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INDUSTRIAL AND ENGINEERING CHEMISTRY
(238) Schor, H., Ind. Heating, 19,1234,1236 (July 1952). (239) Screw Machine Engineering, 24, 55-6 (March 1953). (240) Sheet Metal Inds., 29, 611-23 (1952). (241) Ihid., pp 717-22. (242) Ibid., 30, 217-28, 244 (1953). (243) Shepard, K R., Welcling J., 31,424-5 (1952). (244) Shirley, H. T., and Nicholson, C. G., J . Iron Steel Inst. (London), 170, 111-18 (February 1952). (245) Shirley, H. T., and Truman, J. E., Ibid., 171, 354-8 (August 1952). (246) Ibid., 172, 377-80 (December 1952). (247) Shriver, G. L., Western Metals, 10,51-2 (June 1952). (248) Simmons, W. F., and Cross, H. C., American Society for Tesb ing Materials, Spec. Tech. Pub. 124 (1952). (249) Simpkinson, T. V., Iron A g e , 170, 166-9 (Dee. 11, 1952). (250) Simpkinson, T. V., Metallurgia, 47,18-24 (January 1953). (251) Smith, G. V., and Dulis, E. J., Amer. SOC.Testing Materials, Preprint 82 (June 1952). (252) Spencer, L. F., Metal Finishing, 51,70-7 (March 1953). (253) Spencer, L. F., Steel Processing, 38, 244-9, 257 (1952). (254) Ibid.. DD. 288-94. 298. 34W3. 350. (255j Spen&r, L. F., @eZdi& Engr.’, 37,45-53 (October 1952). (256) Ibid., pp. 55-9. (257) IM., 38,52-6 (March 1953); 53-7 (April 1953). (258) Spindler, B., Foundry, 80, 110-13 (August 1952). (259) Ludlum Steel Corp., . . “Stainless Steel Handbook,” Allegheny ~. . . Pittsburgh, Pa. (260) Steel, 130, 92-6 (June 2, 1952). (261) Ibid., 130, 95 (June 9, 1952). (262) Ihid., 131,90-1 (November 17, 1952). (263) IWd., 131, 102 (Dec. 8, 1952). (264) Ibid., 132, 86, 89 (Feb. 16, 1953). (266) Steel Horizons, 14, 20-3 (Summer 1952). (266) Ibid., 15, NO. 1, 8-9 (1953). (267) Stevens, L. G., Welding Enp., 38, 23-5 (February 1953). (268) Storchheim, S., Iron Age, 171, 140-2 (Feb. 12, 1953). (269) Ibid., 171, 135-8 (April 9, 1953). (270) Streicher, &I. A., ASTM Bulletin, No. 188, 35-8 (February 1953). (271) Sucksmith, W., Metal Treatment and D r o p Forging, 19, 545-6, 649 (December 1952). (272) Sullivan, G. F., ITon A g e , 169, 112-16 (June 26, 1952).
Vol. 45, No. 10
(273) Sully, A. H., Brandes, E. A., and Waterhouse, R. B.,Brit. J . Appl. Phys., 3,97-I01 (March 1952). (274) Sulzer Tech. Rev. (Switz.), No. 3, 17-23 (1952). (275) Talbot, A.M., and F’urman, D. E., Amer. SOC.Metals, Preprint 2 (October 1952). (276) Tennessee Valley Authority, “TVA Chemical Engineering Report No. 2” (1948). (277) Terry, J. G., Steel, 131,82-4 (Sept. 1,1952). (278) Thielsch, H.. Welding Research Council Bull., 14 (September 1952) (279) Thielsch, H., and Pratt, W. E., Iron A g e . 170. 135-9 (July 10, 1952). Tice, E. A., Chem. Eng. Progr., 48,329-32 (July 1952). Timmerbeil, H., Giesserei, 38, No. 2,25-9 (1951). Tremlett, H. F., Welding and Metal Fahricatim, 20, 258-61 (June 1952); 299-303 (August 1952). Tucker, A. J. P., Welding and Metal Fabricationn,20, 253-7 (July 1952). Udy, ILI. C., Battelle Tech. Rev., I: 84-8 (August 1952). Uhlig, H. H., and Woodside, G. E., J . Phys. Chem., 57, 280-3 (March 1953). Viles, P. S. (to Standard Oil Co.), U. S. Patent 2,626,459 (Jan. 27, 1953). Vollmer, L. W., Trans. Can. Inst. Mining Met.. 55, 89-95 (February 1952). Von Hambach, E., Machinist, 96,2714 (Feb. 23, 1952). Waber, J. T., and Waber, S. F., Metal Progr., 63, 204, 206, 208 (January 1953). Wache, X., MBtaux (Corrosion-Inds.), 27,56-68 (February 1952). Welder. 21, 80-3 (October-December 1952). Welding Engr., 37,42-3 (September 1952). Ibid., 37,60-1 (October 1952). Ibid., pp. 64-6. Ihid., pp. 73-5. Ibid., 38, 23 (January 1953). Welty, J. W., Welding J., 31, 3615-65 (1952). Werwach, H., Stahl u . Eisen, 72, 341-5 (March 27, 1952). Western Metals, 1 1 , 5 6 2 (February 1953). Wilshaw, C. T., Metallurgiu, 45, 102-6 (February 1952). Works, G. A., Corrosion,8,217-21 (June 1952). Yellott, J. I., Power Eng ,56,56-9 (May 1952). Zapffe, C. A., Iron Age, 171,138-42 (March 19, 1963).
Tin and Its Alloys ROBERT J. NEICERVIS Tin Research Institute, Inc., Columbus 1, Ohio Restrictions on tin have been removed. For the last five years prcduction has markedly exceeded consumption. The future supply is ample. An unusual new use for tin has been discovered; it imparts weldability and ease of fabrication to high strength titanium alloys. A method of bright electrotinning steel strip in a phenolsulfonic bath has been announced. This is the first instance of bright nontoxic electrotinning of strip. Many marked improvements have been made in existing processes using tin and in recently developed materials containing tin. These include a method of reducing sludge in the “halogen” electrotinning process and improved aluminum-tin strip bearings containing 20 to 30yo of tin.
I
T IS customary to begin these annual reviews with comments
on the supply picture. This year there is plenty of tin. The National Production Authority believed that U.S. tin reserves had reached a level where all controls over uses and stocks could be removed on Feb. 6,1953. The only requirement is that consumers must make monthly reports on consumption and stocks. I n the light of production figures, this bit of news comes none too soon. For five consecutive years tin output has exceeded consumption, and by a considerable amount. I n 1952 tin production was 168,000 long tons, and tin consumption was 128,000 long tons, FUTURE PROSPECTS FOR TIN
The Paley Report (69, 140, 141) showed tha.t the outlook for tin for the next 30 years or so is promising, particularly from the
consumer’s standpoint, since the projected increase in future demand for tin is less than for any of the key commodities. Further, it points out that in the near future tin may not be regarded as critical because of known alternatives. Thus, under conditions of no artificial restraint, a modest increase in consumption with ample supplies is forecast (69). Concurrent with all this reassurance, belated, if not significant, suggestions for conserving tin have appeared (109). These belie the fact that tin is indeed an important constituent in marine engineering by showing that the combined properties of tin babbitts, bronzes, and solders make i t unwise to use tin substitutes for reasons other than scarcity, NEW TIN-CONTAINING MATERIALS
Titanium-Tin and Zirconium-Tin Alloys. Probably the most dramatic use of tin to be announced this year is its use in pounds -per sauare inch Rem-Cru’s titanium alloy A-110 (110,000 . . . yield). The tin constituent strengthens the alloy, but more important it imparts weldability t o the alloy making i t the only
October 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY
weldable high strength titanium alloy. In addition t o this, it makes the alloy easier t o hot fabricate because of its so-called "free scaling" characteristics.. Tin additions strengthen zirconium alloys in much the same manner as in the titanium alloys. It stabilizes the alpha or low temperature phase (73,169). New Bearing Alloys. The recently developed aluminum-tin alloys containing 20 to 30% tin offer a n attractive answer to the need for a bearing alloy which has sufficient strength t o take the heavy loads of modern internal combustion engines and yet are sufficiently soft t o run satisfactorily with ordinary mild steel shafts (107, 169). Methods of bonding these alloys t o steel and duraluminum backings have been developed (169). Examples of these bonded bearings are shown in Figures 1and 2.
CCURTEBY TIN RESEARCH INBTITUTC
Figure 1. Aluminum 20% Tin-Bearing Alloy Bonded to Strong Aluminum-Base Alloy Lining hardness, 25 V.P.H.; backing hardness, 110 V.P.H. Manufactured by Glacier Metal Co. Ltd. by patented proceao
*
s
These aluminum-tin bearing alloys depend on a combination cold working and annealing process t o secure an effective distribution of tin in an aluminum matrix. This new technique is applicable not only t o the binary aluminum-tin alloy, which is very soft, but t o ternary alloys where a third metal converts the aluminum matrix to an age hardening alloy. The binary aluminumtin alloys have a much higher fatigue strength than babbitt at working temperatures, and the ternary alloys have considerably higher fatigue strength than the binary alloys. Other significant bearing alloy developments include a fundamenta'l study of friction phenomena in babbitts and three new tin-containing bearing alloys-a tin-coated, silver-plated bearing ( 4 1 , 166) and two lead-base bearing alloys; one is reported t o have higher than usual strength (60) and the other superior fatigue resistance (163). A tabulation giving detailed information on the properties of tin babbitts has appeared (117)with a similar tabulation, in the same publications, covering tin and tin alloys generally (116). New Solder Alloys and Methods for Joining and Tinning Aluminum. There is room for considerable improvement in solder alloys for joining aluminum, particularly as regards corrosion resistance. An interesting development is the addition of 1 t o 5% cerium t o a tin-rich, tin-zinc solder t o achieve improved salt spray resistance and also better wettability ($2). The salt spray resistance is further improved with an addition of 1 t o 5y0 aluminum ( 2 2 ) . Another tin-rich tin-zinc solder for joining aluminum contains 0.3 to 1.2% each of aluminum and silver (160). Ultrasonic methods for soldering and tinning aluminum have received a lot of attention this year (10, 19, is.@,173, 176, 177). Work is proceeding on a plant that uses an ultrasonic transducer under the tinning bath (30)for the continuous tinning of aluminum wire. Figure 3 shows a proposed layout for such a process (30). The use of ultrasonic soldering for repairing light alloy castings has also received attention (12.2). Improvements in Soldering Methods. Tin-indium solders
2255
are used t o solder glass t o glass and glass t o metal using conventional methods. Vacuum tightness of seals made with 50:50 tinindium solders are considerably better than seals made with other indium alloys (84). A new and unusual mechanized dip soldering technique for television receivers permits the soldering of 424 joints a t once (106).'Figure 4 is an illustration of the dip solder machine used in this particular application (106). Other ingenious production line soldering techniques have been described (48, 66). Manufacturers of solders, soldering fluxes, and pastes have sought t o put them on the market in forms easy t o use. This necessary information has been collected and published (26,110). The paradoxical requirements of an ideal flux-strong attack during the soldering operation and complete inertness afterward-are constantly being sought with new formulations (90, 168, 178, 179). Two of these (178, 179) cover successful commercial applications of the so-called noncorrosive fluxes for radiator soldering. Gaseous reduction of iron carbide t o ferrite in order t o promote easy tinning of high carbon steels has been patented (31). The use of paste solders for joining difficult assemblies is gaining favor (38). New solder-flux paste formulations have been developed (88,161). Lead Alloys Containing Tin. The effect of tin additions on the extrudability of cable lead has been studied (103) and a lead-base alloy having the same hardness and sheet rolling capacity as that of tin has been developed (134). Tin Bronzes. Not many people know that a bell hammer should be softer than the bell which it strikes. Copper-base hammer alloys of suitable softness which contain tin have been developed (1). Bell alloy that produces a good ringing tone contains 80 parts of copper and 20 of tin. A detailed account of the production of thousands of souvenir coronation bells by the socalled shell molding method has been published (170). Higher tin- bronzes-Le., those which have tin contents greater than 13y0 -have received attention (80, 146). A chrome-beryllium tin-
COURTEBV TIN RESEARCH INSTITUTE
Figure 2.
Aluminum 209'0 Tin-Bearing Bonded to Steel by the Tin
Alloy
Research Institute process; lining hardness, 25 V.P.H.
bronze said t o possess remarkable annealing hardness, high strength, and heat- and corrosion-resistance has been patented (130). A new method of electrolytically polishing tin-bronze has been developed (137). Copper alloys containing tin are used t o secure pressure-tight castings. Methods of achieving pressure-tightness received a great deal of attention last year (6,97,98,160). Comprehensive studies of all phases of bronze casting ( 4 ) and the chill casting of tin-bronzes (67) have been published. The effect of lead and nickel on the grain size of tin-bronze and the effect of tin on mold penetration have been studied (27,89). Organotin Compounds. Organotin compounds such as dibutyl tin dilaurate and dibutyl tin maleate fulfill almost all the conditions of an ideal stabilizer for vinyl pla8tics (163). Produc-
INDUSTRIAL AND ENGINEERING CHEMISTRY
2256
tion of organotin compounds for this purpose has reached 300 t o 400 tons per year. Figure 5 illustrates how the organotin compounds prevent discoloration and permit the manufacture of clear transparent sheets. Many patents have been issued on organotin compounds for this purpose (24, 66,49, 85, 86, 111, 112) and for stabilizing rubber and rubberlike polymers ( d , 2 1 ) . A method of preparing stannous dilauryl stannone has been published (164). New Materials Containing Inorganic Tin Compounds. An interesting group of new materials for electrical contacts contains pressed and sintered mixtures of silver and silver alloys with tin oxide (44). A new development in electronic components is a resistor made by depositing a tin-antimony oxide film on a glass
r-l
TRANSLUCW
Vol. 45, No. 10
before, but this is the first time that bright as-deposited plate free from toxic occlusions has been produced. Bright as-deposited plate has one decided advantage over melted coatings; it does not have an alloy layer. Another promising development in both phenolsulfonic and fluoboric acid plating baths for both tin and tin-lead alloys is the discovery that the isomeric ratio of the 4,4'and the 2,4'- isomers of dihydroxydiphenyl sulfone, the addition agent, is critical. Keeping the ratio in the range 60 to 85% by weight of the 4,4'- isomer and the balance essentially 2,4'- isomer permits a wide cathode current density range. Tarry matter in this mixture must be below 1% as it is mechanically occluded in the coating and interferes with solderability ( 7 ) . Improvements in the so-called halogen bath have also been made. The addition of thiourea to the standard halogen bath reduces oxidation and the consequent sludge formation (61). Improved methods of continuously treating tin plate in an electrotinning line to secure enhanced corrosion resistance have been developed (131). This process, which not only inhibits sulfur discoloration but also prevents baking discoloration and has good resistance to abrasion and good phenolic lacquer adherence, is carried out by first making the strip cathodic then anodic in an acid solution of sodium chromate with or without an alkali phosphate. The phenolic lacquer adherence characteristics of plate so treated is better the lighter the anodic protective film.
COURTESY MULLARD L T D
Figure 3. Proposed Plant Layout for Continuous Tinning of Aluminum Wire, Using Ultrasonic Transducer under Molten Tin Bath base (51). Patents have been granted on a method of manufacturing silica extended tin oxide for opacifying vitreous enamels (146)and on stannic oxide refractories containing 1 t o 5% antimony trioxide (166). TIN ALLOY ELECTROCOATINGS
Tin-Bronze as a Replacement for Nickel Undercoats. Probably the most newsworthy item in tin alloy electroplating is the use of bronze as a replacement for scarce nickel in chromium plating (49, 154, 166). Salt spray test comparisons in Figure 6 show that bronze undercoats are much more corrosion-resistant than copper, another frequently used replacement for nickel undercoats. Results for both 90: 10 copper-tin and 80:20 copper-tin are shown in Figure 6. Both are satisfactory as regards corrosion; however, the 80:20 alloy is preferred because of its better leveling characteristics in the pyrophosphate bath used in this particular case. These alloys may be plated bright in the asdeposited condition in the pyrophosphate bath as well as in other baths (156). Alternatives t o chromium plating studied include the only other common nontarnishing coating-65 :35 tin-nickelwhich uses one third as much nickel as chromium-on-nickel for equivalent protection (33,52,55,171). New Tin Alloy Electrocoatings. The electrometallurgy of the many promising new electrotin alloy coatings has been summarized ( 7 4 , 1&), and structure studies have been made of the two most notable ones from the standpoint of combination of corrosion resistance and solderabilit~~-80: 20 tin-zinc and 25 :75 tin-cadmium (8). A patent has been issued on the electrodeposition of the cadmium-tin alloy (68). Other new electrotin alloy developments include methods of depositing tin-antimony ( 3 2 ) and zinc-copper-tin ( 1 5 7 ) . A comprehensive study of the influence of operating variables on the composition of electroplated tin-lead alloys has appeared ( 4 7 ) . ELECTROTINNING
Improvement in Commercial Production of Electrotinplate. By far the most unusual development in electrotinning is the new phenolsulfonic acid plating bath which deposits tin almost as bright as is obtainable by present melting-after-coating methods ( 6 ) . Bright as-deposited electrotin coatings have been obtained
COURTESY (IENERAL ELECTRIC CO.. SYRACUSE. N, Y .
Figure 4. Loading Chassis onto Conveyor of DipSoldering RIachine for Television Assembly Line New Developments in Electrotinning. It is interesting to note that this year a new commercial process for the electrotinning of wire was developed (106), and an independent investigation (120)showed that electrotinned coatings have advantages over hot-dip tinned coatings. Other new developments in electrotinning include the following: 1. An examination of a new method of electrodepositing tin from a pyrophosphate bath ( 1 7 2 ) 2. An investigation of the hydrogen embrittlement of steel in the well established alkaline bath which showed that it is indeed a factor with which to be reckoned (183) 3. A fundamental study of tin sulfate electrolytes ( 3 9 )
The British Standards Institution has issued specifications on five classes of electrotin coatings ( 1 2 ) . The growth of whiskers on the surfaces of some electrocoatings,
I N D U S T R I A L A N D E N G I-N E E R I N G C H E M I S T R Y
October 1953 0
No stabilizer
I5
30
45
eo
75
2257 90
105
120
30
Dibutyltin 31 maleate, 3 parts
Figure 5. Polyvinyl Chloride Plastic Sheet (Geon 101) Stabilized with an Organotin Compound Does Not Discolor after Oven Aging for 120 Minutes at 175”C.
4
among them tin, is cause for concern because of high frequency losses a t low currents. Electron microscope studies have shown that the general shapo of the tip end of the “whisker” persists, thus indicating that growth takes place a s a result of the addition of material at the base of the whisker (9.4). Trends in Electrotinplate Usage. The trend in electrotinplate for canned food products is toward thinner coatings (71, 76, 114). The former standard product of the electrotinning line, 0.50 pound per base box electrotinplate, will soon be superceded entirely by 0.25 pound per base box plate, one half as much as formerly (129). There is hope in the can manufacturing industry that a differentially coated electrotinplate will eventually replace hot-dip plate and thus save 45% of the tin required for cans for the more corrosive food packs (87, 166). So far, manufacturing difficulties with differentially coated electrotinplate have prevented this in all but very few of the more corrosive food packs. Unusual Coating Methods. Sputtering and evaporation processes are related methods of producing thin metallic films on both metallic and nonmetallic surfaces. Sputtering involves the application of high voltage between two electrodes in a partial vacuum which induces a glow discharge. A disintegration of the cathode occurs, and the metal removed is deposited in a thin film on nearby objects. The evaporation process utilizes thermal rather than electrical means. The metal being deposited is heat vaporized by high amperage electricity, and the metallic vapors produced are deposited on nearby surfaces. Sputtering of tin films (40, 86) and the formation of silver-tin alloys by evaporation in vacuum ( 1 2 4 )have been studied. A method of immersion-tin plating of silicon containing aluminum alloys has been patented (83). This method covers both preparation and immersion plating in a stannate bath. Another method for the immersion-tin coating of aluminum has been patented; it is said to be an improvement over the stannate bath (76). This fluoride-sulfate bath is less sensitive to temperature variations and to the composition of the aluminum alloys than is the stannate bath. NEW DEVELOPMENTS I N TINPLATE AND CANNING PRACTICE
X
Probably the recent development most far-reaching in its effect on the tinplate industry is the advent of aseptic canning. This will permit much lighter weight tinplate stock to be used for containers (67). As the thinner coatings of tin on electrotinplate were adopted by the canning industry, the use of protective organic coatings increased enormously. Consequently, organic coatings for cans have continued t o receive attention. Methods of achieving good adherence by pretreatment (14, 16),the effectiveness of lacquers in preventing solution of tin in canned food (fOO),and recent developments in commercial applications (66) have received attention this year. There have been two new and important developments in tinplate manufacturing methods. One is an improved method of finishing hot-dip tinplate. Ordinarily, the last bit of palm oil remaining on a sheet of hot-dip tinplate is removed by mechanically scrubbing the sheet with bran in a “branner.” A successful
“brannerless” machine for cleaning hot-dip tinplate has been patented (128). The other development is a rapid electrolytic method of determining the thickness of tin and the tin-iron alloy layer on tinplate (96). This is an important control tool and will permit rapid checks on the operation of electrotinning lines. Other methods of measuring the thickness of tin coatings have also been described (139). CORROSION RESISTANCE OF T I N AND TIN ALLOYS
A rather comprehensive review of the corrosion resistance of tin and tin alloys has been published (19). Studies have been made of the effect of surface active agents on tin (149), of the effect of fruit and vegetable juices on tin (461,and of the velocity of corrosion of tin in various media (64). Stress-corrosion studies have been made on tin alloy coatings (66). BASIC RESEARCH
Basic research, the starting point of subsequent engineering developments, can be covered only briefly in a review of this kind. Some of the new developments in varied fields of research relating to tin are as follows: Gray tin, the stable form of tin a t low temperatures, has received considerable attention. Because of the natural impurities present in commercially pure grades of tin, it has been difficult to produce gray tin in the laboratory. Methods of producing it by cold working white tin and storing it for 12 to 24 hours below the transformation temperature have been described (76, 81). Germanium has been found to exert an accelerating effect on the transformation of white to gray tin (148). Measurements have been made of the specific heat (78) and magnetic susceptibility ( 1 7 ) of gray tin. The alloy systems, zirconium-tin ( l l S ) , aluminum-indium-tin (18), and silver-magnesium-tin ( 7 7 ) have been studied. The effect of hydrogen on the embrittlement of zirconium-tin alloys has also been studied (127). Other physical metallurgy studies which cover tin and tin alloys include the following: The solid solubility of tin in aluminum (68) The agin characteristics of ternary aluminum-copper alloys with tin (697 Phase changes in silver-tin amalgams (166) Crystal growth phenomenon in antimony-lead-tin alloys (104) Production (180) and structure (9, 166, 167) of single tin crystals Elastic aftereffect of tin single crystals subjected to plastic flow (101) Tin in its liquid form has come in for its share of study as the following list indicates: The structure of liquid tin ( 3 4 ) The viscosity of molten tin (186) The surface tension of tin a t its melting point (166) Kinetics of crystalline nucleus formation in supercooled liquid tin ( I88) The oxidation of liquid tin ( 6 4 ) The heat capacity of tin in the vicinity of its melting temperature (91) The heats of solution of Group I metals in liquid tin (168) Liquid tin alloys, too, have received attention:
INDUSTRIAL AND ENGINEERING CHEMISTRY
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Vol. 45, No. 10
\
--+.
i .
1
r
%-
0.000G5-inct..
10% t i n bronze plus 0.00002-inch ohromium
O.OW&inoh, 20% tin brpnze plus 0.00002-inch chromum
Figure 6.
0.00065-1nch, 10% tin bronze plus 0 00002-inch 0.00055-inch, 20% tin bronze plus 0.00002-incl chromium chromium
0.00065-inch copper plus 0.00002-inch chromium 0.0008hinch copper plus 0.00002-inch chromium
Salt Spray Test Panels (48 Hours) Show That 80:20 Copper-Tin and 9O:lO Copper-Tin Undercoats Are Superior to Copper Undercoats for Decorative Chromium Plating
Fluidity of binary tin-zinc alloys (93) Flowability of tin-bismuth and tin-lead systems (181) Internal friction of liquid copper-tin alloys (185) Thermodynamic properties of the liquid ternary system, bismuth-, cadmium-tin ( 1 21)
ard methods of sampling tin plate have been reviewed, and a new met’hodwas proposed as a result of this study (80).
Oxidation of tin (70) and copper-tin alloys (36) have been investigated. Superconductivity of tin (16, 102, 184) and of tin sulfide (118) has been studied. This includes studies of the effects of isotopes of tin on superconductivity (119, 161). The thermal conductivity of superconducting tin below 1’ K. has been measured (60). Other electrical property measurements on tin and tincontaining materials include:
A method of producing extremely pure tin by vacuum distillation has been described (142). Patents have been granted for the recovery of tin oxide by autoclaving sodium stannate liquors (l47),for the recovery of tin values by the volatilization of tin bearing sulfide ores (176),and for the refining of tin and tin alloys (123). Additional details have been published on the methods of recovering tin from scrap tin plate developed by the Weirton Steel Co (95). Methods of separating a tin-bismuth eutectic alloy by crystallization under the influence of an electrical current (4%) and the separation of tin from impure speculum metal ( 1 1 ) have been described. Flotation methods for tin ores containing sulfides have been investigated (3, 68). Extraction methods practiced a t the Ikieno smelter of the Mitsubishi Mining Co. have been reviewed ( 1 7 4 ) .
Electrical resistance of thin tin films with lattice distortions (133) High frequency resistance of tin (63) Electrical properties of selenium-tin alloys (136) Lattice constants and dielectric properties of barium titanatebarium stannate-strontium titanate bodies ( 4 6 ) Radioactivity of tin has been the subject of numerous investigations (36, 65, 79, 90, 116, 136). NEW METHODS OF ANALYSES
A new publication that might prove useful to the chemical engineer covers methods of sampling and analyzing tin ingots (143). New polarographic methods for detecting tin in plating solutions (37, 68), new potentiometric methods for determining tin in bearing metal and bronzes (W), and new photometric methods for determining arsenic and antimony in tin (29) and aluminum in tin (108) have been published. A new wet method for determining tin in copper-base alloys (92) has been published. Stand-
REFINING AND RECLAMATION
LITERATURE CITED
(1) Aberascher, Dorothea,Austrian Patent 172,169 (Aug. 11, 19.52). (2) Albert, H. E. (to Firestone Tire and Rubber Co.), U. S. Patent 2,626,954(Jan. 27,1953). (3) Allen, J. C., Bull. Inst. Mining Met., No. 553, 62, 81-90 (December 1952). (4) American Foundrymen’s SOC.Inc., Chicago, Ill., “Copper Rase Alloy Foundry Practices,” 2nd ed., 1952. (5) Ames. B. N.,Ibid., “Symposium on Principles of Gating,” pp. 66-74 (1951). (6) Anrlrews, J. W. (to U. S. Steel Co.), U. S. Patent 2,598,486 (May 27, 1952).
October 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY
(7) Ibid. 2,633,450(March 31, 1953). (8) Aotani, Kaoru, J . Electrochem. SOC.Japan, 20, 611-14 (1952). (9) Arlman, J. J., and Bouman, J., “Selected Topics in X-Ray Crystallography from the Delft X-Ray Institutes,” pp. 11335, New York, Intersaience Publishers, 1951. (10) Beresford, L. G., Metal Progr., 63, 103-8 (January 1953). (11) Blanderer, Joseph, Erzbergbau u. MetallhWenw., 5, 90-5 (March 1952). (12) British Standards Institution, London, “Electroplated Coatings of Tin,” Standard 1872 (1952). (13) Britton, S. C., “Corrosion Resistance of Tin and Tin-Alloys,’’ Columbus, Ohio, Tin Research Institute, April 1952. (14) Britton, S. C., Org. Finishing, 13,No. 12,9-12, 17 (1952). (15) Britton, S. C., Sheet Metal Inds., 29,545-8,558 (June 1952). (16) Buckel, W., and Hilsch, R., 2. Physik, 131, No. 3, 420-42 (1952). (17) Busch, G., and Mooser. E., 2.physik Chem., 198,23-9 (1951). (18) Campbell, A. N., Buchanan, L. B., Kuzmak, J. M., and Tuxworth, R. H., J . A m . C h m . SOC.,74, 1962-6 (1952). (19) Can. Metals, 16, 32-3 (January 1953). (20) Capuano, G., Industria Ital. conserve, 27, 115-21 (1952). (21) Carroll. R. T. (to B. F. Goodrich Co.), U. S.Patent2,597,920 (May 27, 1952). (22) . , Chadwick. Richard. and Heaton. W. G. (to Imperial Chemical Industries), Ibid.; 2,552,935(May 15, 1951): (23) Chlebovsky, Teofil, and Brhacek, Lubomir, C h m . Listy, 46, 528-32 (1952). (24) Church, J. M., Johnson, E. W., and Ramsden, H. E. (to Metal and Thermit Corp.). U. 5. Patent 2,591,675(April 15,1952). (25)Ibid., 2,593,267(Agril 15, 1952). (26) Clauser, H. R., Materials & Methods, 35, No.3, 105-20 (1952). (27) Colton, R. A., Turk, F. L., and LaValle, D. L., Trans. A m . Foundrymen’s Soc., 60, 605-10 (1952). (28) Commonwealth Scientific and Industrial Research Orgilnization and Mining Department, Univ. of Melborne, “Concentration of a Tin Ore Containing Sulphides from the Ivy Mine, Emuford, Queensland,” Invest. No. 405 (Nov. 7, 1951). (29) Coppins, W. C., and Price, J. W.,Metallurgia, 46, 52-4 (July 1952). (30) Crawford, A. E., Electronics, 25, 102-5 (Dec. 1952). (31) Crego, F. T. (to Air Reduction Co. Inc.), U. 8. Patent 2,594,129 (April 22, 1952). (32) Cuthbertson, J. W., and Parkinson, N., Electrodepositors’ Tech. Soc., “Electrodeposition of Tin-Antimony Alloys from Chloride-Fluoride Electrolytes,” Advance Copy 6 (1952). 33) Cuthbertson, J. W., Parkinson, N., and Rooksby, H. P., J . Electrochem. SOC., 100, 107-19 (March 1953). (34) Danilova, A. I., Danilov, V. I., and Spektor, E. Z., Doklady Akad. Nauk S.S.S.R., 82,561-4 (1952). (35) De Carli, F. and Collari, N., Engineering Digest 13, 183-5, 193 (June 1952) [Translated from Metallurgia ital., 44, 1-5 (Januarv 1952)1. (36) DescGamps,Yvon, and Avignon, Paul, Compt. rend., 236,47880 (Feb. 2,1953). (37) Diaz, Rafael, Plating 40, 45-6 (January 1953). (38) Dilley, D. C., Elec. Mfo., 51, 119-23, 360 (April 1953). (39) . . Discher. C. A.. J . Electrochem. SOC., 100, 45-51 (January 1953). (40) Dobretsov, L. N., and Karnankhova, N. M., Doklady Akad. Nauk S.S.S.R., 85, 745-8 (1952). (41) Donley, C. 0. (to General Motors), U. S. Patent 2,621,988 (Dec. 16,1952). (42) Drakin, S. I., Izvest. Sektora Fiz. Khimi. Anal., 20,341-4,1950. (43) Duc, F. S., Electroplating and Metal Finishing, 5, 123 (April 1952). (44) Diirrwitchter, Eugen, German Patent 807,416 (June 28, 1951). (45) Duijn, C. van Jr., Polytech. Tijdschr., 7,736a-9a (1952). (46) Dungan, R. H., Kane, D. F., and Bickford, L. R., J . A m . Ceram. SOC.,35,318-21 (1952). (47) Du Rose, A. H., and Hutchison, D. M., Plating, 40,No. 5,470475,497,to be continued in later issues (May 1953). (48) Eadon-Clarke, C. E., Elec. C m m u n . , 29, 179-85 (September 1952). (49) Eberly, K. C. (to Firestone Tire and Rubber Co.), U. S. Patent 2,560,034(July 10, 1951). (50) Ednie, J. F. (to Am. Metal Co. Ltd.), Ibid., 2,597,461 (May 20, 1952). (51) EZec. Mfg., 50, 118-26 (July 1952). (52) Electroplating and Metal Spraying, 5,292-8 (September 1952). (53) Ibki.. 5.361-366 (November 1952). (54) Endo, .Hikozo, &d ‘Yokoyama, Goro., Nippon Kinzoku CfakkaGShi ( J . Japan Inst. Metals), 14B, No. 4,55-8 (1950). (55) Fireman, E. L., and Schwarzer, D., Phys. Rm., 86, 451-3 (1952). (56) Flugge, S. L.,and Briahta, J. C., Modern Packagiw, 25, No. 12,131-4, 388 (1952).
2259
(57) Flugge, S.L.,Iron Steel Engr., 29,127-9,Disc. 129-30 (December 1953). (58) Forso, Bengt., Acta h a d . Aboensis, Math Phys., 17, No. 3, 1-120 (1951). (59) Gonser, B. W., U. 5. Govt. Printing Office, Washington 25, D. C., “Resources for Freedom,” Vol. IV, pp. 55-63,1952. (60) Goodman, B. B., Proc. Phys. SOC. (London), 66A, 217-27 (1953). (61) Gray, A. G. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,585,902(Feb. 19,1952). (82) Gray, Russell D., Jr., and Paecht, W. A. (to Curtiss-Wright Corp.), Ibid., 2,609,338(Sept. 2, 1952). (63) Grebenkemper, J., and Hagen, J. P., Nutl. BUT. Standards, Circ. 519, 103-8 (1952). (64)Gruhl, W., and Gruhl, U., Metall, 6,177-182 (April 1952). (65) . . Habel, C. (to General Motors Corp.), U. S. Patent 2,591,065 (April 1, 1952). (66) Hannon, C. H., Metal Finishing, 50, No. 10, 65-6, 71 (1952). (67) Hanson, D., and Pell-Walpole, W. T., “Chill-Cast Tin Bronzes,” London, Edward Arnold and Co., 1951. (68) Hardy, H. K., J . Inst. Metals, 80, 431-434 (1952). (69) Ibid.. pp. 483-92. (70) Hart, R. K., Proc. Phys. Soc., 65B, 955 (1952). (71) Hartwell, R. R., Modern Lithography, 20, 49,51,53, 113, 115 (March 1952): 61,63 L4pril 1952). (72) Hartwell, R. R., Modern Packaging,25, 136-9, 182,185 (June 1952). (73) Hayes, E. T.,and Stephens, W. W., Metal Prow., 63, No. 6, 97-110 (1953). (74) Hedges, E. S., and Cuthbertson, J. W., Chemistry & Industry, 1952, PP. 1250-4. (75) Hedges, E. S.,and Higgs, J. Y., Nature, 169,621-2 (1952). (76) Heiman, S. (to Philadelphia Rust-Proof CO.), U. 8. Patent 2,624,684(Jan. 6, 1953). (77) Henry, W. G., and Raynor, G. V., Can. J. Phys. 30, 412-21 (1952). (78) Hill, R. W., and Parkinson, D. H., Phil. &fag., 43, 309-16 (1952). (79) Hogg, B. G., and Duckworth, H. E., Phys. Rev., 86, 567 (1952). (80) Hosoi, Y.,Nippon Kinzoku Gakkai-Shi ( J . Japan. Inst. Metals), 16,42-6 (January 1952). (81) Ishikawa, H.. J . Phys. SOC.Japan, 6, 531-2 (1951). (82) Itterbeek. A. van. Greve, L. de, and Heremans, F., Applied Sci. Research, 2B, No. 5, 352-60 (1952). (83) Izumi, T., Japan. Patent 2820 (Sept. 22, 1950). 184) Jaffee, R. I., and Weiss, S. M,, Materials & Methods, 36, 113-5 (September 1952). (85) Johnson, E. W., and Church, J. M. (to Metal and Thermit Corn.). U. 8.Patent 2,570,686(Oct. 9, 1951). (86) Ibid., 2,599,557(June 10, 1952). (87) Johnston, 5. S., Iron Steel Engr., 29,72-75 (May 19623. (88) Kaneko, S. (to Tokyo Shibaura Electric Co.), Japan. Patent 1321 (March 12, 1951). (89) Kashima, J., “Studies on Metal Penetration in Castings,” Repts. Casting Research Lab. Waseda Univ. (Tolcyo) No. 3, 31-6 (1952). (90) Keel, C.G., and Brubacker, C. B., 2.Schweisstech. J . Soudure, 42,95-101 (May 1952). (91) Khomyakov, K. G., Kholler, V. A., and Zhvanks, S. A., Vestnik Moslcov Univ. Ser. Fiz-Mat. i Estestven Nauk No. 2,7 ; NO.3,41-9 (1952). (92)Kinnunen, Jorma. and Merokanto, Bengt., Chemist Bnalyst, 41, 4-5 (March 1952). (93) Kondic, V.,and Yao, T. P., Rev. met., 49, 321-6, Disc. 326-7, (May 1952). (94) Koonoe, S. E., and Arnold, S. M., J . Appl. Phys., 24, 365-6 .(March 1963). (95)Krombholz, A. J., Iron Steel Engr., 30,98-106 (March 1953). (96) Kunze. C. T., and Willey, A. R., J . Electrochem. SOC.,99,354-9 (September 1952). (97) Kura, J. G.,and Eastwood, L. W., “Effects of Gating Practice on Leak Tightness of 85-5-5-5and 81-3-7-9Alloy Castings,” American Foundrymen’s Society, Preprint 52-67 (1952). (98) Ihid., “Effects of Mold Materials on Leak Tightness and Mechanical Properties of 85-5-5-5and 81-3-7-9Alloy Castinga,’’ Preprint 52-55. (99) Leader, G. R., Natl. Nuclear Energy Ser., Div. IV, 9, Radiochem. Studies, “Fission Products,” Book 2,pp. 91%27 (1951). (100) Levi’eva, L. S., Chem. Zentr. 1950, 11, p. 1640. (101) Likhtman, V. I., and Rebinder, P. A., Doklady dlcad iVauk S.S.S.R., 57, 53-56 (1947). (102) Loak, J. M., Proc. Roy. SOC.(London), A208, 391-408 (1951). (103) Loesahman, Arnold, Z.Erzbergbau u Metallhiittenw., 5. 219-23 (June 1952).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
(104) Lohberg, Karl, and Schulz, Elizabeth, Z.1Metallkunde, 43, 50-53 (February 1952). (105) Lord, K. M., Electronics, 26, No. 6, 130-137 (1953). (106) Lowenheim, F. A,, Wire and W i r e Products, 27, 464-7, 506-7 (May 1952); 565-8, 632-3 (June 1952). (107) Lowinger, V. A., Liddiard, E. A. G., and Hardy, H. K., Brit. Patent 666,087 (Feb. 6, 1952). (108) Luke, C. L., Anal. Chem., 24, KO. 7 , 1122-6 (1952). (109) Machol, WI.R., J . Am. SOC.?Caval Engrs., 64, 459474 (1952). (110) MacIntosh, R. AI., Welding J . ( A T . Y.) 31, 881-97 (1952). (111) Mack, G. P., and Parker, E. (to Advance Solvents and Chemical Corp.), U. S. Patent 2,604,483 (July 22, 1952). (112) Ibid., 2,626,953 (Jan. 27, 1953). (113) McPherson, D. J., and Hansen, M., “System Zirconium-Tin,’’ American Society for Metals, Preprint 34 (1952). (114) Maier, C. E., “Trends of Iliterest to the Canner,” presented a t the Pittsburgh Section Rleeting of the Institute of Food Technologists (Feb. 10, 1953). (115) Mandeville, C. E., Shapiro, E., nIemIenhal1, R . I., Zucker, E. R., and Conklin, G . R., Phys. Re?,.,88, 554-5 (1952). (116) Materials & Methods, 37, 127 (hIarch 1953). (117) Ibid., p. 129. (118) Matthias, B. T., and H u h , J. K., Phus. Rev., 87, i9!!--806 (1952). (119) Maxwell, .E., Ibid., 86, See. 2, 235-342 (1952). (120) Meiswinkel, Helmut, Werkstofe u Korrosion, 3, 355-5i (September-October 1952). (121) Mellgren, Svanta, J . Am. Chem. SOC.,74, 5037-40 (1952). (122) Metallurgia, 46, 251-252 (November 1952). (123) Meyer Metallurgical Corp., Brit. Patent 681,622 (Oct. 29, 1952). (124) Michel, Pierre, Contpt. rend., 235, 377-9 (Aug. 4, 1952). (125) Mochel, 2. M. (to Corning Glass Works), U. S. Patent 2,585,341 (Feb. 12, 1952). (126) Moffett, J. C., Ryge, G., and Barkaw, A. G., J . Appl. Phvs., 23, 1188-9 (1952). (127) Mudge, W. L., Jr., “Effect of Hydrogen o n the Embrittlement of Zirconium and Zirconium-Tin Alloys,” ASTM Symposium on Tin, Los Angeles (March 23, 1953). (128) Murphy, P. N. (to U. S. Steel Co.), U. S. Patent 2,601,863 (July 1, 1952). (129) Mutschler, W. J., Proc. Natl. Canners Assoc., 46th Contention Issue, Inform. Letter 1425. (130) Nakasato, S., Japan. Patent 3055 (June 12, 1951). (131) Neish, R. A. (to U. S. Steel Co.), E. S. Patent 2,606,866 (Aug. 12, 1952). (132) Neppiras, E. A., MetaZ Ind. (London),81, No. 6, 103-6 (Aug. 8, 1952). (133) Niebuhr, J., 2. Physik, 132, No. 4, 468-81 (July 1952). (134) Nishihara, S., et al., Japan. Patent 1936 (April 13, 1951). (135) Numata, Tadasi, Busseiron Kenkyu (Researches on Chem. Phys.), NO.27, 1-10 (1950). (136) Pearoe, R. M., and Darby, E. K., Phgs. Rev., 86, 1049-50 (1952). (137) Perryman, E. C. W., Metallurgia, 46, 55-7 (1952). (138) Pound, G. hl., and La Mer, V. K., J . Ant. Chem. SOC.,74,2 32332 (1952). (139) Prandetskaya, E. A., Zhur. Priklad. Khim., 25, 1066-71 (1952). (140) President’s Materials Policy Commission, U. S. Govt. Printing Office, Washington 25, D. C., “Resources for Freedom,” Vol. I, 1952. (141) Ibid., Vol. 11. (142) Price, J. W., Nature, 169, 792 (May 10, 1952). (143) Price, J. W., “Sampling and Analysis of Tin Ingots,” Bull. Tin Research Institute (England) (August 1951).
Vol. 45, No. 10
(144) Products Finishing, 16, 76, 78, 80 (September 1952). (145) Reeve, M. R., Rowden, J. S., and Cuthbertson, J. W., Metal I n d . (London),82,23-25 (Jan. 9,1953);49-52 (Jan. 16,1953). (146) Richter, H. W. (to Metal and Thermit Corp.), U. S. Patent 2,600,689 (June 17, 1952). (147) Ibid., 2,621,109 (Deo. 9, 1952). (148) Rogers, R. R., and Fydell, J. F., J . Electrochem. SOC.,100,161-4 (April 1953). (149) Ross, T. K., and Holness, H., J . Appl. Chem., 2,520-31 (1952), (150) Rutherford, N. B., J . Inst. Metals, 80, Paper No, 1381, 555-68 (1952). (151) Saito, Tero, Japan. Patent 3664 (July 13, 1951). (152) Sampson, D. F., Proc. Natl. Canners Assoc., 461h Conventional Issue, Inform. Letter 1426 (Feb. 28, 1953). (153) Schaefer, R. A., and Nohler, J. B. (to Cleveland Graphite Bronze Co.), E. S. Patent 2,605,149 (July 29, 1952). (154) Schmerling, G., Electroplating and Metal Finishing, 5 , 115-118 (April 1952). (155) Schmerling, G., Metal Ind. (London),80, 267-8 (April 4, 1952). (156) I b i d . , 81, 487 (June 12, 1953). (157) Schockley, R. E. (to Roy E. Schockley, Inc.), U. S. Patent 2,600,699 (June 17, 1952). (158) Schoenfeld, W. H., Jr., Ibid., 2,626,881 (Jan. 27, 1953). (159) Schwope, A. D., Metal Progr., 63, No. 5, 75-81 (1953). (160) Seidl, Karl, and Swetlik, Emerick, Austrian Patent 173,928 (Feb. 10, 1953). (161) Serin, B., Reynolds, C. A., and Lohman, C., Phys. REV.,86, Ser. 2, 162-164 (ilpril 15, 1952). (162) Smirnova, V. I., and Ormont, B. F., Doklady Akad. Nauk. S.S.S.R., Kew Series, 82, 751-753 (Feb. 11, 1952). (163) Smith, H. Verity, Plastics (London), 17, 264-6 (Sept. 1952). (164) Solario, Adriano, Gam. chim. ital., 81, 664-7 (1951). (165) Tabor, D., Australia, Advisory Council Sci. Ind. Research, Bull. 212 (1947). (166) Teghtsoonian, E., and Chalmers, Bruce, Can. J . Phys., 29, 37081 (1951). (167) Ibid., 30, 388-401 (1952). (168) Ticknor, L. B., and Bever, M. B., J . Metals, 4, 941-6 (Sept. 1952). (169) Tin Research Inst., Tin a i d Its Uses, 28, 2-4 (June 1953). (170) Ibid., pp. 6-7. (171) Ibid., pp. 10-11. (172) Vaid, J., and Char, T. L. Rama, Current Sci. (India),21,31011 (1952). (173) Walter, Leo, Can. Metals, 16, 18, 20 (January 1953). (174) Watanabe, &I., Japan Sci. Rev., 1, No. 4,67-74 (1950). (175) ?Fells, D. F., Thompson, R. B., and Roberts, E. J. (to Dorr Co.), U. S. Patent 2,600,351 (June 10, 1952). (176) Wenk, Paul (to Siemens-Schuckertwerke A.-G.), Ger. Patent 814,765 (Sept. 24,1951). (177) Wenk, Paul, and Boljahn, Heinrich, 2. Metallkunde, 43, 322-4 (September 1952). (178) Willard, R. H., and Gale, W. S. (to McCord Corp.), U. S. Patent 2,612,459 (Sept. 30, 1952). (179) Ibid., 2,612,460 (Sept. 30, 1952). (180) Yamamoto, Mikio, and Watanabe, Jiro, Science Repts. Research Insts., TOhOkU Univ., Ser. A, 3, 165-74 (April 1951). (181) Yanagihara, Tadashi, Ibid., Ser. A, 2, 843-55 (1950). (182) Yao, T. P., and Kondic, V., J . Inst. Metals, 81, Paper No. 1410, 17-24 (September 1952). (183) Zapffe, C. A,, and Haslem, >I, E., Plating, 39, 468-469, 485 (May 1952). (184) Zavaritsku, N. V., Doklady Akad. Nauk. S.S.S.R., 86, 601-4 (Sept. 21, 1952). (185) 2. Metallkunde, 43, 292-296 (August 1952).
Twelve Continuous Flow Reactors at the Government Synthetic Rubber Plant Operated by theB.F. Goodrich Chemical Co. at Port Neches, Tex
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