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By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By C. F., Christopher

The purpose of any steel-making process is to convert the two raw materials iron and scrap into steel. The chemical analysis of the steel is set within certain limits which involve the physical proper- ties desired by the consumer. In addition to tensile properties a large number of other properties are at the present time desired, such as impact resistance, grain size regulation, specific degrees of hardenability, resistance to creep at high temperatures, resistance to expansion on heat treatment, the ability of the product to undergo extreme amounts of cold deformation without failure, and many other properties which are not directly related to the specified chemical analysis. Variations in many of the properties of plain-carbon steels are due to elements and compounds not included in the ordinary "five element"§ composition. Such variations result primarily from variations in oxidation of the metal in the furnace and from the deoxidation method employed. The steel-making problem therefore resolves itself into two distinct sections: (I) the elimination of certain elements from the charge (the iron and scrap entering the furnace) and the addition of materials to meet the chemical specifications for the heat; (2) the manipulation of the slag and metal and the process of deoxidation to give certain desired properties in the steel entirely apart from the chemical analysis specified. Each of 'these two ends must be attained

Jan 1, 1957

By John Mathews

IT is a great honor to be asked by. the Board of Directors of this Institute to deliver the Henry Marion Howe lecture. The invitation carries with it a great responsibility, which I accept with considerable hesitation and with a feeling of unworthiness to perform the duties expected of me in this hour devoted to the memory of the life, character, and work of the late Professor Howe. Many of you recall the scholarly address delivered here a year ago by Prof. Albert Sauveur, and the beautiful tribute he paid-to his friend and colleague of many years in the great work of changing the art of iron making into the science of iron. My association with Professor Howe, was of brief duration-only one year-and the relation was that of pupil to teacher. My feeling toward him in later years was always that of a humble disciple at the feet of a master. He attained his third academic degree in the year that I was born. I recall the pride I felt when, after entering the, steel industry, I received from him, from time to time, letters asking for information or, perchance, asking my opinion, and he was always most punctilious in acknowledging the source of such bits of information in his writings. It was also my good fortune to sit at the feet of another great teacher-Sir William Roberts-Austen, at the Royal School of Mines. I mention him because his name was used by Osmond in coining the word "austenite," which is the subject of this address, and Osmond's suggestion was heartily approved by Howe. These three international metallurgists were the best of friends and delighted to honor the achievements of one another. There are other reasons for mentioning Roberts-Austen at this time. It was an introduction from Howe that opened to me the door of his -laboratory as well as of his heart. It was while at Roberts-Austen's laboratory that I .worked side by side with William Campbell

Jan 4, 1925

By John A. Mathews

It is a great honor to be asked by the Board of Directors of this Institute to deliver the Henry Marion Howe lecture. The invitation carries with it a great responsibility, which I accept with considerable hesitation and with a feeling of unworthiness to perform the duties expected of me in this hour devoted to the memory of the life, character, and work of the late Professor Howe. Many of you recall the scholarly address delivered here a year ago by Prof. Albert Sauveur, and the beautiful tribute he paid to his friend and colleague of many years in the great work of changing the art of iron making into the science of iron. My association with Professor Howe was of brief duration—only one year—and the relation was that of pupil to teacher. My feeling toward him in later years was always that of a humble disciple at the feet of a master. He attained his third academic degree in the year that I was born. I recall the pride I felt when, after entering the steel industry, I received from him, from time to time, letters asking for information or, perchance, asking my opinion, and he was always most punctilious in acknowledging the source of such bits of information in his writings. It was also my good fortune to sit at the feet of another great teacher— Sir William Roberts-Austen, at the Royal School of Mines. I mention him because his name was used by Osmond in coining the word "aus-tenite," which is the subject of this address, and Osmond's suggestion was heartily approved by Howe. These three international metallurgists were the best of friends and delighted to honor the achievements of one another. There are other reasons for mentioning Roberts-Austen at this time. It was an introduction from Howe that opened to me the door of his laboratory as well as of his heart. It was while at Roberts-Austen's laboratory that I worked side by side with William Campbell

Jan 1, 1925

By H Haas

H. HAAS, San Francisco, Cal. (communication to the Secretary?). -Fig. 1 plainly shows that the comparison of the steam-turbine and Diesel-engine plants was made on a basis of 6,000 kw. continuous operating load. The tabulation of costs for an 8,000-kw. load is merely done to show the relation of increased output on' the unit power costs. Both plants would sacrifice their reserve capacity, which is to insure continuous operation, if operated to generate 8,000 kw. continuously; unless Mr. Hawkins advocates the operation of one of the turbines at 33.33 per cent. overload, retaining the other as a standby, which, besides overtaxing the turbine, results in a great loss of efficiency. It would he well for Mr. Hawkins to qualify certain of his statements. Thus, under the caption "Diesel Engines, Selection of Units," he says that "two of the largest Diesel-engine builders take the position that, in the present state of the art, they would not attempt to put out units over 1,000 kw.;" he should qualify it by saving that "two of the largest American Diesel-engine builders take the position that, in the present state of the art in the United States, they would not attempt to put out units over 1,000 kw." The reason that American manufacturers restrict themselves at present to units of that size is to be found not so much in a lack of experience in building large units as in a lack of a sufficient, demand for them in the United States to justify the heavy capital outlay connected with the development of such engines. There are relatively few localities in the United States where fuel prices are as high as they are in the Southwest, and regions of high fuel prices are sparsely settled and have a very limited demand for power. Where low fuel prices obtain, steam turbines are active competitors of Diesel engines for large power plants, particularly when the station load factor is low. As most of the American manufacturers of Diesel engines work under license agreements with European manufacturers, which limit their market to the United States and its possessions and Canada, a further limitation is imposed upon them, leaving to European firms practically the entire world as a market.

Jan 5, 1917

By J. L. Christie, R. H. Leach

SO much has been written recently about the use of silver to replace scarce metals that certain facts about silver and its uses should be of interest. Figures for the production and use of silver, taken from the Handy & Harman annual reviews of the silver market, are given in Table 1. It will be seen that the rate of production has remained fairly constant and has been affected in recent years by the production of base metals, of which silver is a by-product. In each of the years 1937, 1938, and 1939, the U.S. Government acquisitions alone exceeded the entire world production, the difference, of course, being made up by imports of previously accumulated stocks. In 1940 and 1941 the U. S. Government acquisitions plus the United States and Canadian uses in the arts and industries exceeded the Western Hemisphere production. The U.S. Government pays a premium price for silver newly mined in the United States, at present 71.11c. compared with the price of 35'/8c. for foreign silver, with the result that the current U. S. production is not used commercially for the arts and industries. At the time this is written (June 1942) there is much uncertainty as to the future effect of this situation.

Jan 1, 1942

By Herty, C. H.

The effect of temperature on the physical properties of structural materials has been the subject of many investigations during the past decade. The literature on the effect of elevated temperatures. is voluminous, and during the last four years a great deal of experimental work has been carried out on the effect of low temperatures on the impact properties of steel. For many engineering purposes it is important to know the shock resistance of steels at low atmospheric temperatures, and with the ever-developing field of refrigeration and separation of materials at low temperatures, the normal limits of atmospheric temperature have been exceeded in practice. Iron and its alloys in the unnotched condition have a high impact strength at low temperatures, but in practice variations in type of notches result either from design or accidentally through scratches and surface or internal defects. A study of notched bar impact tests is, therefore, highly important to the engineer. A survey of the literature on low temperature impact testing indicates that chemical composition, heat treatment and method of testing have been the variables which have been considered in most previous work. In only a few instances has any mention of the steel- making method been mentioned and in these the comparison was between steel-making processes and not between steel-making methods on the same process. In view of the wide variations in impact properties at room temperature, in quench and strain ageing and in grain growth of steels of identical chemical composition, (by this is meant the usual five element analysis reported), it was felt

Jan 1, 1957

By H.E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By H. E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By J. O. Brittain, N. R. Adsit

It has been suggested that grain boundary motion during creep is a two-stage process, i.e., sliding followed by migration. Wienbergl found alternate sliding and migration of aluminum tricrystals tested in shear. He concluded that curves of grain boundary sliding (G. B. S.) vs time were not reproducible from specimen to specimen. Couling and Roberts,' who worked on polycrystalline magnesium, found that sliding and migration were interdependent. They were able to correlate the amount of sliding with the number of sliding-migration cycles, i.e., the amount of migration observed metallographically. Rhines, Bond, and Kissel found that the curves of grain boundary sliding vs time were spasmodic but they did not find any migration of the boundary. Some recent creep tests on bicrystals of high-purity zinc (99.99 pct) help to elucidate the role of grain boundary migration in the G. B. S. process. The experimental technique and apparatus are described elsewhere. The tests were conducted in vacuum or a protective atmosphere of argon. All specimens were stressed in simple shear along

Jan 1, 1961

CONTENTS RUSSIA-R. C.-BECKSTROM 3 VENEZUELA-F. H. KAY 9 TRINIDAD-W. J. MlLLARD 20 RUMANIA-1. I. GARDESCU 26

Jan 1, 1932

By Robert L. Fleischer

A well known but unexplained experimental fact is the observation1 that aluminum shows a pure <111> wire texture, in contrast with other fcc metals, which have a mixed <100> <111> texture at moderate reductions. A possibly related single crystal observation on aluminum is the following:2 under tensile deformation <111> single crystals are stable (maintain their original axial orientation), while <100> crystals are unstable at room temperature and become stable at lower temperatures. This suggests that at room temperature, as proposed by Yen and Hibbard,3 the single <111> texture obtains be- cause <100> orientations are unstable in the poly-crystal. It also implies that for wire drawing at lower temperature a <100> component of the texture might be expected since that orientation is then stable. This possibility has been examined by wire drawing at temperatures near 77°K. The apparatus was designed to be used with an existing draw-bench, a steel trough acting as die holder and containing sufficient liquid nitrogen to immerse the wire entering the die. The trough is insulated by a styrofoam container to prevent excessive boiling of the bath. The wire emerging from the die enters a polyethylene tube, into the far end of which the grips are inserted. Liquid nitrogen is funneled into the tube to maintain the low tem-

Jan 1, 1962

By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers&apos; was followed by a more systematic study of Wentrup and Hieber.&apos; These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All&apos; . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954

AALL,Christian H.,(M &apos;49), Asat.Research Dir , Phosphate Div Monsanto Chem.Co.,Monaanto, Tenn. AAMOT,Olav Crone, (M &apos;29), Dir of Tech., Chromium Min. & Smelt. Co Ltd Box 6215, Hillyard, Spokane, Wash. AARING, Floyd Daniel, (J &apos;48), Prod. Engr., Canadian Gulf Oil Co., 8035 - 102nd St., Edmonton, Alta., Canada AASE, Glenn D., (J &apos;40), Met Engr Western Research Div. ,Amer. Smelt. & Refin. Co., Selby, Calif ABADIE, Henry G (M &apos;43), Senior Prod Engr., Long Beach Oil Dev Co., 255 S Santa Clara Ave Long Beach 2, Calif. ABBOTT,Clarence E (M &apos;04), Civil Engr., 901 Insurance Bldg., Raleigh, N.C. ABBOTT, John, H., (M &apos;46), Resident Mgr., Hickman, Williams & Co., Rm 2205,230 N Michigan Ave., Chicago 1. I11.

Jan 1, 1952

The growth and influence of Sherritt Gordon Mines Ltd. in the nickel producing industry has been quite phenomenal. Although the company&apos;s Lynn Lake deposit in Manitoba was actually dis- covered in 1941, it was not until 1945, when men and materials were more readily available as a result of the end of World War II, that the area was staked and news of the discovery leaked out. As a result of the discovery, Professor Frank Forward of the University of British Columbia was commissioned by Eldon Brown, then President and Man- aging Director of Sherritt, to develop a new nickel refining process. A pilot plant, based on the results of Professor Forward&apos;s research, was constructed in Ottawa, and after the successful testing of the Lynn Lake ore, Chemical Construction Co. was given a con- tract in 1952 for construction of a producing plant. By 1954, the Fort Saskatchewan refinery was operating at an annual production of 15 million lb of nickel metal in the form of briquetts or powder. Capacity has since been increased to 30 million lb.

Jan 10, 1968

By William H. Bassett

RECENTLY it has become the custom of retiring presidents to talk of the relations of the Institute to its membership and its constituency- and it seems a good precedent to follow. Past-president Smith reviewed our relations to materials and to society in general. Mr. Bradley spoke of the value and use of our publications and of our educational duties. My message will be in regard to the coordination of our various groups of member interests and of service to industry. This Institute has, within its organization, four divisions and fourteen technical committees--each interested in a separate put very definite subject, and each covering a phase of mining engineering interest. These vary from geology and the geophysical methods of prospecting, to the physics of the structure of metals, truly "from the mine to the consumer"-from the preparation for mining to the final use of that which has been mined.

Jan 1, 1931

The Nominating Committee desire to submit the following nominations. President and Director: SIDNEY J. JENNINGS District 0 Vice-President and Director: H. S. DRINKER District 2 R. M. RAYMOND District 0 Directors: G. C. STONE District 0 HENNEN JENNINGS District 9 S. A. TAYLOR District 2 F. G. COTTRELL District 6 ARTHUR THACHER District 3 These nominations were unanimous. By order of the Committee J. V. N. DORR, Chairman. Oct. 10. 1917.

Jan 12, 1917

By C. F. Smart

THE heat treatment of the bronze composed of 88 per cent. copper, 10 per cent. tin, and 2 per cent. zinc, has been investigated by H. S. and J. G. S. Primrose,1 and also by the U. S. Bureau of Standards.2 The results obtained by H. S. and J. G. S. Primrose on dry-sand castings subjected to reheating followed by air cooling, or by quenching in water, are shown in Figs. 1 and 2. The values for tensile strength have been FIG. 1.-EFFECT OF QUENCHING ON DRY SAND CASTINGS (H. S. AND J. G. S. PRIMROSE.) converted from tons per square inch to pounds per square inch. Figs. 3and 4, have been plotted from values obtained by the Bureau of Standards on material of the same composition and treatment. Both investigations show that the ductility of the cast bronze is improved by heating to 700° C. and cooling in air, the strength not being impaired by this treatment. They are not in agreement, however, as to the effect of quenching, Messrs. Primrose reporting a decrease, and the Bureau of Standards an increase, in both strength and ductility when the cast bronze is heated to 600° or 700° C. and quenched.

Jan 9, 1919

By John Fritz

MEMBERS of the American engineering societies who were in London and Paris during the last days of. June and early July were present at many interesting gatherings. The official delegates of the Founder societies were the specially honored guests of the foreign engineering societies, but other American engineers took part in the meetings. The members of the delegation were: Arthur S. Dwight, Charles F. Rand, William Kelly, representing A. I. M. E.; Ambrose Swasey (general chairman of deputation), Ira N. Hollis, Jesse M. Smith, representing A. S. M. E.; F. B. Jewett, A. E. Kennelly, G. O. Squier, representing A. I. E. E.; Charles T. Main, Robert A. Cummings, John R. Freeman, D. C. Henny, representing A. S. C. E.

Jan 1, 1921

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970