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By Erskine Ramsay

The following description of the Alabama coal-,fields is taken (with slight omissions) from the report " On the Warrior CoalField, by Henry McCalley, A.M., C. and M. E., Assistant State Geologist:" The coal lands of Alabama are of the great coal basin of the Ohio, or of the great Appalachian coal-field, and are estimated at 8660 square miles. They formed one connected field prior to the great Appalachian revolution, when there was pushed up through them long, narrow, anticlinal ridges which have been denuded into the present well-known anticlinal valleys, and thus this great field has been divided up into three more or less distinct parts. These parts were named by Prof. Tuomey, in 1849, the Warrior, the Cahaba and the Coosa coal-fields, respectively, from the names of the rivers which drain them. They are of very unequal size, the Warrior, with an area of 7810 square miles, being nearly ten times as large as the other two combined, and about two-thirds as large as the coal-area of Great Britain. This Warrior field is the most northwestern of the three coal-fields of Alabama, and comprises all of the coal-measnres in Alabama, northwest of the Alabama Great Southern railroad, or all of those drained by the Warrior and Tennessee rivers. The greater part of this field, almost all of it away from the present railroad lines, has never received more than a surface-examination. Still, we have in the Warrior coal-field one of the richest coal-basins of this or any other country. As a whole, the Warrior coal-field is a broad, shallow, tray-shaped depression, sloping towards the southwest, and with its southwest end covered by a newer formation and its southeast side, especially, complicated by folds and fractures. As is the case with all of our Coal Measures. it is composed of a series of sandstones. conglomerates, shales, slates and coal-seams, with some little limestone at several horizontal positions, but contains no thick bed of this last rock like the Measures of Pennsylvania and other States. The thickest conglomerates are near the bottom and top of the series, and hence these coals might be said to belong mainly to the

Jan 1, 1891

By H. M. Morse

Tinsley Oil Field.—Mississippi joined the oil-producing states when on Sept. 13, 1939, the Union Producing Company's G. C. Woodruff well No. 1, sec. 13, T. 10 N., R. 3 W., Yazoo County, was completed after drilling plug at 4540 ft. in the Woodruff sand of the Eutaw formation of Cretaceous, producing 300 bbl. per day of 34.4" gravity oil through a ¼-in. choke, with a gas-oil ratio of 80 to 1 and bottom-hole pressure of 2045 lb. This was the discovery well in the Tinsley oil field. The well was drilled to a total depth of 4567 ft. and no salt water was encountered. The sand underlies the Selma chalk formation. Nine producing oil wells and one dry hole were drilled and completed by the end of 1939. Two producing sands have been found in the Eutaw and a third sand in the top of the Tuscaloosa formation, called the Woodbine sand in Louisiana and Texas. Faulting is an important factor in the Tinsley field. Total oil production has been approximately 250,000 bbl. from the nine flowing wells. Total depth to top of productive zone was 4540 ft.; to bottoms of productive wells, 4580 ft. Net thickness of the producing formation is 20 to 40 ft., and its porosity is 24 per cent. The deepest zone tested was the Tuscaloosa, in which the depth of hole was 6112 feet. Six hundred and forty acres has been proved for oil production. Jackson Gas Field.—The Jackson gas field has shown a steady decline in the number of wells but the pressure has been maintained. This field is a perfect example of a water-driven field and the time of wells going to salt water is predictable. Five wells were drilled in the Jackson field, of which only one produced. Amory Gas Field.—Interest was renewed in the Amory gas field, where a new well was started in the fall of 1939. Geological Formations.—The deepest well drilled in 1939 was the Willmut Gas and Oil Company's Cleve Love S. F. Johnson No. 1, sec. 29, T. 6 N., R. 1 W., Hinds County. This well encountered the Lower Cretaceous, Trinity series from 3770 to 6422 ft.; Lower Mesozoic from 6422 to 6484 ft. The geological correlations and nomenclature of the formations in Mississippi are shown in the accompanying strati-graphic section.

Jan 1, 1940

By H. M. Morse

Tinsley Oil Field.—Mississippi joined the oil-producing states when on Sept. 13, 1939, the Union Producing Company's G. C. Woodruff well No. 1, sec. 13, T. 10 N., R. 3 W., Yazoo County, was completed after drilling plug at 4540 ft. in the Woodruff sand of the Eutaw formation of Cretaceous, producing 300 bbl. per day of 34.4" gravity oil through a ¼-in. choke, with a gas-oil ratio of 80 to 1 and bottom-hole pressure of 2045 lb. This was the discovery well in the Tinsley oil field. The well was drilled to a total depth of 4567 ft. and no salt water was encountered. The sand underlies the Selma chalk formation. Nine producing oil wells and one dry hole were drilled and completed by the end of 1939. Two producing sands have been found in the Eutaw and a third sand in the top of the Tuscaloosa formation, called the Woodbine sand in Louisiana and Texas. Faulting is an important factor in the Tinsley field. Total oil production has been approximately 250,000 bbl. from the nine flowing wells. Total depth to top of productive zone was 4540 ft.; to bottoms of productive wells, 4580 ft. Net thickness of the producing formation is 20 to 40 ft., and its porosity is 24 per cent. The deepest zone tested was the Tuscaloosa, in which the depth of hole was 6112 feet. Six hundred and forty acres has been proved for oil production. Jackson Gas Field.—The Jackson gas field has shown a steady decline in the number of wells but the pressure has been maintained. This field is a perfect example of a water-driven field and the time of wells going to salt water is predictable. Five wells were drilled in the Jackson field, of which only one produced. Amory Gas Field.—Interest was renewed in the Amory gas field, where a new well was started in the fall of 1939. Geological Formations.—The deepest well drilled in 1939 was the Willmut Gas and Oil Company's Cleve Love S. F. Johnson No. 1, sec. 29, T. 6 N., R. 1 W., Hinds County. This well encountered the Lower Cretaceous, Trinity series from 3770 to 6422 ft.; Lower Mesozoic from 6422 to 6484 ft. The geological correlations and nomenclature of the formations in Mississippi are shown in the accompanying strati-graphic section.

Jan 1, 1940

By J. H. Hamilton, J. R. Lewis, J. C. Nixon, C. L. Graverson

Recently there has been much speculation concerning the advantages of using oxygen enriched air or pure oxygen in pyrometallurgical processes. The advantage of using oxygen in the iron blast furnace and elsewhere in ferrous production metallurgy has been given careful consideration and, as a result, several experiments have been tried and a number of papers have recently appeared on this subject.1,2 The use of oxygen in nonferrous smelting likewise poses interesting problems, therefore any experimental data obtained in this area should likewise be of general interest.3 Ashcroft4 in 1933 claimed to have obtained improved results when copper concentrates were roasted in pure oxygen. However, his paper gives neither data nor experimental details. A few years ago a research program was started in this laboratory which had for its objective the determination of the mechanism of oxidation of metallic sulphides under varying conditions. To date we have studied the oxidation of galena,5 sphalerite, and chalcocite. It is a well known fact that copper sul-phde minerals are oxidized slowly by weathering agents, so that the sulphides of copper which find their way into a tailing pond are gradually changed into water-soluble and acid-soluble compounds. Commercially, the oxidation of copper sulphide minerals is accomplished by roasting them at elevated temperatures in air using a suitable (usually multiple hearth) roaster. Most copper smelters are equipped with such roasters. In this phase of the study we were especially interested in determining the effect of temperature on: (I) the air oxidation of chalcocite and (2) the oxidation of chalcocite using commercial oxygen. The amount of sulphur removed as sulphur dioxide, the percentages of water-soluble copper, and of acid-soluble copper were determined for the air oxidation tests. In the tests using commercial oxygen, the percentages of sulphur dioxide, water-soluble copper, acid-soluble copper, water-soluble sulphur and acid-soluble sulphur were determined. For these experiments the temperature was varied from 250 to 700°C. Experimental Preparalion of Chalcocite (Cu2S) Natural chalcocite is not pure, Minerals such as bornite, covellite, and chalcopy-rite may be present. It was decided, therefore, to prepare some chalcocite in our own laboratory. An intimate mixture of sulphur and hool divided metallic copper in the ratio of 4 g of copper to I g of sulphur was prepared. TO this was added a slight excess of

Jan 1, 1949

By Axel Hultgren, B. Herrlander

THE original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between At and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880° was free from veining. Bannister and Jones4 considered veining in ferrite to be a manifestation of microscopical and submicroscopical inclusions. Northcott,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berglund. Tritton (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling.

Jan 1, 1946

By R. A. Pallanch

SODIUM sulfite as a zinc retarding agent in the selective flotation of complex lead-zinc sulfide ores was discovered by the writer in the summer of 1919 in the testing laboratory of the U. S. Smelting, Refining & Mining Co.'s gravity concentrator at Midvale, Utah. It proved to be the first reagent to give consistently good results in the laboratory on the company's Bingham ore. In December, 1919, C. A. Lemke, concentrator superintendent, recommended that a flotation unit be added to the existing gravity mill to handle the mill slimes, using sodium sulfite as the zinc depressant. Owing to the poor lead and zinc markets and the unfavorable royalty schedules offered by the Minerals Separation Co., the project fell through at this time. In 1921, a number of laboratory tests were made at Midvale on other ores, among them ore from the Sunnyside mine at Eureka, Colo. Both sodium and calcium sulfites were used with success on this ore. Early in 1923, further tests were made at Eureka, shortly after the Sunnyside company had resumed operations after a two-year shutdown. As a consequence sodium sulfite was given a trial in the mill. The results showed sufficient improvement over previous work as to warrant continuous use of this reagent in the lead circuit. Except for a week or so in 1926 and for several weeks in April, 1927, when sodium cyanide and zinc sulfate were given trial runs in this mill, sodium sulfite has been used ever since. Sodium sulfite was chosen rather than the calcium sulfite because of its greater solubility, making it possible to introduce the reagent as a solution. This solution is introduced into the Marcy ball mills along with the original feed of ore. The consumption of sodium sulfite in the Sunnyside mill varies from ¼ to ½ lb. per ton of ore, the smaller amount probably being nearer the average. In February, 1924, laboratory work at Midvale demonstrated conclusively that good results could be obtained on the company's Bingham ore and on most of the custom ores tested by using sodium sulfite as the zinc depressant, xanthate as the lead enhancer in the lead circuit, followed by copper sulfate and additional xanthate to float the zinc. Sodium sulfide was used to float the iron pyrite after the lead and

Jan 1, 1928

By R. A. Pallanch

Sodium sulfite as a zinc retarding agent in the selective Hotation of complex lead-zinc sulfide ores was discovered by the writer in the summer of 1919 in the testing laboratory of the U. S. Smelting, Refining & Mining Co.'s gravity concentrator at Midvalc. Utah. It proved to be the first reagent to give consistently good results in the laboratory on the cornpanj's Bingham ore. In December, 1919, C. A Lemke, concentrator superintendent, recommended that a flotation unit be added to the existing gravity mill to handle the mill slimes, using sodium sulfite as the zinc depressant Owing to the poor lead and zinc markets and the unfavorable royalty schedules offered by the Minerals Separation Co., the project fell through at this time. In 1921, a number of laboratory tests were made at Midvale. on other ores, among them ore from the Sunnyside mine at Eureka, Chlo. Both sodium and calcium sulfites were used with succcss on this ore. Early in 1923, further tests were made at Eureka, shortly after the Sunnyside company had resumed operations after a two-year shutdown. AS a consequence sodium sulfite was given a trial in the mill. The results showcd sufficient improvement over previous work as to warrant continuous use of this reagent in the lead circuit Exeept for a week or so in 1926 and for several weeks in April, 1927, when sodium cyanide and zinc sulfate were given trial runs in this mill. sodium sulfite has been used ever sinee.. Sodium sulfite was chosen rather than the calcim sulfite brcauscl of its gre1ater sollubility, making it possitdr. to introduee the reagent as a solutiun. This Solution is introdueed into the Marry ball mills along with the original feed of ore,. The consumption of sodium sulfite in the Sunnyside mill varies from 1/4 to 12 lb per ton of ore, the smaller amount probably being nearer the average. In February, 1924, laboratory work at Midvale demonstratcd conclusivcly that good results could be obtaincd on the company's Bingham ore and on most of the custom ores tested by using sodiuin sulfite as the zinc depressant, xanthate as the lead enhancer in the lcad circuit, followed by copper sulfate and additional xanthate to float the zinc Sodium sulfide was used to float the iron pyrite after the lead and

Jan 1, 1928

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

CARL HENRICH (communication to the Secretary*).-I have read with much interest the discussions of my paper by Messrs. A. S. Dwight, E. P. Mathewson, Win. B. Boggs, Jos. W. Richards, and W. C. Smith. Mr. Dwight's acknowledgment that he always-in lead smelting¬obtained better results by figuring A1203 as an acid in his slags, I may take as a confirmation of my views, notwithstanding his later conversion by, the late T. S. Austin to the latter's empirical view and way of neglecting the consideration of A1203 altogether in the composition of slags-letting the slags "dissolve" in Al203. I have a strong suspicion that Mr. Austin, in a large custom smelting plant at El Paso, has been able to keep the alumina percentage of his slags sufficiently low, not to give him much trouble, although I have also a suspicion that his furnace foreman may have had a somewhat differing opinion of the practical working of the "dissolving" theory,, whenever its applicability was tested to its limits. That Austin should have conceived the notion that the Ca of CaF2 would enter into a slag as CaO, seems hardly in accord with the recognized ability of that late metallurgist. It is a well-recognized fact that even small amounts of CaF2 will reduce the viscosity of a slag; but I did not think anyone ever had an idea that CaF2, in some mysterious way, parted with its F and coupled itself with 0 to satisfy a craving for CaO on the part of 802-least of all in a lead furnace. The "dissolving" theory for CaF2 was doubtless appropriate, and an improvement on figuring the Ca of CaF2 as CaO to satisfy the demand of Si02 for RO bases. However, I cannot understand the rationality of extending this "dissolving" theory to A1203 and to ZnO. It would be interesting to have more specific data from Mr. Mathewson in regard to the actual composition-analyses-of the slags made, when he had these unusually high alumina slags in Colorado. We "old" smelters all know that within certain limits, usually found out by rather tough experience, we could safely "disregard" A1203. In fact, I believe, we never really analyzed for alumina, except in slag analyses, when we

Jan 6, 1917

By Harold Markus, Gerhard Derge, Arthur Grobe

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from ½ to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.1°. Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Harold Markus, Arthur H. Grobe, Gerhard Derge

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study. has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from 1/2 to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.? After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been damped. The pH of the electrolyte was controlled? by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.10. Potentials were measured against a saturated calomel electrode connected. to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By A. U. Seybolt, R. A. Oriani

The pressure and composition of the solid solution of nitrogen in chromium has been investigated as a function of temperature. The partial molal heat of solution, the activity of nitrogen in solid solution, and the partial molal free energy have been computed. The enthalpy of three reactions is summarized: N + 2Cr(3) = Cr2N(4), H° = —28,500 cal per mol 1/2N2(p) + 2Cr(8) = Cr2N(3)1 ?HO = —23,500 cal per mol 1/2N2(p) = N, ?H° = 5,000 cal per mol. WORKERS who have investigated the problem of the preparation of ductile chromium have been concerned with the effects of minor amounts of impurities upon this refractory metal. In particular, gaseous impurities such as oxygen and nitrogen have been suspected of causing trouble because of many known cases where brittleness in transition elements has been definitely traced to these elements. In order to evaluate the possible effects of the nitrogen impurity in chromium, it appeared desirable to learn something of the dependence of the nitrogen solubility upon temperature and pressure. Previous Work Maier3 in 1942 in his treatise on sponge chromium reviewed the thermodynamics of the chromium nitrides Cr2N and CrN, both of which are well-estab- lished compounds, but which apparently have not been studied in much detail. Maier presented some free energy-temperature expressions for the reactions 2 Cr,N = 4 Cr + N2 [1] and 4 CrN = 2Cr2N + N2 PI based mainly on the work of Satoh2 and Sano." Pearson and Ende3 in 1953 briefly reviewed the thermodynamics of Cr-N using the same data available to Maier, and also derived a free energy-temperature expression for reaction 1. Of the two nitrides mentioned previously, the present investigation was only concerned with Cr,N, since this nitride is in equilibrium with the metal phase, at least over most of the temperature range, Blix4 in 1929 established the structure of Cr2N (close-packed-hexagonal) by X-ray diffraction methods, and indicated that its homogeneity limits extend from 11.2 pet to 15.1 wt pet N. At a temperature of 1200°C, 38 mm Hg from the Maier expression and 43 mm Hg from the Pearson

Jan 1, 1957

By C. H. Mathewson, W. R. Hibbard, Robert Maddin

A satisfactory mathematical relationship between shear, elongation and change of orientation in the axial straining of a single crystalline rod or wire may be based on a simple model in which blocks, representing glide lamellae, glide over one another and rotate so as to maintain the original fixed position of the axis as the wire elongates.' Obviously such a model gives no information concerning strain-hardening or the atomic adjustments at the sliding surfaces and their influence on the internal structure of the blocks. Moreover such an operation could be conducted with rigid blocks only by using self-aligning grips or a flexible attachment which would permit the adjacent blocks to freely assume their changing orientations. There are many unsolved problems (see Andrade2) concerning the manner in which nature departs from the simple model in permitting the essentials of slip, rotation and elongation to occur along with strain-hardening and the appearance of glide lamellae of various dimensions and special characteristics, not fully appreciated at the present time. This paper describes part of an extensive investigation on the development and characteristics of glide ellipses in single crystalline alpha brass rods and is especially concerned with the observation of cross-slip in crystals oriented wholly within the range of slip on a single system according to the generalizations first presented by Taylor and Elam in 1923.³ Experimental Procedure Half-inch rods of alpha brass (nominally 70 pet Cu, 30 pet Zn)* were converted into single crystals by melting and gradual solidification in a graphite mold according to the Bridgman method.4 In order to remove any coring, the crystals were homogenized at 800°C for 16 hr and tested by etching with a 50 pet nitric acid solution. The back-reflection Laue technique as described by Greninger6 was used for determining the orientations of the crystals. Standard stereographic operations were employed to locate the specimen axis in a triangle of the Taylor and Elam3 projection so that the slip plane and direction could be predicted. The lineage structure reported by Buer-ger6 was present in the crystals used in this investigation. However, only crystals were used in which the internal differences in orientation did not exceed two degrees. Very little is known concerning the effect of the presence of a lineage structure on the detailed mechanism of plastic deformation.

Jan 1, 1949

By C. H. Mathewson, Robert Maddin, W. R. Hibbard

A satisfactory mathematical relationship between shear, elongation and change of orientation in the axial straining of a single crystalline rod or wire may be based on a simple model in which blocks, representing glide lamellae, glide over one another and rotate so as to maintain the original fixed position of the axis as the wire elongates.' Obviously such a model gives no information concerning strain-hardening or the atomic adjustments at the sliding surfaces and their influence on the internal structure of the blocks. Moreover such an operation could be conducted with rigid blocks only by using self-aligning grips or a flexible attachment which would permit the adjacent blocks to freely assume their changing orientations. There are many unsolved problems (see Andrade2) concerning the manner in which nature departs from the simple model in permitting the essentials of slip, rotation and elongation to occur along with strain-hardening and the appearance of glide lamellae of various dimensions and special characteristics, not fully appreciated at the present time. This paper describes part of an extensive investigation on the development and characteristics of glide ellipses in single crystalline alpha brass rods and is especially concerned with the observation of cross-slip in crystals oriented wholly within the range of slip on a single system according to the generalizations first presented by Taylor and Elam in 1923.³ Experimental Procedure Half-inch rods of alpha brass (nominally 70 pet Cu, 30 pet Zn)* were converted into single crystals by melting and gradual solidification in a graphite mold according to the Bridgman method.4 In order to remove any coring, the crystals were homogenized at 800°C for 16 hr and tested by etching with a 50 pet nitric acid solution. The back-reflection Laue technique as described by Greninger6 was used for determining the orientations of the crystals. Standard stereographic operations were employed to locate the specimen axis in a triangle of the Taylor and Elam3 projection so that the slip plane and direction could be predicted. The lineage structure reported by Buer-ger6 was present in the crystals used in this investigation. However, only crystals were used in which the internal differences in orientation did not exceed two degrees. Very little is known concerning the effect of the presence of a lineage structure on the detailed mechanism of plastic deformation.

Jan 1, 1949

By C. E. Birchenall

DaVIES and Richardson1 have measured composition changes for Mn1-Owith variation in the equilibrium partial pressure of oxygen at 1500°, 1575°, and 1650°C, where 6 is the deviation from the simple stoichiometric ratio. No trend in this relationship with temperature was observed, so these remarks apply to the whole temperature range. The experimental values and their spread are shown by the bounded straight-line segments in the figure. Davies and Richardson assume that the stoichiometric oxide shows Frenkel disorder, given by the equation Mn2+Mn2+ + Mn" [1] where Mn2+ is a normal lattice ion which moves into an interstitial site (Mni2+) leaving a vacancy (Mn,"). The superscript dashes indicate that there is an excess charge on the anions surrounding the vacancy. Schottky disorder, in which a perfect crystal acquires equal numbers of cation and anion (Ov") vacancies according to leads to equations of exactly the same form in the analysis below. In view of the neutron diffraction results of Roth,2 which shows extensive Frenkel disorder in Fe1-o, Eq. [I] seems more appropriate. The deviations from stoichiometric composition, MnO, result from the addition of oxygen according to In effect Davies and Richardson ignore the variation of Mn3+in constructing equilibrium constants. This approximation might not appear to be very serious if the excess positive charges are really free posi- tive holes (P+) and if the intrinsic conductivity is high as a result of the reaction where e- is a conducting electron. However, the calculations of Buessem and Butler3 indicate that the partition functions of the free charges make a large contribution to the equilibrium constant, and this approximation would not be a desirable one. Furthermore, Morin4 shows that the positive holes are probably localized in MnO and therefore are described better by the mass action principle than by a degenerate gas model. Davies and Richardson's considerations require that activity corrections be applied beyond a 6 value of about 0.005. It is proposed to show here that the dissociation pressure curve can be calculated reasonably well over the whole composition range studied without activity corrections by choosing appropriate equilibrium constants for reactions 1 and 2. As stoichiometric composition The mass action constant, Ks, for reaction [I.] and the equilibrium constant, K,, for reaction [2] are given by where the concentrations which do not change significantly have been absorbed into the constants. The brackets denote concentrations. The deviation from stoichometric composition is given by gardless of [Mni2 ]. Substituting Eq. [7] in [6]

Jan 1, 1961

By Gerald Edmunds

The liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the composition of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. Apparatus By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 13/4-in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 181/2 in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By Gerald Edmunds

The liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the composition of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. Apparatus By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 13/4-in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 181/2 in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

R. M. Raymond, New York, N. Y.—The filling and drawing down of the overhead material was done at considerable depth, which is not the usual method in which it starts at the surface.. R. J. Mechin.— It is a little more than 1000 ft. at El Bordo. The vein above had been caved practically to the surface and some of the ore had been excavated, using underhand and overhand square-set methods. This was far enough away from the shaft to prevent any bad effects. When the sill floor was taken out, to insure the old cave material following down well, we put chutes in the square sets for several weeks until we were sure that the material from above was moving down; on each level above, several crosscuts were driven into the old fill by which we could see the material coming down and thus be sure it was following the first. We had to dynamite it very little because it was dry and dusty. The only trouble was that timber starting from the old square sets would get across the chute and hang up. R.. M. Raymond.—HOW many floors did you operate at once? R.. J. Mechin.—We would operate one floor through the whole length and prepare for the second. F. W. SperR, Houghton, Mich.—Could you have worked it in steps? R.. J. Mechin.—Yes; but working it all on one floor was much better for ventilation. The passage between steps would tend to become heavy and blocked and, as the passages from the mining floor down are usually filled with ore, there would be no way for the air to pass up. By means of doors and fans, air was driven to the extreme end of the orebody through the stope and up the other end; but it could have been worked in steps. F. W. SpeRR.—D the following-up material ever become so heavy that you could see weight on the caps before you had to take out the posts?

Jan 1, 1927