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By F. P. Dewey

At the Wilkes-Barre Meeting of the Institute, Dr. J. Lawrence Smith, in the course of his remarks on some peculiarities in the composition of irons, alluded to the so-called " bucltshot" iron, and exhibited a specimen of this material. He said that when the small granules, or shot, were separatetl from the mass, they could be flattencd under the hammer, and inferred that these particles had been decarburized by the blast before sinking into the hearth of the furnace, and thus we had the exceptional production of wrought iron in the blast furnace. I have recently obtained a characteristic specimen of this variety of iron from one of the furnaces at Orbisona, Pa. Considerable uncertainty existed as to its true nature and the conditions of its production. Its weight seemed to preclude the idea that it containetl much or any slag, yet its lack of strength indicated that it was not homogeneous cast iron. At times considerable quantities had been produced, which could only be utilized by charging in the furnace and remelting. The specimen, on the freshly fractured surfacc, appeared to consist of flattened globules of iron cemented together by a bluish material which one would naturally suppose to be slag, and qualitative examination for lime strengthened this supposition. It was quite difficult to obtain drillings, as there was a tendency to split in several directions as soon as pressure mas applied; but enough was obtained to undertaltc quantitative determinations. They were found to consist of two portions—one attracted by the magnet, and the other not. By repeated separation the magnetic portion was found to be 94.44 per cent., and the non-magnetic 5.56 per cent. Analyses of these gave the following results: Magnetic Portion. Non-magnetic Portion. Percent, Percent. Graphite,.....3.480 Lime,. . 71.41 0 = 24.028 Combined carbon,. .. 0.260 Magnesia,. trace. Silicon,..... 2.790 Protox. of Phosphorus,.... 0.412 iron,. trace. Sulphur,.....0.292 Sulphide of Copper,.....0.110 caleium, 3.67 S= 1.72 0 = 3.440 Manganese,.... 0.500 -Iron (by dif.).,. .. . 91.206 27.468 --Silica,. 24 62 0 = 13.131 100.000 99.90

Jan 1, 1879

The oil production in Bahrein for the year 1937 was 7,762,264 bbl., a monthly average of 646,855 barrels. Sufficient potential production had been developed in the Second Pay (Main Pay) at Bahrein by the end of 1936 to supply the anticipated crude demand, and the drilling program was changed from straight development to partial exploration during 1937. Two nonproductive wells were drilled to test the Third Pay at a depth of about 2900 ft., or some 900 ft. below the top of Second Pay. As a result of this exploratory work, the normal drilling program was slowed down and only eight new wells were completed in the Second Pay during 1937, making a total of 45 producers from the Second Pay. The deep test was drilling at 5081 ft. at the end of the year. A 550-ft. section (termed Fourth Pay) of porous limestone interbedded with anhydrite was topped at about 4150 ft. Numerous drill-stem tests indicated that the limestone was very permeable and that it carried large volumes of natural gas under high pressure together with a small amount of high-gravity oil or condensate. Drill-stem tests also indicated that the bottom 50 ft. of the 550-ft. section carried an encouraging amount of heavier oil, gravity about 37" A.P.I., with characteristics similar to the oil produced from the Second Pay. A well was started somewhat down-structure from the deep test to better determine the oil-producing possibilities of the Fourth Pay. Some refinements in drilling technique were adopted during the year. All wells started to the Second Pay were drilled with rotary from the surface. The top 1500 ft. of porous limestone section, formerly drilled with cable tools, is now drilled with rotary without circulation, using water to wash the cuttings into cavities. The shale section from this point to the top of the oil horizons is drilled with natural mud circulation. The productive horizons are drilled with oil circulation under pressure control. A second satisfactory method of completing wells was developed when the two Third Pay test wells were plugged back and gun-perforated through cemented casing opposite the Second Pay, with good results.

Jan 1, 1938

IN welcoming the attending members of the Ameri-can Zinc Institute's Ninth Annual Meeting to St. Louis on April 18, the president of the Chamber of Commerce stressed the notable progress that had been made during nine years, marked by many price de-pressions and internal dissensions, while controversies between miners and smeltermen threatened to wreck the organization, prices dropped, and consumption grew languid for want of organized publicity and research. The reports and recommendations of Percy B. Butler, chairman of the Adjustment Committee, and F. C. Wallower, chairman of the Galvanizing Committee, might well be adopted as the institute's objectives. In reply to the speeches of welcome to St. Louis, Arthur Thacher reminded the delegates that the cor-ner stone of progress in the mineral industries was laid by the formation of the American Institute of Mining Engineers in Wilkes-Barre, Pa., in 1871, and the dedication of that organization to the exchange of ideas and methods of the winning of metals and non-metals from their crude state. The activities of the American Zinc Institute constitute, he said, a valuable phase of that work. Mr. Thacher forecast the treat-ment of 1 per cent zinc ore. After the reading of the report of the board of directors, in which Scott Turner and Louis Boschern were named as honorary members of the institute, a survey of world zinc conditions by A. J. M. Sharpe of London was presented. He held pres-ent conditions in China responsible for much of the present depression in zinc. World stocks on, April 1, 1927, were estimated as 52,900 metric tons. Adolph Boldt's paper on "Solidarity in Industry" was followed by a survey of the Tri-State district by Otto Ruhl, who emphasized the importance to the dis-trict of the organization of the Tri-State section of the A.I.M.E., which already has 135 members and asso¬ciates. He also mentioned .that flotation in the Tri¬State field is adding 1500 tons of concentrate to the weekly production. "Mining Economics" was the subject of Julian D. Conover, secretary of the Tri-State Zinc and Lead Ore Producers Association. He gave a detailed report on the costs of mining and milling in the district.

Jan 5, 1927

T. R. HARRISON, Washington, D. C. (written discussion). *-Mr. Kowalke shows that a high resistance millivoltmeter is subject to smaller errors, due to change in resistance of the thermocouple to which it is attached, than is a low-resistance instrument. He uses as examples instruments having resistances of 30 and 2 ohms, respectively. At the Bureau of Standards, resistances above 300 ohms would be considered high and 30 ohms rather low. In the tests on calorized-iron thermocouples, a difference between the first and third calibrations of the couples serves to show changes due to the intermediate heat treatment and only under certain conditions would changes in calibrations due to changes in the wire be detected by ,a recalibration after 1 1/2 in. had been cut from the hot-junction end of the couple and the ends rewelded. The calibration of a couple depends only on the thermoelectric prop-erties of that part of the couple which lies within the region of non-uniform temperature, i.e., the temperature gradient; hence, so long as the temperature gradient falls along wires of similar thermoelectric properties no change in the electromotive force is produced by altering the metals of those parts of the circuit that are at uniform temperature. Usually at the cold-junction end of the circuit, copper leads, brass binding posts, manganin resistance coils, and various other materials form part of the circuit, but so long as all are at a uniform temperature (or if for each junction between unlike metals there is a similar opposing junction at the same temperature) no resultant thermoelectromotive force will be produced thereby. Likewise, if a length of several inches at the hot-junction end of the couple is at uniform temperature, it matters not if this section is unlike other parts of the couple, so long as there is good metallic connection and no source of e.m.f. other than thermoelectric is present. Cutting off part of the hot end of the couple within such a region of uni-form temperature would not alter the e.m.f. of the couple.

Jan 12, 1919

This fund was established in 1929 for support of research and especially refers to non-ferrous mining and metallurgy. It is administered under the Board by a committee consisting of the President and Secretary and three members selected by the Board. HOWE MEMORIAL LECTURE The Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and outstanding attainment in the science and practice of iron and steel metallurgy or metallography, chosen by the Board of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectarers for the years indicated: Albert Sauveur—1924 Bradley Stoughton—1927 John A. Mathews—1925 Henry D. Hibbard—1928 William Campbell—1926 John Howe Hall.—1929 JOINT ACTIVITIES The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers, and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Society This is a corporation organized by the American Institute of Mining Engineers, American Society of Mechanical Engineers, and the American lnstitute of Electrical Engineers, to hold the title and administer the property at 29 West 39th St. In 1916, the American Society of Civil Engineers was admitted, and each society now has an equal one-fourth interest in the ownership, occupancy, and administration of the building. . The cost of this property has been over two million dollars. A. I. M. E. representatives are: Arthur S. Dwight, John V. N. Dorr and H. A. Guess. Alfred U. Flinn, Secretary, 29 West 39th St., New York City. Engineering Foundation This is a fund established by the United Engineering Society in 1915 with a gift of $200,000 from Ambrose Swasey. Subsequent gifts had increased the fund to about $620,000 on March 1, 1929. The income of the fund is used to further research in science and engineering and to advance the profession of engineering and the good of mankind. A research project in alloys of iron is being conducted in

Jan 1, 1929

By S. B. Sargent, V. J. Collins, Lester C. Uren

[The conclusions arrived at by authors in paper read before the Petroleum Division and the California Sections of the Americam Institute of Mining and MetallurgicaI Engineers and the Standardization Division of the American Petroleum Tnstitute, at a joint session held at Los Angeles, Cal., Jan. 21, 1926, are presented below.] From the theoretical discussion and experimental evidence presented in this paper, the following conclusions may be drawn: 1. The efficiency of the oil-well plunger pump is dependent to an important degree upon the submergence provided. 2. Ample submergence must be secured in order to provide sufficient static pressure to force the oil through the restrictions interposed in the oil path at the standing valve and at the plunger nut surrounding the garbutt rod. These restrictions should be no smaller than is structurally necessary, in order to reduce resistance to oil flow to a minimum. 3. A part of the static pressure developed below the standing valve by submerging the pump is dissipated in overcoming the inertia and in providing upward acceleration for oil left between the pump valves at the conclusion of the down-stroke of the plunger, and of oil below the standing valve in the gas anchor above the oil inlet. This loss in effective static pressure can be reduced to a minimum by dispensing with the garbutt rod and placing the working valve at the lower end of the plunger. The valves should be as near together at the conclusion of the down-stroke of the plunger as is consistent with security in avoiding striking of the lower end of the plunger on the standing-valve crown. Gas anchors should be short, and oil inlets should be as near the standing valve as is consistent with proper gas exclusion. 4. Because of the presence of gas in solution in the oil, which tends to escape from solution under the reduced pressure conditions above the standing valve, the effective length of stroke of the plunger is reduced, and the suction effect of the rising plunger is largely nullified. The influx of oil through the standing valve is therefore chiefly dependent on static pressure developed by submergence.

Jan 1, 1927

By W. T. Ober

the hammering effect acts only to a point 3 in. back from the cutting edge, and the hardening heat extends back only 1 in. from the cutting edge. Then, as a steel is taken from the fire, the grain condition is as shown in Fig. I. After the forging operation has been performed the condition shown by Fig. 2 exists. The heating operation to harden the cutting edge produces the effect shown in Fig. 3. The questions that naturally arise are: Will the cost of the extra heat treatment necessary to change this condition (annealing) be more than the saving that may be effected in the drill steel or will the extra heating be an economical as well as a wise thing to do? Is this condition necessarily detrimental to the maximum service of the drill steel? Can this annealing action be obtained in the hardening heat by heating more of the bit, say at least 5 in., to the hardening temperature but quenching only the end of the bit by a shallow immersion? Short Rock-drill Steels Reclaimed by Welding By W. T. Ober, Lynn, Mass. Experimental tests by the Thompson Company have shown that short lengths of rock-drill steels may be reclaimed by electric butt welding. The drills used in the experiments were hollow drills l1/4-in. in diametcr containing 0.95 per cent. to 1.05 per cent. carbon. The ends to be joined must first be ground off fairly square and the greater part of the rust, scale, etc. removed for 3 or 4 in. back in order to insure good electrical contact with the dies of the welder and countersunk, with an 80° countersink, approximately 1/4 in. The steels are then clamped in the copper dies of the welder, so that a length projects from the inside edge of each pair of dies equivalent to from one-half to three-quarters the diameter of the drill. The drills should also be brought into accurate alignment. The first step is to bring the ends into close proximity and then close the primary circuit of the transformer, slowly bringing the steels together until their ends lightly touch, when they will "flash," that is, minute

Jan 1, 1922

By Henry M. Howe

If a bar of wrought iron or steel is suddenly cooled from a bright red-heat, the contraction which then occurs is considerably greater than the expansion previously caused by heating the bar, so that its final length is considerably less than its initial length. Mr. Thomas Wrightson has investigated this phenomenon,* and has shown that not only does this permanent contraction occur on sudden cooling, but, if the heating and cooling be repeated, say fifty times, a further permanent contraction occurs at each successive cooling. In Mr. Wrightson's opinion, this contraction cannot be explained on mechanical grounds, and he ascribes it to some molecular change caused by sudden cooling; but I think that we need not invoke mysterious molecular changes to explain this phenomenon, which appears to me to be due to very simple and purely mechanical action. Let us consider the cooling as divided into two periods, in the first of which the exterior or skin of the bar becomes almost completely cooled, and hence tends to contract almost to its initial dimensions, while the still hot arid plastic interior contracts but little; in the second period the already cool skin remains nearly constant in temperature, and hence tends to contract but little, while the interior cools from a comparatively high temperature to the ordinary temperature, and hence undergoes great contraction. The excess of the contraction of the skin over that of the interior during the first period tends to make the bar bulge in the middle of its length. This, as well as the decrease of density which occurs, Mr. Wrightson correctly explains. The interior of the bar just sufficed to fill the skin when both were in their initial condition, before being heated at all. At the end of the first period, the volume of the still hot interior is more than the now contracted skin can hold while maintaining its initial shape; and the effect is much the same as when we powerfully blom into a soft India-rubher Lag of the shape of the skin of the bar—it bulges, and tends to approach the spherical shape, in which the ratio of surface to

Jan 1, 1886

By C. R. Boyd

The sulphuretted ores of Carroll and Grayson Counties, Va., Ore Knob, Ashe County, N. C., and Ducktown, Tenn., in their general position, are in the prolongation of the same massive deposits. The existence of the extensive ore-bodies has been well-established, not only in a practical way, but by the careful research of a number of men of science, including Dr. T. S. Hunt, Professor Kerr, Dr. Genth, Rogers, Safford, Professor Egleston, Dr. H. E. Colton, the writer, and others, and described in one or more of the volumes of our Transactions, as well as in other publications. The greater quantity of' these ores being pyrrhotite, although much of them carry nonmagnetic disulphide, their reduction on the gronnd will probably lead to better results than an attempt to mine and ship them to distant places; and their use as sulphuric acid producers, to be employed in the cheap manufacture of valuable fertilizers, will be chiefly the subject of this paper. The great deposits of Carroll County, Va., are now nearer to railway transportation than any of the others, being six to eight miles from the Cripple Creek extension of the Norfolk and Western Railway, now being constructed, the grading of which is in an advanced state of completion. I am not able to state what are the present prospects of an early completion of the contemplated line of railway to Ducktown. For a long while, during the time those deposits were mined and reduced for their copper, the works were forty miles from any railway ; and the same may be said of Ore Knob, N. C. The deposits in Carroll and Grayson Counties, Va., being now the most accessible to cheap transportation, will naturally claim the greater part of our attention ; though it may be pertinent to remark, just here, that the ores of Ducktown, like those of Carroll and Grayson, Va., exist in the undecomposed levels as iron and copper sulphurets, much of which is a non-magnetic disulphide, as stated, with occasional exhibits of sulphides, such as covellite, erubescite, etc. There are, now and then, small quantities of silver, lead, and zinc,

Jan 1, 1886

By W. T. Ober

the hammering effect acts only to a point 3 in. back from the cutting edge, and the hardening heat extends back only 1 in. from the cutting edge. Then, as a steel is taken from the fire, the grain condition is as shown in Fig. I. After the forging operation has been performed the condition shown by Fig. 2 exists. The heating operation to harden the cutting edge produces the effect shown in Fig. 3. The questions that naturally arise are: Will the cost of the extra heat treatment necessary to change this condition (annealing) be more than the saving that may be effected in the drill steel or will the extra heating be an economical as well as a wise thing to do? Is this condition necessarily detrimental to the maximum service of the drill steel? Can this annealing action be obtained in the hardening heat by heating more of the bit, say at least 5 in., to the hardening temperature but quenching only the end of the bit by a shallow immersion? Short Rock-drill Steels Reclaimed by Welding By W. T. Ober, Lynn, Mass. Experimental tests by the Thompson Company have shown that short lengths of rock-drill steels may be reclaimed by electric butt welding. The drills used in the experiments were hollow drills l1/4-in. in diametcr containing 0.95 per cent. to 1.05 per cent. carbon. The ends to be joined must first be ground off fairly square and the greater part of the rust, scale, etc. removed for 3 or 4 in. back in order to insure good electrical contact with the dies of the welder and countersunk, with an 80° countersink, approximately 1/4 in. The steels are then clamped in the copper dies of the welder, so that a length projects from the inside edge of each pair of dies equivalent to from one-half to three-quarters the diameter of the drill. The drills should also be brought into accurate alignment. The first step is to bring the ends into close proximity and then close the primary circuit of the transformer, slowly bringing the steels together until their ends lightly touch, when they will "flash," that is, minute

Jan 1, 1922

CONTENTS PAGE UREN, LESTER C.-Increasing Production of Petroleum by Increasing Diameter of Wells. Discussed by A. Beeby Thompson 1 LAHEE, FREDERIC H.-Comparative Study of Well Logs on the Mexia Type of Structure. Discussed by W. A. I. M. van Waterschoot van -der Gracht.... 4 Increasing Production of Petroleum by Increasing Diameter of Wells Discussion of the paper of LESTER C. UREN, presented at the New York Meeting, February, 1925, and issued, as Paper No. 1364-G, with MINING AND METAL-LURGY, October, 1924. A. BEEBY THOMPSON, London, Eng. (written discussion).-The subject discussed in this paper has long been debated by operators in European fields, where very strong views are held regarding the advisability of controlling gas pressures by shutting in wells. While unwilling to theorize on the subject of restricted flow, the writer has always been disposed to associate himself with those who hesitate to impose any obstruction to a natural transitory state that breaks up the oil-containing strata and establishes a feeder system which no subsequent events, natural or artificial, can approach in intensity. In both Russia and Roumania, where the oil is concentrated in discontinuous, disturbed, and irregular lenticles of sand varying, within short distances, in coarseness of grain, extent of impregnation and degree of cementation, it has been the practice to let the wells run wild in order to provoke disruption of strata. By encouraging violent eruptions, an extended feeder system is created and the ejection of enormous quantities of sand, rock, and clay creates a sump and seepage area that it would be difficult to imitate by any artificial means, not excluding actual mining. Before discussing the somewhat novel method suggested for enlarging the infiltration area, the writer would like to confirm the fact that many valuable data applicable to oil are forthcoming from a study of water phenomena. Long association with water-supply problems in many parts of the world has shown how closely the phenomena of underground movements of water and oil are related, so that it is pleasing to note the author's use of water formulas. But there is one great distinction;

Jan 7, 1925

IN discussing the art of the goldsmith, it is apparent that it is an art requiring skill. He who wishes to be acclaimed a good master therein must be a good universal master in several arts, for the different kinds of work that come to his hands to be done are infinite. Those who work in gold and silver must outdistance all other craftsmen in learning and achievement to the same degree that their materials outdistance other metals in nobility. Therefore, it is necessary first of all to be a good designer, because design is the key that opens the doors not only to the goldsmith's craft but to all others. Then it is necessary that he understand melting and that he know well how to work with a hammer and how to use flat gravers and burins in engraving, as well as files and chisels. He must also possess certain secrets that are needful to the art, which in truth are parts of alchemy, such as softening gold when it is brittle and raw, coloring it when it has little color, soldering, enameling, working in niello, blanching, gilding, and an infinite number of things which must all be known in detail. But above all he who wishes to do this art well must be very patient in working, must know how to mould and how to proceed with the melt and with the file, hammer, chisel, or other implements for bringing his gold or silver work to the final state which he plans. He must also have good judgment in gems and know well how to recognize every [134v] good or defective quality they possess, and to distinguish the false gem from the true, either when set or when unmounted, as there is need; also how to value them both in buying or selling and in satisfying others who seek his appraisal. He should also be experienced not only in the technique of melting but also in the methods of assaying, parting, refining, cementing, and the like, and still many others. But if I wished to tell you of every part

Jan 1, 1942

By R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, 'pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.' However, the components which are strongest in the recrystallization texture are in this range.'________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,' 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.'~-'~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.' In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2'13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,'~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.' state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By Henry R. Linden

The demand for natural gas continues to increase at higher than anticipated rates, partly because of its widening price advantage over most other fossil fuels when the cost of air-pollution control is included. However, there are clear indications that the natural gas supply from the conliguous 48 states and continental shelves will not keep up with this rapid growth in demand indefinitely. Projections are presented which define the extent of potential deficiencies from the 1970's to the year 2000. Among the sources of supplemental gas - imported pipeline natural gas from Canada and Mexico, tanker import of liquefied natural gas, and synthetic pipeline gas from coal and oil shale -by far the most abundant at potentially competitive costs is pipeline gas from coal. The state of development and relative economics of the various coal gasification processes are reviewed. It is shown that synthetic pipeline gas could become a very substantial market for bituminous coal and lignite at current mine-mouth prices - 60-70 million tons of coal for each trillion cubic feet of synthetic pipeline gas produced. This corresponds to only slightly more than the current annual increase in gas demand. Although annual discoveries (gross additions to proved reserves) of natural gas in the United States are still on a general upward trend from the current level of 22 trillion cu ft annually, most forecasters do not expect this to increase substantially in the foreseeable future. For example, the updated (to include 1966 and 1967 data) mathematical model of natural gas discovery and production in the U.S. developed by the Institute of Gas Technology (IGT)' projects that discoveries will level out at about 25 trillion cu ft annually in the late 1970's and during the 1980's and then decline to about 21 trillion cu ft by the year 2000 (Fig. 1). This adds up to a new supply for the period 1968-2000 of about 790 trillion cu ft. Experts who usually reflect the producers' viewpoint, such as Radford L. Schantz of Foster Associates,* are relatively more pessimistic. In contrast, a forecast just made by the U.S. Dept. of the Interior is much more optimistic.3 It assumes an increase in gas discoveries of 2.2% per year over the period 1965-80, reaching about 30 trillion cu ft in 1980. If this rate of increase were extended to the year 2000, annual discoveries would reach 46 trillion cu ft at that time, for a total over the period 1968-2000 of about 1100 trillion cu ft. To these forecasts of new gas discoveries must be added proved reserves of roughly 290 trillion cu ft,4 bringing total U.S. supplies for the rest of the century to nearly 1100 trillion cu ft (IGT) and possibly as high as 1400 trillion cu ft (U.S. Dept. of the Interior). This is approximately the same range as that of two estimates of total remaining recoverable natural gas supply: Potential Gas Committee, 980 trillion cu ft5 and IGT, 1450 trillion cu ft.6 Only the 1965 estimate by the U.S. Geological Survey7 suggests that economically recoverable natural gas supplies will not be exhausted around the end of the century. These forecasts are, naturally, based on the assumption that changes in technological, economic, and regulatory environment as they affect the gas industry will be of an evolutionary, not revolutionary, nature. The various forecasts of potential natural gas supply must now be compared to forecasts of natural gas demand (Table I). The general consensus is that the recent Future Requirements Committee projection to 1990' (extended to the year 2000 by the most recent U.S. Bureau of Mines (USBM) projection9) represents the minimum gas requirements (Table 11). They add up to a total of 1030 trillion cu ft for the period 1968-2000. Even this minimum anticipated gas demand exceeds the total remaining supply estimate by the Potential Gas Committee and would nearly exhaust the proved reserves plus new discoveries projected by IGT. The supply situation would appear much tighter if the demand projections of the Texas Eastern Transmission Gorp.10 and the American Gas Assn.(A.GA.)'' were used (Table I). Yet, these higher forecasts probably do not include the effects of such new markets as gas fuel cells, use of liquefied natural gas as a transport fuel, etc. They also may not fully reflect the impact of air quality control on the fuel market. Obviously, the probable discrepancy between projected supply and demand can only be accommodated in four ways. 1) Rapid increase in exploration and drilling activity to provide new supplies in the amount projected by the optimistic U.S. Dept. of the Interior forecast, coupled with an increase in net pipeline imports from Canada and Mexico from the present 0.5 trillion cu ft per year

Jan 1, 1970

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones' studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.' Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:'-' the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis' developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By Eugene S. Machlin

A classical theory of solid solutions involving neavest-nergkbor intevactions with both central and linked-central forces between atoms has been developed. It has been found that the theory, where it can be checked quantitatively, is in ageement with experiment. The theory encompasses a description of many diverse pkenomena, such as antiphase shift structures, size effect, relative stabilities of various solutions, lattice para,neters, and order-disorder transitions. In particulav. a quantitative prediction not involving adjustable pavameters is made concevning the deviation of the Au-Cu interatonlic distance in long-range ordered (Ll,) Cu-Au I fronl the average distance based on the distances in pure gold and copper. This prediction, which is in agreement with expel-intent, has not been encompassed by any preuious theory. The theory of order-disorder is fragmentary. That is, no one theory exists that can explain the variety of qualitative phenomena observed. Further, many theories are not in good quantitative agreement with experiment. This subject has been reviewed by Muto and Takagi, Tuttman, and Oriani.3 There exists no doubt that the quasi-chemical approximation is not a complete description and that the inclusion of strain energy using macroscopic elasticity theory concepts leads to results in disagreement with experimenL4 The observation of antiphase domains and ordering systems such as Cu-Pt has led to Brillouin zone treat-ment of the order-disorder transition as opposed to the classical Ising model. The objective of this paper is to demonstrate that it is possible to develop a pairwise approximation model that can explain many of the observed order-disorder phenomena that have puzzled investigators in the past. This theory is based upon an empirical model due to ergmman' for the elastic constants of metals. This model is generalized for multicomponent systems. As will be shown, the theory yields a short-range ordering energy for the disordered solution which differs from the ordering energy calculated from the differences in energy of disordered and long-range ordered solutions. It will be demonstrated that there is no necessary correlation between heats of formation and the tendency to order or between size effect and the tendency to order. Also, the existence of antiphase domains and iso-short-range-order systems that form superlattices (Cu-Pt) is predicted on the basis of the theory. Further, the relative stability of competing superlattices is calculable from the theory. If single-crystal elastic-moduli data are available for the pure components and one superlattice then there exists but one adjustable parameter in the calculation of lattice parameters for both the disordered and ordered solid solutions. In one special case, no adjustable parameters are required and a quantitative prediction is made. For the calculation of energies and partial order, there exists but one additional adjustable parameter, the pair-exchange energy V used in the quasi-chemical approximation (or the Ising model.) However, in these calculations, much more precise values are required for the single-crystal elastic moduli than available if the quantitative uncertainties in the predicted values of the energies are to be sufficiently small. THEORY ~er~man' has developed a model with which he was able to obtain fair agreement with experiment for the relations between the elastic constants for metals. This model which we shall call Bergman's model is a linear combination of his models I and 11. In effect, Bergman, in this model, considers that each interatomic distortion is composed of two components: a classical central force distortion with an associated central force constant and what we shall call a linked-central force distortion with an associated linked central-force constant. The linked-central force distortion component obeys the constraint that the sum of such distortions over all the bonds equals zero. No constraint is imposed on the classical central force distortion component. Bergman' derives the constraint on the linked-central force distortion on the basis of application of Pauling's relation between bond distortion and bond number to metals.ga This assumption is not logically necessary, however, and the Bergman model may be taken as a mathematical model for elastic constants, e.g., a purely empirical model without a physical basis. In the present work, the method of Bergman has been applied to two-component systems (solid solutions). In place of an external strain—which would allow a calculation of the elastic constants for the two-component system—it is considered that internal interatomic distortions exist as a consequence of having three potentially unequal distortion-free interatomic distances and but one "average" interatomic distance. It is assumed that the distortion-free interatomic distances between atoms of the same element are those found in the pure element having the same undistorted crystal structure as the solid solution. The distortion-free interatomic distance between unlike atoms is in general not measurable except in the probably nonexistent

Jan 1, 1967

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.&apos; The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965