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By Oliver C. Ralston

THE two chemical compounds, natural sodium carbonate and sodium sulphate, in their anhydrous condition are dealt in as "soda ash and "salt cake”-names from an earlier day that are not as precise as the present accepted terminology. Once a large part of the sodium carbonate recovered was in the ash of seaweed, so it was logically called soda ash, and the corresponding potassium carbonate, once mainly recovered from wood ashes, was called potash. The term "salt cake" was applied to the sodium sulphate resulting from interaction of sodium chloride with sulphuric acid or sodium bisulphate, to form hydrogen chloride gas and an anhydrous cake of sodium sulphate. It was called "salt cake" and also "glassmaker's salt cake" because much of it was used in the production of glass. The two salts occur in nature in a variety of forms, but whereas an- hydrous sodium sulphate (thenardite) is fairly common, the anhydrous normal sodium carbonate, Na2CO3, is almost never found in nature. The monohydrate (thermonatrite), Na2CO3.2H2O, is seen occasionally, but it is never a major constituent in natural "soda" deposits. The high solubility of normal sodium carbonate is one reason for this. While both compounds occur widely in brines, the solid salts found in nature are usually trona (Na2CO3.NaHC03.2H2O) and thenardite (Na2SO4). The natural brines containing workable quantities of the two sodium salts are largely found in the arid and semiarid portions of the western United States and other countries. The classical discussion of the resources of these brines are those of Clarke,5 Chatard.4 Packard,19 Gale,11 and Wells.28 From North Dakota to California and from Arizona to the Canadian provinces of Alberta and Manitoba, saline lakes, dried-up lakes, playas, and similar land-locked depressions contain accumulations of saline matter. Sodium chloride is the predominant salt but some of the lakes contain predominantly either sodium carbonate or sodium sulphate. Often sodium carbonate

Jan 1, 1949

Jan 1, 1949

By Richard P. Schoemaker

Introduction In underground mining operations the effects of economic and mechanical factors on costs and profits can readily be appreciated and can perhaps be expressed in exact figures and percentages. Less apparent, but frequently more important, is the influence of physical stress. Stress causes failure of supports, collapse of openings, rockbursts, and other damage which directly affects the costs of maintenance, and also to a certain extent the accident rate. Stress can, however, if properly directed, be an aid to mining operations. The caving methods in metal mining and the long-wall method in coal mining are well-known examples. In large-scale mining operations it is almost impossible to neglect stress-control. A better understanding of the mechanism of rock pressure and the application of its principles to practical mining will inevitably lead to a reduction in operating costs. Many theories have been advanced to give the mining engineer a practical outline for stress-control but, although today most experts agree upon the principles of stress distribution around underground openings, there is still no generally accepted theory that explains all phenomena. The main reasons for this incomplete understanding of the problem are the lack of accurate knowledge of the physical properties of rocks under field conditions, and the great complexity of these conditions due to in-homogeneity of the rock, stratification, tectonic disturbances, and many other unknown factors. The research on the rock pressure problems has, however, yielded some valuable facts which, expressed in practical terms, and adapted to local conditions, may become a valuable aid for mining operations. The purpose of this paper is to give a review of the most important accomplishments of this research with respect to the stress phenomena around small underground openings, such as tunnels and shafts, so as to arrive at an outline of the problem as it stands today. Special emphasis is placed on a new theory by the German mining engineer, Rudolf Fenner, which has never before been published or discussed in English. The Pressure Dome Theory The formation of a dome-shaped space around underground openings is well known from field observations. When openings are made in rock under stress, the rock in the top of the openings will often fail, and caving will continue until the openings have assumed a dome-shaped form, after which equilibrium apparently is re-established. The oldest theory which attempted to explain the phenomenon is the "beam" theory, which postulates that the hanging wall consists of stratified measures that behave as independent beams with fixed ends and a uniformly distributed load. When failure of the beam occurs, inward shearing at the ends will cause the formation of a dome-shaped space. The pressure dome theory, which more or less evolved from the beam theory, merely

Jan 1, 1949

By G. L. Kothny

Developments of well-surveying instruments, coring .and core orientation, were in an advanced state when drilling for oil began—these developments actually originated with the mining industry.' Surveying of oil wells was not generally used in the United States until Alexander Anderson2 disclosed that the majority of wells drilled with rotary tools were crooked, with average horizontal drifts of about 516 ft. for holes 5000 ft. deep and about 793 ft. for holes 6000 ft. deep. This disclosure brought about the development of many additional instruments for surveying oil wells during the progress of drilling and after their completion. Surveying of boreholes, during the process of drilling at regular depth intervals, became a standard practice in the petroleum industry. Some producing states even established laws making check surveys mandatory, during drilling and under certain conditions also after completion. The surveying of boreholes also brought about changes and improvements in drilling practices. It provides information for the guidance of the hole while drilling, and for plotting the course as the work progresses, enabling the driller to take corrective measures immediately and with the least expense. The reasons for drilling straight holes are too well recognized to warrant any full discussion of them here. Straight holes are less costly to drill, because they reach the object on the shortest course. Table I shows the horizontal drift and loss in vertical depth for various angles of inclination. It is not surprising, therefore that many drilling contracts for oil wells today limit the drilling contractor to a maximum inclination off the vertical of 2° or 3O. In the mining industry the reasons for drilling straight holes are still more serious. A crooked hole may miss an ore body underground or provide incorrect information regarding an ore body. Types of Surveying Instruments The surveying instruments used in oil-well drilling may be classed in two types: I. Inclinometers, recording inclination only.

Jan 1, 1949

By J. J. Lander, L. H. Germer

Molybdenum and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved onlv limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150°C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1949

By M. B. Willey

The Louisiana Continental Shelf is a submarine area extending offshore as much as one hundred miles. The Gulf bottom in this region varies considerably in extent, profile and composition and consists largely of sedimentary deposits, predominantly those of the Mississippi River. It is very young in a geological sense. Up to the present time few major structures have been erected offshore in the Gulf and no comprehensive preliminary tests have been carried out. Results of pile driving tests are of little value as actual bearing capacities far exceed the dynamic resistance to driving as measured by conventional formulas. Soils encountered are, with few exceptions, cohesive and piling consequently develop their supporting power through surface friction. Because of the time required and relatively high costs, no complete load tests have been made. The results of those tests which have been made, and information obtained from pulling piling in one structure, indicate that design loadings could be considerably increased, and it is contended that comprehensive preliminary investigations including an actual load test, combined with borings and examination of materials encountered by competent soil experts, would effect economies in design far in excess of their cost. The Louisiana Continental Shelf—General The Louisiana . . . continental shelf is a submarine area which extends seaward for as great a distance as one hundred miles off the present shoreline. The Gulf bottom in this region is characterized by low slopes and its outer margin is outlined by the fifty fathom (300 ft.) contour. South of the margin of the shelf the slopes steepen abruptly in the continental slope zone and plunge into the deeps of the Gulf of Mexico.l The engineer who is called upon to design a structure on this shelf is concerned only with the uppermost portion to a depth generally not to exceed Ioo to 150 ft. This layer is very young in a geological sense, and it has the characteristics usually associated with infancy. A few of these are lack of strength, lack of uniformity, and high water content. It consists of the sedimentary deposits of the various rivers and streams entering the Gulf. These streams are all heavily burdened in quantities sufficient to fill the areas at their mouths, were it not for the fact that continual subsidence, equal or greater in amount and acting directly opposite, prevail over the sedimentary workings of the streams. This subsidence has been estimated by geologists to be at the rate of at least one foot per century. Influence of Mississippi River The Mississippi River, which has been the predominant factor in the formation of practically all the Louisiana continental shelf, is one of two rivers flowing into the Gulf that have been able to build protruding deltas. The Mississippi has done so because of its enormous size and load. It deposits sediments in amounts sufficient to replace and actually gain on the amount of subsidence.

Jan 1, 1949

By A. B. Clayton

The Bumpus Cove area is in Unicoi County, Tenn., about 9 miles south of Jonesboro and 5 miles northwest of Erwin. Iron and lead ores were mined in the Bumpus Cove area before the American Revolution. The production of those metals continued intermittently until 1916. In 1850 this area was the most important producer of iron in the South. In 1911 several carloads of zinc ore was recovered from old dumps and shipped to Missouri smelters. In 1913 systematic mining of zinc ores was begun and continued until 1916. After that year, mining again became sporadic and continued so until discontinued in 1943.

Jan 1, 1949

By J. L. Bruce, G. W. Nicolson

ThE country rock of the Mavrovouni mine of the Cyprus Mines Corp. is hydro-thern~ally altered, disintegrated pillow lava, with very little tensile strength ("short" ground). In places, especially when wet, it is heavy ground, though not extremely heavy except where movement has been caused by underlying or nearby stoping operations. Damage by caving from roof or sides of galleries is not sudden but progressively faster when the size of the cave increases as a result of the fall of small pieces. CeMent and Concrete Linings During early operations, galleries in the country rock were supported by customary mine-timbering methods. Available timber, howcver, was of poor quality and of relatively high price, and replacements were frequent and expensive. Furthermore, the massive sulphide ore bodies required large volumes of fresh air for ventilation and cooling, and it was therefore desirable to provide smooth-lined galleries with low resistance for the introduction of air to the ore bodies. It was also desirable to eliminate hazards of fire in shafts and underground workings insofar as this would be practical. Cement and concrete were relatively cheap, and plans for using these in support of shafts, underground galleries, raises, and chutes, were developed steadily. Circular shafts with diameters ranging from 10 to 15 ft were adopted for all permanent shafts and airways. In places these were lined with concrete poured behind sectional pressed-steel forms especially constructed for this purpose. In other places, they were lined with precast-concrete blocks. It was found that such precast concrete of good quality could be produced on mass production scale and delivered at the mine from most favorable point of manufacture, at a cost of about 25 cents per cubic foot of concrete. This refers to prewar costs. As the use of concrete blocks in circular lined galleries was developed, it was found that there were very great advantages in the reduction of air resistance as compared with customary timber supports. After best methods had been developed, it was found that breakage and replacements were extraordinarily low, averaging only about 11\2 pct per year during a period of about 15 years. Furthermore, it has been possible to reclaim for re-use a very large percentage of the concrete blocks from abandoned galleries. During the history of the operations precast-concrete blocks have been used for lining shafts, raises, ore chutes, galleries, and shaft stations, ranging from 3 to 16 ft id. The thickness of lining has varied from 5 to 10 in.; with 12 in. thickness in a few cases. Junctions of two galleries at angles ranging from about 30 to 60° are usually made of poured concrete behind sectional forms, or of a combination of poured concretc and precast blocks. In nearly all cases it has been found advisable to make the point of the wedge at the junction, of

Jan 1, 1949

By C. E. Sims, G. A. Moore

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By C. P. Besse, G. W. Osborne

Drilling operations on the Gulf of Mexico continental shelf are following two general plans. The first plan placed all buildings. equipment, and materials on a large platform while the second copies Lake Maracaibo drilling methods by placing a minimum of equipment on the platform and using a floating drilling tender or drill barge anchored adjacent to the platform in an attempt to take maximum advantage of flotation in an effort to reduce costs. A complete power rig, mud pits, pipe racks, and small auxiliaries have been placed on the platform as shown in Figure 1, to assure proper handling of drilling operations under the most adverse weather. This has the economic advantages of eliminating the fabrication of a large structure, a material reduction of rigging up time on each structure. and elimination of delay time on equipment while quarters and equipment placed on the tender are being rigged up. These factors have certainly proved their economic value in drill barge operations in the Louisiana and Texas coastal area. Naturally the heart of such an operation is the anchorage. This anchorage, to permit taking advantage of maximum economies. must hold the ship in a relatively fixed position under the following weather conditions: (1) Winter northwesters (2) Southeasterly gales (3) Severe rain squalls In hurricane weather all operations must be suspended regardless of method of operation and the floating tender will, if possible, be moved to a protected location. However, in case of an emergency the floating tender should be prepared to swing with the wind and seas on a single anchor as there is considerable doubt that either ship or anchorage could withstand the severe strains imposed by fixed anchorage in hurricane weather. Northwesters are reported to have developed wind gust velocities as high as sixty miles per hour and steady winds of approximately forty-five miles per hour. Fortunately these winds do not travel a great distance over water before arriving at our location, and, while they can possibly develop seas approximately eight feet high, the waves are short, and if taken on the bow or stern of a ship 250 feet or more in length they should not present a difficult problem. On the other hand southeast gales having a long fetch and maximum steady wind velocities of approximately thirty miles per hour can possibly develop long swells approximately twelve feet in height. These should develop the most severe anchorage problem. To combat these waves any workable anchorage plan should permit maneuvering the ship in such a manner as to head the bow or the stern into the seas and still maintain contact with the structure. Rain squalls develop wind gust velocities as great as sixty miles per hour. However, they are local and the seas have not been a source of great trouble. To permit continuous operation the anchorage must be able to withstand these winds broadside to the ship as the wind direction often changes radically in a very sliort time. All of these weather conditions are dangerous to small craft, deck cargoes,

Jan 1, 1949

By Burton H. Boyum

Greater depth of exploration drill holes and increasing cost of drilling have been principal factors in reviving interest on the Mar-quette Iron Range in controlled directional drill-hole deflection. This deflection is obtained by the application of the Hall-Row wedging technique. Modifications were made in the technique and equipment in the effort to simplify and strengthen the procedure. The practice is similar in many respects to the oil well type of deflection with a whipstock. Introduction The deflection of diamond drill holes by wedging was a widespread practice in Canada, South Africa and the Lake Superior District as early as 1907 to 1920. Several basic schemes were used, with local variations.' The deflecting wedge assembly was the idea of Mr. Welldon and Mr. Payne-Gallwey operating under the supervision of Mr. William Gallagher of Johannesburg, South Africa. All schemes employed some means of plugging the old hole. A footpiece of various styles was placed in the hole on the plug. In some methods, the orientation of this piece was determined before placing the deflecting wedge. Some techniques permitted continuing the hole the same size after wedging, while others necessitated a size reduction. Interest in wedging diamond drill holes in the Lake Superior District waned after 1920. The Hall-Row patented system for deflecting holes was developed in Canada about 1918.2 Interest centers on the wedging process for the following applications: 1. Maintaining a given course and inclination of the drill hole. 2. By passing an obstruction in a drill hole. 3. Resampling an ore body. 4. Exploring an area overlain by surface conditions not favorable to drilling. During the period of 1913 to 1920, The Cleveland-Cliffs Iron Co. used the wedging technique under a variety of conditions. In general, the practice was not applicable again until 1946. Meanwhile the Hall-Row system of drill-hole deflection survived years of application as the best technique available. In the intervening years, our depth of exploration has increased as well as the overall cost of drilling. As exploration becomes deeper, there is the possible economy of cutting the ore body at a moderate distance from the parent hole without redrilling from surface. Thus a branch hole started near the mid-point of a deep hole can reach the ore horizon at a considerable offset from the parent hole. This permits a greater interval between surface drill holes as drilling becomes deeper. Our interest revived in the subject and a wedging program was initiated. General Description Results The maximum theoretical angular deflection possible, based on the deflecting

Jan 1, 1949

By Boyd Guthrie, J. D. Lankford

A progress report on the oil-shale and shale-oil processing research program at the U. s. Bureau of Mines Oil-Shale Demonstration Plant. Legislation providing for the program and aims are briefly noted. The remoteness and rugged nature of the terrain at the plant site are important factors in construction and operations. Large-scale units now in operation are the crushing plant and two 40-ton N-T-U retorts. These are described in detail. Under construction are several retorting pilot plants and a 200 bbl per day refinery. The refineiy incorporates several types of thermal operation, three-stage low-temperature acid treating, doctor sweetening and rerunning. Data are presented on typical N-T-U retort runs. Yields of 90 to loo pct of assay are realized on 30 gal to the ton shale with a retort cycle time of 18 hr. Data also are presented showing a comparison of a Mid-Continent petroleum and N-T-U shale oil. This comparison indicates that shale oil has a high pour point, low API gravity, and contains about 0.8 pct sulphur and 2 pct nitrogen. The naphtha fraction contains 3 pct tar acids, 9 pct tar bases and jo pct olefins. The problems involved in refining shale oil into usable products are discussed in detail. Introduction The Bureau of Mines oil-shale program now under way at Rifle, Colo., was begun in July 1944 under the provisions of the Synthetic Liquid Fuels Act, which was passed in the spring of that year under the sponsorship of Senator Joseph C. O'Ma-honey of Wyoming and Congressman Jennings Randolph of West Virginia, aided by Michael W. Straus, former Assistant Secretary of the Interior, and others. The oil-shale plant is only a part of the Office of Synthetic Liquid Fuels, Bureau of Mines, which has under way projects to develop synthetic liquid fuels from coal and other solid materials at Pittsburgh and Bruceton, Pa., Morgantown, W. Va., Louisiana, Mo., as well as the Petroleum and Oil-Shale Experiment Station at Laramie, Wyo., and the oil-shale demonstration plant at Rifle. The oil-shale program is entirely experimental. It is not intended that oil will be produced in great quantities. Production will be limited to the volume obtained from plant-scale experimental operations, which will be kept to the minimum size needed to develop techniques and processes and to demonstrate costs. After the passage of the enabling act in the summer of 1944 a survey of the oil-shale resources of the Nation was made to determine the most suitable general area in which to establish the demonstration plant. The most suitable area was found to be in the Rifle-De Bequearea in Garfield County, western Colorado. Bureau of Mines field parties covered this entire area thoroughly

Jan 1, 1949

PRESIDENT L E Young', Pittsburgh, Pa PAST PRESIDENTS Clyde Williams, Columbus, Ohio W. E Wrather, Washington, D C VICE-PRESIDENTS Robert W Thomas', Ray, Ariz C Harry Benedict, Lake Linden, Mich D H McLaughlin, San Francisco, Calif A B Kinzel, New York, N Y Philip Kraft, New York, N Y VICE-PRESIDENT AND TREASURER Andrew Fletcher, New York, N Y

Jan 1, 1949

By W. W. Agey

As a result of a field examination made during the Bureau of Mines intensive manganese program, three lots of ore were procured from the famous old Paymaster District, 7 miles from Midway Wells, Imperial County, Calif. This district is an old producer and shipped approximately 10,000 tons of 45-percent manganese ore during World War I. A 2-ton lot of ore was taken of a Bureau engineer from the exposure of a small fissure vein in conglomerate on the Turtle Group of claims; 1 mile east of the Pacific Coast Manganese Corp. claims. The vein material consisted of manganese oxides, calcite, and quartz in fairly coarse association.

Jan 1, 1949

By Frank R. Milliken

This paper is a running commentary on metallurgical problems and developments, stressing ilmenite flotation, since the start of operations five years ago, at the mill of National Lead Company, Titanium Division, MacIntyre Development, Tahawus, New York. In early 1941, when world conditions threatened to cut off the supply of ilmenite (obtained largely from India) to this country, the National Lead Company started to develop and bring into production their MacIntyre Development. This operation supplied the bulk of the ilmenite used during the war period for the manufacture of the much needed titanium pigments. MacIntyre Development is at Tahawus, New York, on the headwaters of the Hud- son River in the center of the scenic Adirondack Mountains. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. Operating tonnages and production have increased since 1943, however. Nearly 10,000 tons of.ore and waste is broken and loaded daily in the open-pit mine. About half of this tonnage is ore, from which is produced nearly 800 tons of ilmenite concentrate and 1600 tons of magnetite concentrate daily. Ore—types From an ore-dressing standpoint, there are five rather distinct ore types and two waste-rock types in the mine. The ore types are shown in Table I. The anorthosite waste is a coarse-grained white rock, largely labradorite feldspar. The gabbro waste is generally finer grained, and contains, in addition to feldspar, 35 to 75 pct iron silicates such as hornblende, in garnet and biotite. A minor mineral mineralogically, but important metallurgically, is apatite. A few calcite

Jan 1, 1949

By H. S. Kalish, F. J. Dunkerley

Introduction and Previous Work THE determination of the low temperature tensile properties of tin and tin-lead alloys was initiated as part of an extensive research program on the phasial equilibria of tin binary systems below 13.2°C and the property changes associated therewith. A survey of the literature revealed that, although some room temperature tensile data were available for tin and a few tin-lead alloys, there existed no survey report of the low tcmPerature tensile properties of these alloys. Accordingly, the tensile data for tin and a series of pure tin alloys containing from 0.01 to 50 pet lead were measured at eleven temperatures horn — 196 to +20°C and are presented here in survey form. In addition to the importance of these tensile data as a preliminary to certain fundamental research, this information promises also to be of commercial importance because of the extensive use now being made of tin-lead solders in refrigeration and gas liquefaction equipment. Occasional failures of the solders in low temperature service have been attributed by some metallurgists to low temperature embrittlement, while others hold that failure results from the transformation of the tin-rich phase of the solder from the solid white (beta) to the powdered gray (alpha) form. From the data previously available in the literature, neither of these explanations can be completely corroborated. cohen and van Lieshout have estab-lished the beta to alpha tin transformation at 13,2°C and have shown that strain accelerates the transformation. Further, they showed that although I pct lead retarded the transformation, it was not eliminated. It will be pertinent, then, to note whether the beta to alpha transformation of the tin.rich phase will occur in a short-time tensile 'test. polanyi and schmid2 studied the tensile properties of tin single crystals at — 185°~ and report that tin is britlle at this tem-perature. In 1946, Kostenets3 reported that pure tin was brittle at —Ig6 and — 253°~, while lead remained ductile at both these temperatures. He also studied the tensile properties of tin-lead alloys containing from 10 to 75 pet lead at —253, —196 and + I~OC. The ultimate tensile strength increased more than two times in going from room temperature to — I96°C and about three times that value on further cooling to — 253 C- All the alloys were brittle at — 196'C except those containing more than 75 pct lead. Even at — 253'C, the 75 pct lead alloy retained 36 pet elongation in a 30 mm-ga. length. Creep is also an important phenomenon

Jan 1, 1949

By J. W. Hickman

Most of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.' In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,~ nickel,= chromium,= copper,z tungsten,s molybdenum,3 beryllium,' uranium,' thorium,' titanium6 and zirconium6 while investigations are in progress on tantalum and columbium. The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally. Examples of solid solutions which may present difficulties are MOO* and WOp, Fe304 and FeO.CrnOa since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of loglo Kg for the several temperatures. AF"B = -RT In KR AF°R and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the the given in I 1 to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium oxide to form

Jan 1, 1949

By J. N. Hobstetter

It is widely believed that the nucleation of phase transformations in solid metals is accomplished by some type of local atomic fluctuations in the parent phase which arise from spoutaneous difiusion in the metal or alloy system. Under appropriate conditions, these fluctuations are believed to be stable in the sense that the free energy of the entire system is lowered if the fluctuations, or nuclei, grow. Under other conditions they are thought to be unstable in the sense that the free energy is lowered if they redissolve. The criterion for stability is usually taken as the size of the fluctuation. This view has been rationalized by Beckerl in terms of the free energy released by the volume of the nucleus and the free energy associated with the formation of a new surface surrounding the nucleus. The qualitative result of this reasoning is shown in Fig I where the changes in free energy for the surface and volume effects are plotted together with their sum against the radius of the nucleus. There is evidently always a critical size r, beyond which the release of free energy which is proportional to the volume always dominates the increase of free energy which is proportional to the surface area. Borelius2 has also attempted to rationalize the stability criterion for binary alloys, but in terms of the internal concentration of the fluctuations. He has found that, if surface energies are entirely ignored, the fluctuation must still reach a critical concentration if it is to become stable and avoid subsequent dilution. Although the Borelius theory fails to predict many observed nucleation phenomena such as the vanishing of the nucleation rate at the critical temperature, the major premise must certainly be valid. In this paper a reconciliation of the Becker and Borelius views is made by means of a search for nuclei which are at once stable with respect to both size and internal concentration. The increase in free energy per mole accompanying the formation of a nucleus which is just stable, AF., is independent of the path whereby the nucleus is brought into being. It is thus appropriate to seek critical nuclear attributes without reference to the fluctuation mechanism. The rate of nucleation, however, cannot be treated without a detailed understanding of the exact fluctuation process which produces stable nuclei. In this and succeeding papers the purpose will be to find the size, shape and internal concentration of the stable nucleus which is formed with a minimum increase in free energy in a wide variety of systems. The Nature of the Nucleus It is necessary ti have rather detailed knowledge of the nature of a nucleus if AF, is to be computed. Fortunately, enough facts are known or suspected about the nucleus to make possible a detailed analysis. X ray diffraction studies have shown

Jan 1, 1949

Jan 1, 1949

By W. Crafts, J. L. Lamont

Secondary hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to thc secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at II00 F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader. Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to IIOOOF, but the mechanism of the process has received little consideration.

Jan 1, 1949