 147.4
+21 5.6 17.6 32 42
+
+
++
averaging 14yGhigher breaking strength than regular nylon rope. Polypropylene is now rivaling polyethylene for rope and other heavy duty applications, as well as for outdoor furniture, shade cloth, and the like. A new technique has been announced for drawing single strand polypropylene filaments of exceptional strength. The new yarns are said to be ultraviolet stabilized, chemically and biologically inert, abrasion resistant, strong and flexible even at low temperatures, and to have reduced creep under constant load. Their low specific gravity, giving yield per pound about 20% higher than nylon and 70% higher than saran, is a further advantage in that polypropylene ropes will float (7A). Industrial Rayon and Reeves Bros. are producing polypropylene yarns. Other companies are building plants. Dyne1 is used in the membrane of the electrolytic deionizing process for producing potable water from brackish and sea water ( I A ) . Goodyear has brought out a new pneumatic ship fender constructed of heavy duty nylon tire cord and rubber similar to that in passenger tire treads (7A). Dacron is being used in lint-free, chemically and biologically inert industrial garments (7A). Liquid containers and tanks up to a capacity of 100,000 gallons are constructed of a new synthetic-coated nylon. Some are used by the Army Engineer Corps for offshore fuel storage ( I A ) . I t has been suggested that habitable space stations can be constructed by shooting foamed-in-place plastic into the space between the outer and inner fabric walls of the structure after it has been expanded to its final shape. Other applications are listed in Table
11. Nonwoven Fabrics Nonwoven fabrics continue to expand, after a slight slump in 1958, although they have failed to live up to earlier expectations. I t is estimated that 1959 production was well over 100 million pounds. VOL. 52, NO. 1 1
NOVEMBER 1960
959
an)'.+rd
Materials of Construction Review acetate), poly(viny1 chloride), butadienestyrene, butadiene-acrylonitrile, acrylic polymers, and combinations.
New Fibers
Seals are made from modified wool felt by combination with elastomeric sheet materials
However, technology hasn't kept pace. I n spite of new developments, such as fibrillating and hollow filament rayons and various self-bonding fibers, improvements are needed in binders, fiberbinder relationships, and methods of depositing the fibers in the weblike structure. Problems are binder systems which will permit utilization of the full strength of the fibers and avoid delamination.
Table
II.
Industrial Applications of Fibers Application Ref. Arresting and re(75B) straining devices (ajrcraft) Bearings (7A) Belting ( I A , 79B, 21C, 24C) Chemical handling ( IA, 73B) equipment Cordage (nets, slings, ( I A , 3A-54, 3B, 7B, ship fenders, web75B) bing) Covers (tarpaulins) ( I A , 5B, 79B) Dams (irrigation) (IAj Filters (7-4,7B, SB, 20B, 22B) Garments (dispos(7'4, ZB? 8 B ) able, protective) Hose ( 7 4 , 5B, 7B, 74B, 6C) Insulation ( ] A ,8B) Outdoor (awnings, ( 7A) furniture) Reinforcement ( 6 B , 70B, 12B, 76B, 78B>79%, 27B, 7lDj Structures (air-sup- (7A, ZB, 72B, 79B) ported, containers, tanks) ( 7 A , 3A, 7A, 4B, Tire cord 77B, 27C)
960
All kinds of fibers are used in nonwovens and about 607, are man-made, mostly rayons. The trend is toward higher quality fibers. The higher price of many of the synthetics limits them to end uses \$!here exceptional resistance to flexing, abrasion, or chemicals is required. An example is nonwoven polyester fiber tapes for electrical use. Among the bonding agents, the principal polymers being used are poiy(viny1
Acetate producers, Celanese, Eastman Chemical Products, and D u Pont, brought out neJv modifications of acetate yarn and staple during the past year. Oil and air-conditioner filters and maps are among the industrial applications. Alon was developed in Japan and is made by the Toho Rayon Co., Lcd. It is cellulose acetate made by a radically new and cheaper process. It is first spun as viscose rayon from an aqueous solution and is then acetylated in the fiber form (73C). Spandex is the neiv generic name for elastic urethane-based fibers. It has 650Yo elongation, and, compared 1% ith rubber, lower density, t\vo to three times the restraining power, availability of finer deniers, greater flex life and durability, and ability to be used withoui: covering. Lycra and Vyrene are the respective trade names for Du Ponr and U. S. Rubber Co. fibers. Vinal is the generic name for poly(vinyl alcohol) fibers. There is a wide variety of subtypes of various degrees of solubility, resulting from postspinning treatment with formaldchyde, by acetylization, and various processing sleps. This was developed in Japan. Air Reduction Chemical Co. is importing from Kurashiki Rayon Co. and carrying on further development. In Japan last year 30 million pounds of Vinal 5F were produced.
Wound reinforced plastic cylinder, believed to be the largest ever produced, i s being made for Lockheed Missile and Space Division, Sunnyvale, Calif. The cylinder, nearly 5 feet in diameter and 25 feet long, serves as a missile shipping containe r
INDUSTRIAL AND ENGINEERING CHEMISTRY
anT h e RHT grade of Vinal 5F has tenacities of 4.5 to 6.0 and elongation of 15 to 25%, the same wet and dry. T h e new MCM grade will have about 10% greater tenacity and slightly less elongation. T h e stress-strain relationships are unusual. There is a steep rise in the lower region, followed by a slight yield point, then a continued rise which, when projected back, passes very close to the origin. Abrasion resistance is about twice that of cotton. Vinal 5F has been used in fish nets, rope, thread, and belting. Vinal FO, a nonacetylated type, has good adhesion to compounding materials and is being used in automobile tires in the Far East ( 3 A , 7 A ) . Vycron is the trademark of Beaunit Mills’ new polyester fiber. It differs from other polyester fibers in chemical constitution and is claimed to be stronger. I t is reported to have a tensile strength of 5.6 grams per denier; elongation a t break, 35%; modulus of elasticity, 0.5 gram per denier; moisture absorption, 0.6%; specific gravity, 1.36; and melting temperature, 455O F. (72C). Zantrel is the “trademark-appliedfor” of the Hartford Fibres Co. new fiber which it has been licensed to produce in the United States by Societt Chimatex of Switzerland. Hartford has a n application before the Federal Trade Commission to establish “polynosic” as the generic name in the United States. Zantrel is a reconstituted cellulose fiber produced by a process entirely different from any used heretofore. I t has a round and homogeneous cross-section and consists of very fine, highly oriented microfibrils-a structure closer to cotton than to rayon.
Bibliography General a n d Reviews (1A) Campbell, J., Modern Textiles M a g . 40, No. 9, 66 (1959). (2A) Harris, M., Mark, H. F., “Natural and Synthetic Fibers,” Interscience, New Ydrk, 1959. (3A) Hindle, W.H., iModwn Textiles M a g . 40. NO. 9. 55 11959). (4A)’Nebel, R: W.,Textzle Research J . 29, 777-86 (1959). (SA) Press, J. J., ed. “Man-Made Textile Encyclopedia,” Interscience, New York, 1959
(6A) Textile Organon 31, No. 2 (1960). (7A) Wells, R. D., Modern Textile M a g . 40, No. 9, 51 (1959).
Industrial Applications (IB) Butterworth, E., Fibres Plastics 20, No. 1 1 , 327 (1959). (2B) FibresZntern. 20, No. 6, 213 (1959). 13B) Ibid.. D. 216. (4Bj Fibr&’Plastics 20, No. 10, 297 (1959). (5B) Zbid., p. 300. (6B) Zbid., p. 312. (7B) Zbid., p. 320. (8B) Zbid., pp. 320-1. (9B) Zbid., No. 12, p. 312. (10B) Zbid., p. 363. (11B) Zbid., pp. 366-7.
(12B) Zbid., p. 367. (13B) Zbid., p. 370. (14B) Furvik, N. B., Zbid., 20, No. IO, 295 (1 959) \ - - - ’ I .
(15B) Hargreaves, Gladys, Materials in Design Eng. 49, No. 4, 108 (1959). (I6B) Kassack, F., Kunststoffe 49, 425 (August 1959 A., Modern Textiles M a g . (17B) Litzler, 41. No. 3. 24 (19601. (18Bj Parratt, N. J., Rubber €8 Plastics Age 41, 263 (1960). (19B) Rubber @ Plastics Age 41, 279 (1960). (20B) Shaikh, A. M., Mushtaq, A., Pakistan J . Sci. Znd. Research 2, 27 (1959). (21B) Stutz, H., Kunststoffe 49,406 (August
&:
1&,.,,,. Q5Q)
(22B) Zagrodzki, S., Niedzielski, Walerianczyk, E., Gaz. Cukrownicza 342-5 (1959). Properties (1C) Algie, J. E., Textile Research J . 1-6 (1959). (2C) Bobeth, W., Melliand Textilber. 913-18 (1959). (3C) Conrad, C. M., J . Textile Inst. T133-60 (1959). ( 4 0 Erlich. V. L., Textile Research J . ’ 679-86 (1959). ’ /SC\ Hearle. J. W. S.. El-Beherv. H. ‘ A‘. E., Thakur, V. M’., J . Textiie’Znst. T83-111 (1959). (6C) Hinrichs, B. R., Melliand Textilber. 40, 919-20 (1959). (7C) Holden, G., J . Textile Znst. 50, T41-54 (1959). (8C) Howell, 13. G., Mieszkis, K. W., Tabor, D., “Friction in Textiles,” Butterworth’s Scientific Publications, London, 1959. (9C) Kenny, P., Chaikin, M., J . Textile Znst. 50, T18-38 (1959). (IOC) Lefferdink, T. B., Briar, H. P., Textile Research J . 29, 477-82 (1959). (4C) Lord, Joan, J . Textzle Znst. 50, T56982 (1959). (12C) Modern Textiles M a g . 40, No. 8 , 33 (1959). (13C) Moncrieff, R. W., Fibres Plastics 20, No. 8, 269 (1959). (14C) Niven, C. D., Textile Research J . 29, 826-33 (1959). (15C) Riley, Malcolm W., Materials in Design Eng. 50, No. 1, 115 (1959). (16C) Rochas, P., Martin, J. C., Bull. inst. textile France No. 83, 40-82 (1959). (17C) Satlow, G., Textile Research J . 29, 841-43 (1959). (18C) Schlatter, C., Olney, R. A., Baer, B. N., Zbid., 29, 200-10 (1959). (19C) Simms, D. L., Fibres Plastics 21, No. 10 (1959). (20C) Smith, J. C., McCrackin, F. L., and Schiefer, H. F., J . Textile Znst. 50, T55-69 (19591. (21C) Somer, H., Barth, R., Faserjarsch. u. Textiltech. 10, 8-21 (1959). (22C) Symes, W. S., J . Textile Zmt. 50, T241-48 (1959). (23C) Taylor, H. M., Zbid., 50, T161-88 (1959). (24C) TBth, G&e, Koiahtui 8, 298 (1958). (25C) Trivedi, S. S., Chitale, A. G., J . Textile Znst. 50. T390-92 (1959). (26C) Warburton, ‘F. L., Z6id:, 50,’ T1-17 (1959). (27C) Wood, J. O., Goy, R. S.,Durwalla, F. S., Textile Research J . 29, 669-78 (1959). (28‘C) Zaukelies, D. A., Zbid., 29, 794-801 (1959). Chemical Modifications a n d Treatments (ID) Berard, W. N., Gautreaux, G. A., Reeves, W. A., Textile Research J . 29, 126-33 (1959).
Materials of Construction Review (2D) Chance, L. H., Perkerson, F. S., McMillan, 0. J., Jr., Zbid., 29, 558-64 (1 9591 ,---,,.
(3D) Conrad, C. M., Zbid., 29, 287-302 (1959). (4D) Cooper, A. S., Jr., Cruz, M. D., others, A m . Dyestuff Reptr. 48, No. 20, 43-9 (1959). (5D) De Marco, C. G., McQuade, A. J., Kennedy, S . J., Modern Textiles M a g . 41, No. 2, 50 (1960). (6D) Esteve, R. M., Jr., Wright: G. E., Mack, P. B., A m . Dyestuff Refitr. 48, 139-42 (1959). (7D) Esteve, R. M., Jr., Wright, G. E.: Mack, P. B., Textile Research J . 29, 760 (1959). (8D FibresZntern. 20, No. 6, 193 (1959). (9D)) Fibies Plastics 20, No. 7, 231 (1959). (10D) Zbid., No. 11, p. 329. 111D\ Zbid.. NO. 12. DD. 368-70. Zbid.; 21, No.’1,’73 (1960). (14D) Grajeck, E. J., Petersen, W. H., A m . Dyestuff Reptr. 48, No. 13, 37 (1959). (15D) Hall, A. J., Fibres Plastics 21, No. 3, 78 (1960). (I6D) Immergut, E. H., Fiber Society Meeting, ”. Princeton, N. J., September 1959. (17D) Lotz, E. L., A m . Dyestuff Reptr. 48. NO. 4. 50-2 (1959). (18Dj Majors, P.‘ A., ’lbid., 48, No. 3, P91-3 (1959). (19D) Rubber @ Plastics Age 41, 679 (1960). (20D) Sandholzer, M. W., A m . Dyestuff Reptr. 48, 37-41 (1959). (21D) Schiffner, R., Lange, G., Faserforsch. u. Textiltech. 9, 417-24 (1958). 122D) Valko. E. I., Tesoro, G. C., Textile ‘ Reiearch J . 29, 21-31 (1959). (23D) Ziifle, H. M., Eggerton, F. V . , Segal, L., Zbid., 29, 13-20 (1959). Nuclear Irradiation a n d Tracer Techniques (IE) Demint, R. J., Arthur, J. C., Jr., Textzle Research J . 29, 276-8 (1959). (2E) Henslev, J. W . , Inks, C. G., ?bid., ‘ 29, 505-13 (1959). (3E) Pan, Huo-Ping, Proctor, B. E., others, Zbrd., 29, 415-21 (1959). (4E) Ibtd., pp. 422-4. (5E) Takayanagi, M., Aramaki, T., Konomi, T., Sen-r Gakkaishi 15, 124-8 (1959). Nonwoven Fabrics (IF) Carlson, W. E., Arnold, K. A., IND.ENG.CHEM.51, 911 (1959). (2F) Gillick, T. J., Jr., Zbid., 51, 904 (1959). (3F) Homier, P. A., A n . Dyerluff Rtptr. 49, No. 1 , 40 (1960). (4F) Nicely, D. C., Zbid., 49, No. 1, 41 (19601. (5F) Nicely, D. C., IND. ENG. CHEM. 51, 910 (1959). (6F) Petterson, Dew. R., Zbid., 51, 902 ‘ (i959). (7F) Pole, E. G., Rubber Deuelofments 12, No. 3, 70 (1959). (8F) Read, R. H., T h e Frontier 22, No. 1, 1-5 (1959). (9FI Shailar. L. L.,, Jr.,, IND.ENG.CHEM. ‘ 51, 901 (1759). (10F) Shearer, H. E., 137th Meeting, ACS. Cleveland. Ohio. Ami1 1960. (11F) Sherwood, N. H.,’II&. ENG.CHEM. 51, 907 (1959). (12F) Taylor, J. T., 137th Meeting, ACS, Cleveland, Ohio, April 1960. (13F) Till, D. E., Modern Textiles 40, 26-42 (1959). \ - - - - I
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