Nickel and High Nickel Alloys W. Z. FRIEND, The International Nickel Company, Inc., New York, N. Y.
A
CONTINUED trend in the utiliwttion of high-nickel alloys has been toward their increased use for vital applications where full advantage can be taken of special properties such as high temperature strength and oxidation resistance, corrosion resistance, magnetic properties, or other unique physical properties. There has been corredpondingly less accent on borderline applications where less highly alloyed materials are likely t o give satisfactory performance. This summary is, for the most part, confined to a consideration of nickel and high-nickel or nickelbase alloys containing more than 50% nickel. Some attention also is given to cobalt-nickel base alloys, as these may not fit readily into other categories of the review. ALLOYS
As in the case of the immediately preceding years reviewed in a previous summary (55),the major developments in composition of high-nickel alloys probably occurred in the high temperature field in connection with materials for jet engine and gas turbine service. Experimental work was directed to the adjustment of alloy compositions to obtain further improvement in such properties as oxidization resistance, creep resistance, and stress rupture strength a t temperatures of 1500' F. and higher. Additional test data have been obtained on the high tempeqature mechanical properties of such nickel or nickel-chromium base alloys as Inconel, Inconel X, Nimonic 80, Nimonic 75, Nichrome, Chromel, and Hastelloy B, and upon such cobalt or cobalt-nickel base alloys as Vitallium, X-49, 73J, X-40, and K42B, and Refractalloy 26 and 70,61,422-19,6059, and S816. Grant, Fredericlrson, and Taylor (38)presented a coniprehensive summary of the high temperature alloys in which they correlated and evaluated much of the experimental work done on these alloys during the past 7 years by industrial and governmental agencies. This reference lists the composition of 53 ulloys, and provides physical property data on density, coefficient of expansion and tensile properties up to 2000' F. for most of them, and stress-rupture and elongation values for the more promising forged and cast alloys a t various temperature levels up to 1800" F. Freeman, Reynolds, and White ( S I ) also presented a review of the high temperature properties of the jet engine materials, giving typical compositions and alloys for rotor disks and blades, flame tubes, tail pipes, and nozzle assemblies, The metallurgy of the various groups of alloys is discussed with the presentation of some working theories for the high temperature performance obtained. High temperature physical and mechanical properties as well as information on the heat treatment and fabrication of the S-816 alloy (42.28 (30-20.17 Ni-20.88 C r 4 . 2 6 W-3.77 Cb) were given by Henry (41). Data on the high temperature properties, heat treatment, and fabrication of Inconel X and heattreated 50 Ni-20 Cr (copper, manganese, silicon, columbium, titanium, calcium) alloys were provided by Crawford (23). Properties of Nimonic 75 and 80 a t temperatures up to 700' C. were presented by Griffiths (39). Mudge (60)summarized the effects of additions of various metallic elements upon age-hardening characteristics of nickel and high-nickel alloys. With the most widely used group of addition elements-magnesium, silicon,
beryllium, titanium, and aluminum-age-hardening can be accomplished by additions of only 1 to 5% A second group, including molybdenum, tungsten, zinc, tin, and manganese. requires the addition of 15 to 45% of the hardening element. A third group, including gold, indium, zirconium, oxygen, and phosphorus, has little commercial significance. Several agehardening elements may be added simultnneously as in the case of Inconel X which contains aluminum, titanium, and silicon. Some work has been done on beryllium-nickel alloys. Williams (81)presented data on the hardness, tensile and impact properties, fatigue and corrosion-fatigue strength, and corrosion in salt water of an age-hardened beryllium-nickel alloy containing 1.62% beryllium. According t o Losana (49), high strength after suitable heat treatment can be obtained by the presence in nickel alloys of beryllium and molybdenum together, such as an alloy containing 1.6% beryllium and 2.5% molybdenum. Neuhaus (63) described the spectrographic methods of analysis of nickel alloys. Hicks (42) reported the results of tests to determine the effects of changing temperature upon the magnetic permeability of nickel-iron core materials, including 4750 (48 Ni-Fe), Monimax (47 Ni-3 Mo-Fe), Sinimax (43 Ni-3.25 Si-Fe), and Mumetal (76 N i 4 . 5 Cu-1.5 Cr-Fe). Moehring (66) surveyed the properties of magnetic metals and metallic mixtures, including combinations of nickel and iron, when subjected to high-frequency currents. A new magnetic alloy (79 Ni-5 Mo-15 Fe-0.5 Mn) used by the Navy has initial permeability several times as high as alloys previously used in communications transformers ( 7 ) , A new alloy developed primarily for watch springs is strong, hard, nonmagnetic, and highly resistant to corrosion. I t s analysis is. cobalt 40%, nickel 15.5%, chromium 20%, iron 15%? molybdenum 7%, manganese 2%, carbon 0.15%, and beryllium 0.03y0 (7). FABRICATION
WELDINGAND MECHANICAL FORMING. The application of oxyacetylene powder cutting proccsses continued to receive favorable attention as applied t o high-nickel alloys. Fleming (29) described the application of powder cutting and scarfing t o Monel and nickel, with an example of the shape cutting of elliptical Monel fins for a pressure,vessel. Descriptions of the Oxyarc process were given by Clauser ($0)and by Jefferson (44), including applications to the cutting of Monel, nickel, and Hastelloy B. Description of a powder welding process for nickel-base alloys was given by Clason (19). Chisholm (18) described the welding characteristics of some of the high temperature alloys including cobalt and cobalt-nickel and base, nickel-base, and cobalt-nickel-iron base materials. The first group is more difficult t o weld than the other two. Weldability and welding methods for nickel and high-nickel alloys were reviewed by West (79). I n a description of methods used in fabrication of sheet metal parts for jet engines, Knight (46)described the procedure used in drawing and annealing Inconel domes for the ends of combustion chamber liners. A line of die-formed wrought fittings of Inconel, nickel, and Monel is now available in eleven types of tees, elbows,
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INDUSTRIAL AND ENGINEERING CHEMISTRY
reducers, and adapters (4). Procedures for the drop-forging of Hastelloy B and 5-816 alloy (42 Co-20 Si-20 Cr-4 W-4 C b 4 Fe) were given by Demirjian (94). Forging practice for various high-nickel alloys was summarized by Ashburn (9). Problems Involved in the rolling and forging of high temperature alloys were discussed by Mohling (57). Close control of temperatures, the use of artificial atmospheres, and longer than normal heating cycles have solved most of the problems. The use of shot peening t o increase the fatigue resistance and stress-corrosion resistance of metals has been effective under some conditions. Examples given by Mattson and Almen (52) include applications to nickel, Monel, and Inconel. Other examples were cited by Knight (46). Evans, Cotton, and Thexton (28) described the investigation leading to the development of suitable techniques for precision casting of high-melting nickel alloys, particularly Nimonic 80, by the "lost wax" process. Hudson (43) also discussed the precision casting of these alloys with some suggested new applications. A brief summary of the melting practice in production of wrought Monel, K Monel, nickel, and Inconel was given by Mudge (59). I n a progress report of the A.S.M.E. Special Research Cornmittee on Vessels under External Pressure, Hartman (40) presented charts for determining the thickness of cylindrical unfired vessels of Monel, A nickel, and Inconel, when subjected to external pressure. Sturm and O'Brien (75) gave a brief discussion of factors that must be considered when designing a pressure vessel for a collapsing load. Calculations and charts are shown for A nickel and Type 301 stainless steel. Long (48) discussed factors t o be considered in the design of laboratory and full-sized autoclaves to operate under high pressures and temperatures. There is continued increase in the use of steel clad with nickel or nickel alloys for corrosion-resisting applications. A review (6)of the production, fabrication, properties, and uses of clad steels included the nickel alloys. Sullivan (76) described some current applications of clad steels. ELECTROFORMING. The use of electrodeposition or electroforming is preferred over customary pyrometallurgical processes In some engineering applications because the physical properties of metals can be varied over wider limits in the plated form and can be controlled more closely. Important features t o be considered in the electroforming of nickel were described by Roehl (71). A range of hardnesses from about 140 t o 400 Vickers and of tensile strengths from 50,000 to 155,000 pounds per square inch can be obtained for the as-plated nickel deposit, depending upon the type of plating solution used. Applications cited for heavy nickel plating for corrosion or abrasion resistance include oil well sucker rods, hopper jaws, pump rods and plungers, ball mills, printing cylinders, plug cocks, lehr rolls, drum plugs, turbine blades, plastic molds and dies, press plates, nickelplated pipe, and nickel-plated chemical process equipment. Uses of eIectroformed nickel cited by Diggin (26) include phonograph record master plates, facing soft lead-base stereotype metah for printing, forming of parabolic mirrors, strainers, screens, and hypodermic needles. Orbaugh (66) reviewed the history of electroforming with several examples of the use of nickel. Milton et al. (63)described in detail the procedure used in electroforming nickel molds for production of rubber gloves. The use of thick nickel deposits for building up worn or mismachined metal parts was described by Chambaud (15). Coxon ($2) reviewed electroforming, citing the production of an electroformed three-dimensional nickel cam. Raymond (68) reviewed 1947 progress in metal finishing with examples of electroformed nickel for industrial use. Roehl (72)furnished data on hardness, ductility, and tensile strength of electroplated nickcl deposits as affected b y p H and temperature of electrolyte, current density, annealing temperature, and time. Stout (74) referred t o the large scale application of nickel plating on diffusers used in uranium separation.
Vol. 40, No. 10
APPLICATIONS
HIGHTEMPERATURE. As would be expected from the continued emphasis upon the high temperature properties of the nickel alloys, many of the newer developments in uses of these alloys are in the high temperature fields where both useful physical properties and corrosion resistance are required. Although there is still accent on jet engine and gas turbine applications, uses for heavy-duty engine valves and seats, furnace and heat treating equipment, thermocouple protection tubes, instruments and springs, and high temperature chemical process equipment have been multiplying. Robertson (70) discussed some of the fundamental considerations involved in the use of metals under high temperature conditions. Gibb and Bowden (37) discussed materials used in gas turbines and relationship of their properties to turbine design with special reference to industrial applications. Mochel ( 5 5 ) also discussed the general requirements for gas turbine materials including temperatures involved or likely to be involved, testing methods and equipment, and applications of materials t o specific parts of gas turbines. Nimonic 80 was used for the blades of a gas turbine developed for driving the central shaft of a 100-foot triple-screw boat for the British Admiralty (6). Nickel-chromium alloy wire with diameter not exceeding 0.05 mm. was used in forming the regenerator of the Philips hot-air engine ( 1 ) . A number of the high temperature nickel alloys have been tried as valves and seats on heavy-duty engines in the work described by Colwell @ I ) . Inconel X has shown particular promise at temperatures u p to 1500" F. Nichrome and Stellite are among the hard-facing materials used and the results of endurance and corrosion tests for these materials are given. Dike and Bradley (26) discussed materials, including nickel alloys used in pyrometric instruments in the smelting, refining, and melting of nonferrous alloys. Experience reported by Murphy (61)showed Inconel t o be a suitable material for thermocouple protection tubes in industrial furnace applications below 2000" F. when sulfur content of gases is below 1%. Flexible tubing with Inconel inner core and braid is supplied for temperatures up t o 1700" F. Applications include flexible exhaust tubing for automotive power plants, fuel and oil lines for airplanes (Zone l),and chemical equipmcnt ( 2 ) . Inconel X appears (23)to offer promise as a spring material at 900' F. or even higher. It has given ( 5 5 ) good performance as bolting material a t 1200" F., with resistance to galling. PETROLEUX REFIXING. The continued expansion of petrochemical production has accounted for further uses of nickel alloys, especially for handling mixtures including hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, or sodium hydroxide under elevated temperature conditions. Friend (34) presented the results of plant and laboratory corrosion tests in sulfuric acid solutions in petroleum refinery processes, many of them at elevated temperatures. Friend and Mason (36) published the results of corrosion tests in refinery distillation equipment where corrosion is due either to dilute hydrochloric acid or t o sulfur compounds a t elevated temperatures. Among the high-nickel materials included in both of these summaries were nickel, Monel, Inconel, Hastelloy alloys, and Illium. A summary of uses of Hastelloy alloys in the petroleum industry, given by Chisholm ( l 7 ) , included the use of Hastelloy B linings for towers handling aluminum chloride, Hastelloy C for strong oxidizing agents, and Hastelloy D for evaporation of sulfuric acid. Inconel reaction tubes have been used in gas conversion processes at temperatures up to about 1800" F. Morton ( 5 8 ) reviewed the steps taken by the production, transportation, and refining divisions of the oil industry to counteract destruction of equipment by both corrosion and abrasion. Considerations involved in planning, conducting, and interpreting the results of refinery corrosion tests were described by Wachter and Treseder (78). Pray, Fink, and Peoples (67) published a literature review
INDUSTRIAL AND ENGINEERING CHEMISTRY
October 1948
on corrosion of metals by flue gas condensate, in which some highnickel alloys were included. CHEMICAL PROCESSING. The trend in chemical processing has been toward the use of higher temperatures and pressures, coinciding with the increased availability of metals and alloys resistant to such conditions and expanded data on their high temperature physical properties. Some applications cited by Friend (33) include the use of Inconel for reaction coils in continuous hydrolysis of fats at 600" F. and 3500 pounds per square inch pressure, clad and lined towers for continuous hydrolysis of fats at 500' F. and 700 pounds per square inch pressure (also referred to by Barnebey and Brown, 11), heaters and bubble towers in fatty acid and tall oil distillation up to 625" F., heat exchangers handling petroleum products of high-naphthenic acid content at 700 F., reaction tubes handling sodium hydroxide solutions at 800" F. and 4000 pounds per square inch pressure, heaters for molten caustic soda baths at 900' F., and superheating coils heating steam to 1500" F. Other examples cited include the use of L nickel for evaporation of sodium hydroxide to 95 to 98% concentration at 700' t o 900" F. and for holding and heating molten sodium nitrate baths at 920" F. There was continued interest in processes involving the use of hydrogen fluoride and fluorine at elevated temperatures. Myers and D e Long (61)reported the results of corrosion tests in fluorine at temperatures up t o 700" C., in hydrogen fluoride at temperatures up to 600" C., and in mixtures of hydrogen fluoride and steam at temperatures u p to 750" C. Nickel was shown to be the most resistant of the materials tested in fluorine. Nickel, Monel, and Inconel showed suitable resistance to hydrogen fluoride at 600 O C. In a series of published symposia describing the performance of materials of chemical plant construction with various common chemicals, Friend (82) dealt with the performance of nickel, Monel, Inconel, and Ni-Resist, while Chisholm (16)dealt with the performance of the Hastelloy alloys, and Staley (78), Traub (77), and Luce (60) dealt with the Chlorimet alloys. The chemicals covered to date in these symposia include acetic acid, phosphoric acid, chlorine, sulfur dioxide, nitric acid, sodium chloride, and sulfuric acid. West (80) discussed performance of nickel and nickel alloys in sulfur and sulfides at elevated temperatures. Niakel, Monel, Hastelloy C, and Chlorimet 3 are among materials included by Fontana (30)in a discussion of construction materials for making and handling acetic acid. Corrosion rates of Chlorimet 2 (nickel-molybdenum) and Chlorimet 3 (nickelmolybdenum-chromium) alloys in sulfuric acid and hydrochloric acid solutions and of Chlorimet 3 in ferric chloride solutions were given in a recently issued booklet (27). I n a plant producing a variety of fatty acids, drying oils, and other organics, uses of Monel for Twitchell fat splitting tanks and of Inconel fatty acid and oil heating were described (3). Applications of Monel in the storage and piping of frit, and of nickel-chromium alloys for heating elements and furnace tooling, in a porcelain enameling plant, were described by O'Donnell (64). Nickel-clad steel is applied to the construction of newly developed hydropulpers in the pulp and paper industry (8). Nickel and nickel-clad steel are used for tanks, tank cars, and drums in the storage and shipment of liquid bromine and ethylene dibromide. I n a discussion of equipment design, Brown (11)referred to the uses of nickel and Monel for chlorine condensers, Monel heating tubes in salt evaporators, and nickel for caustic soda evaporators. MISCELLANEOUS. The uses of some high-nickel alloys in tho handling of milk were described by Pattison (66). Mason (61) gave the results of corrosion tests of a number of metals, including nickel, Monel, Inconel, and Hastelloy alloys B and C in the production and handling of food products including fruit juices and sirups, pectin, gelatin, salad dressing, vinegar, canning brines, oleomargarine, monosodium glutamate, baker's yeast, and carbonated beverages. I n a study by Roberts (69) of corrosion and O
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contaniination in wine-handling equipment, Inconel a a$ among the materials shown to have least effect on the wines. The same considerations have led to the use of Inconel or Inconel-clad steel for whisky blending and bottling tanks and bottling lines, Nickel, Monel, Z nickel, and Inconel were included among the spring materials discussed by Zimmerli (83). Monel and Hastelloy alloys B and C were among the alloys included by Koch (47) in a discussion of materials for diaphragm control valves handling acids and wet and dry gases. Mochel (54) reported the results of seizing tests with various materials including rolled Monel, cast Monel, cast S Monel, rolled nickel, and BTG Alloy (60 Ni-12 Cr-3 W-1 Mn) at 750' F. Yamaguchi (83)investigated by electron diffraction the nature of films and corrosion products formed upon a number of materials including nickel and Hastelloy A in several corrosive environments including hydrogen chloride, hydrogen iodide, and the atmosphere. There is evidence of "selective oxide structure" in the case of some alloys, such as Hastelloy A, in which the oxide of only one of the ingredients of the alloy is formed on the surface. Carlin (14) presented charts showing supersonic wave penetration into several materials including nickel and Monel. Stable radioactive isotopes of nickel are being prepared along with those of some other metals for use in tracer research, espocially in the petroleum industry. The use of nickel isotopes in a new method for estimating the age of the elements was referred to by Brown (13). Because the nuclear properties of materials used for reactors producing fissionable materials or new materials are of particular importance, Bacher (IO) suggested that it may be necessary to prepare separated isotopes of some metals in sufficient quantity to be used as certain vital parts of such reactors. LITERATURE CITED
(1) Anon., Autocar, 92, 649, 654 (1947).
(2) (3) (4) (5) (6) (7)
(8)
(9) (10) (11)
Anon., Automotive und Aviation, 97, No. 10, 58 (1947). Anon., Chem. Eng., 54, No. 8 , 109 (1947). Anon., Heating, Piping A i r Conditioning, 19, No. 7, 180 (1947), Anon.,Iron Age, 160, No. 15, 140-41 (1947). Anon., Materials & Methods, 26, No. 3, 97-108 (1947). Ibid., 27, NO. 1, 87-106 (1948). Anon., Paper TradeJ., 124, No. 9, 155 (1947). Ashburn, A., A m . Machinist, 91, No. 10, 117-32 (1947). Bacher, R. I?., X e t a l Prooress, 52, 800-2 (1947). Barnebey, H. L., and Brown, A. C., J . Am. Oil Chem. SOC.,25, 95-9 (1948).
(12) (13) (14) (15) (16)
Brown, C. O . , IND. ENG.GHEM.,39, No. 10.89 A, 90 A (1947). Brown, €I., Phys. Rev., 72, No. 4, 348 (1947). Carling, B., ProductEng., 18, No. 10, 169 (1947). Chambaud, D., M t h n i q u e , 30, 285-9 (1946). Chisholm, C. G., Chem. Eng., 53, No. 7, 222-6, No. 12, 206-8 (1946); 54, NO. 2, 228-31, NO. 9, 230-2 (1947); 55, NO. 1,
228-30, NO.2,233, NO.5,238-42 (1948). (17) Chisholm, C. G., Proc. Am. SOC.Me&. Engrs., Petroleum Mech. Eng. Conf., 46-7 (June 1947). (18) Chisholm, C. G., Steel, 121, No. 26,54-6, 58, 60 (1947). (19) Clason, C. B., Welding Eng., 33, No. 2, 60-62 (1948). (20) Clauser, H. R., Materials & Methods, 25, No. 1, 78-81 (1947). (21) Colwell, A. T., Trans. SOC.Automotive Engrs., 2, No. 1, 84-103 (1948) (22) Coxon, W. F., MetalInd., 71, No. 9, 170-2 (1947). (23) Crawford, C. A., Trans. Am. SOC.Mech. Engrs., 69, 609-12 (1947). (24) Demirjian, S. G., Materiala & Methods, 26, No. 3, 68-71 (1947). (25) Diggin, M . B., Metal Finishing, 45, No. 6,78-80 (1947). (26) Dike, P. H.. and Bradley, M. J., Am. Inst. Mining Met. Engrs., Inst. Metala Div., "Symposium on Non-Ferrous Melting Practice," 1-46 (1946). (27) Duriron Co., "Chlorimet," Bull. 114 (May 1948). (28) Evans, H., Cotton, P. S., and Thexton, J., Foundry Trade J., 82, NO. 1609,205-10; NO. 1610, 223-7 (1947). (29) Fleming, D. H., Jr., Steel, 121, No. 22, 97, 120, 123, 126 (1947). (30) Fontana, M. G., IND.ENQ.CHEN.,40, No. 7 , 7 3 A (1948). (31) Freeman, J. W., Reynolds, E. E., and White, A. E., J. Aeronaut. S C ~ 14, . , 693-702 (1947). (32) Friend, W. Z., Chen. Eng., 53, No. 9, 203-6, No. 12, 218-19 (1946); 54, NO. 3, 220-2, NO. 7, 222-23; NO. 12, 225-6 (1947); 55, KO,4, 219 (1948).
.
INDUSTRIAL AND ENGINEERING CHEMISTRY
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Friend, W. Z., Chem. Eng. Progress, 44,501-10 (1948). Friend, W. Z., Corrosion, 4, 101-11 (1948). Friend, W. Z., IND. ENQ.CHEM.,39, 1228-34 (1947). Friend, W. Z., and Mason, J. F., Jr., Petrol. Engr., 18, No. 8, 192, 194, 198, 201, 204 (1947).
Gibb, C. D., and Bowden, A. T., J . Eoy. SOC.Arts, 95, 265-314 (1947).
Grant, N. J., Fiederickson, A. F., and Taylor, M. E., Iron Age, 161, NO. 12, 73-8; NO.15,75-81 (1948). Griffiths, W. T., Sheet MetalZnds., 24,2451-2,2466 (1947). Hartman, F. V., Trans. Am. Soc. Mech. Engrs., 69, 337-61 (1947). Henry, J. B., Jr., Iron A g e , 159, No. 24,58-64 (1947). Hicks, L. C., Steel Horizons, 10, No. 1, 16-17 (January 1948)
(Allegheny-Ludlum Steel Corp.). Hudson, F.,Metallurgia, 37, 243-7 (1948). Jefferson, T. B., W e l d i n g Engr., 32, No. 8,45-7 (1947). Knight, H. A., Materials & Methods, 24, 1461-5 (1946). Ibid., 26, NO.5 , 83-6 (1947). Koch, A. J., Chem. Eng.,54, No. 6,207-5,210,212,214, 216,218 (1947), Long, C. A , , Machine Design, 19, No. 8,101-4 (1947). Losana, L., Attirealeacad. sci. Torino, 79,234-8 (1943-4). Luce, W. A,, Chem. Eng., 55, No. 1,223-4, No. 2, 233 (1948). Mason, J. F., Jr., Corrosion, 4,305-20 (1948). Mattson, R. L., and Almen, J. Q., Compressed Air Mag., 52, No. l(1947). Milton, C. L., Jr., Cort, I., Nielson, @. A,, and Cowan, I., Metal Finishing, 45, No. 8 , 61-2 (1947). Mochel, N. L., Materials & Mefhods,26, No. 3, 113 (1947)* Moohel, N. L., Trans. Am. SOC.Mech. Engrs., 69, 561-8 (1947). Moehrinrt. D.. Air Tech. Intellieence. Translation P-TS-1047-RE (March 1947). Mohlina, G., Iron SteeZ Engr., 24, No. 8, 106 (1947). MortonTB. B., J.Inst, Petroleum, 34, No. 289, 1-59 (1948). I
of
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(59) Mudge, W. A., Am. Inst. Mining Met. Engrs., Inst. Metals Div.? “Symposium on Non-Ferrous Melting Practice,” 74-8 (1946) (60) Mudge, 1%’. A., Znd. Heating, 14, 1282 (1947). (61) Murphy, E. A . , Materials & Methods, 25, No. 133 (1947). 8~ (62) Myers, W. R., and De Long, 1%’.B., Chem. Eng. P r o g ~ e ~44, 359-62 (1948). (63) Neuhaus, C. J . , Iron A g e , 161, No. 4,62-5 (1948). (64) O’Donnell, D. S., Can. Chem. & Process Inds., 31, 527-9, 536 (1947). (65) Orbaugh, M. H., Monthly Rev., Am. Electropleters Soc., 34, No. 7, 810-15 (1947). (66) Pattison, F. R., Dairuznds., 12, 329-37 (1947). (67) Pray, H. A., Fink, F. W., and Peoples, R. S., Am. Cas Assoc., Rept. 1, Project DGR-4-CM (February 1947). (68) Raymond, W. A , , Metal Finishing, 46, No. 1,56-60 (1948). (69) Roberts, D., Wine Rw.,15, No. 5, 16, 18 (1947). (70) Robertson, J. M., Iron and Coal Trades Rev., 154, 1135-42 (1947). (71) Roehl, E. J., Metal Finishing, 45, No. 6,56-9, 71 (1947). (72) Roehl, E. J., Monthly Rev., Am, Electroplaters Soc., 34, No. 10, 1129-40 (1947). (73) Staley, W. D., Chem. Eng., 53, No. 11,256-60 (1946). (74) Stout, W. W., “Secret,” Chrysler Corp., 1947. (75) Sturm, R. G., and O’Brien, € L., I. Trans. Am. &c. Mech. Engrs., 69, 353-8 (1947). (76) Sullivan, G. F., Iron Aye, 160, No. 124, 137-9 (1947). (77) Traub, J. L., Chem. Eng., 54, No. 3,240 (1947). (78) Wachter, A., and Treseder, R. S., Chem. Eng. I3.ogres8, 43, 31526 (1947). (79) West, E. G . , Sheet Metal Ind., 24, 2265-71 (1947) ; 25, 147-54, 360 (1948). (80) West, J. R., Chem. Eng., 53, No. 10,226-38 (1946). (81) Williams, W. L., Trans. Am. SOC.Metals, Preprint 11 (1947). (82) Yamaguchi, S., Bull. Chem. Soc. J a p a n , 18,53-91 (1943). (83) Zimmerli, 3. P., SOC.Automotive Engrs., Preprint ($Jun~ 1947).
RECEIVBD August
19, 1918.
Standards, Washington, D . @,
HREE full years have gone by since the end of World War 11. During the war period, 1939 to 1945, the plastics industry quadrupled in size, and many wondered whether it could maintain this high level of production in peacetime. The years 1046 and 1947 have supplied the answer. Each of these years has seen the establishment of new production records, new materials, and new applications. Developments in this field in recent months are reviexed in this article. VINYL RESINS
Considerable attention was focused on the vinyl resins (71, 77) during the past year as several new plants came into production or neared completion. Further advances in the art of coating, dipping, molding, and casting with resin-plasticizer pastes ( 16, 68, 41) were recorded. Synthetic rubber of the butadiene-acrylonitrile type has been compounded with vinyl chloride resins t o combine the oil-, chemical- and age-resistant properties of the latter with the solvent resistance and flexibility of the former ( g 2 , 7 0 ) . The combination avoids the troublesome factor of plasticizer migration. A polyblend stock made by colloidal blending of polyvinyl chloride resin and butadiene-acrylonitrile rubber possesses properties heretofore obtained only bv mill mixing. By varying the ratio of nitrile rubber and polyvinyl chloride resin, products ranging from hard plastic materials to soft rubberlike compositions are produced, Thermoplastic tubing and hose can be made which are superior to plasticized elastomers in dimensional Btabilitv when aged a t high temperatures, and, in addition, are
not subject to stiffening because of plast,iciser extraction. Such tubing can be used for transferring beverages, gasoline, oils, solvents, and industrial chemicals (81). The polyblend may be combined with phenolic resins to form tough, durable thermosetting materials (78). A material for sealing porous castings or seams in metallic structures consists of a metallic filler and a vinyl resin. It is said to be resistant to alcohol, gasoline, oil, water, saturated salt solution, carbon tetrachloride, and 10% solutions of x a n y acids, including nitric and sulfuric (28) Moistureproof shipping bags made of vinyl plastic are being used for handling met mixes as well as for cher,iicaIs that must, be protected from contamination n-ith lint and other impurities picked up from ordinary containers. The vinyl bags have high tear resistance and chemical inertiless. and can bz l i e d repeatedly ($9) A copolymer of vinyl chloride and acrylonitrile (vinyl cyanide) has been made into a fiber which is of interest, to chemical engineers in the form of filter fabric, dust fume bags, and the like. The oriented and heat-stabilized material is resistant to many acids, bases, and solvents; it is attacked by ketones, 70% nitric acid, and 5 % phenol a t 25’ C., and by 25% chromic acid, 70% ferric chloride, 30y0 silver nitrate, and 70% sulfuric acid at 100” C. ( 6 , 8.5). ~
o
POLYVINYLIDENE CHLORIDE
Polyvinylidene chloride extended its markets as film (76), filament (19, 7 4 , and latex (24, 80). The saran latex produces coatings on paper, fabric, yarns, and leather which have a high
