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By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By Lyden, Joseph P.

THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.- This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications.

Jan 1, 1950

By Henry C. Freeman

During the early period of the construction of the Illinois and Michigan Canal, about 1838, in excavating for the canal, where the present town of Utica stands, hydraulic limestone was discovered, and its value was recognized. A kiln for calcining and a mill for grinding were erected, and the cement was used in the construction of the locks of the canal. This property was subsequently bought by the present owner, Mr. James Clark, and the work has been continued to the present time in much the same primitive manner as it was begun. The bed is exposed in the Illinois River valley by stripping off a few feet of the covering rock. It is from 4 feet to 6 feet 9 inches thick, and nearly level, dipping gently to the northeast. The Utica Cement Company's establishment, which is two miles west of Utica and two miles east of La Salle, was an outgrowth of the Illinois geological survey. The writer was in charge of the district which included La Salle county, and, in working out the details of the geology of that county, discovered, below the Utica bed, another workable hydraulic limestone, which makes its appearance in the northern bluff of the Illinois River valley, rising above the water level at the point where the company's works are established. This cement group, of which there are several thin beds, lies just below the St. Peter's sandstone, with a few feet intermediate of transition-rock, which appears to represent the Calciferous, and is exhibited in place, in concretionary form, at the top of the bluff. The hydraulic beds are very regular, and the one worked by the company is 10 feet thick; or, speaking more definitely, there are two beds, separated by 18 inches of sandstone, lying about two feet above the bottom, and the two beds are worked as one, the sandstone being first cut out and removed, to prevent mixture. In 1869 I was invited to join with a company, and to take charge

Jan 1, 1885

By W. F. Boericke

THE recent completion by the United States Aluminum Company of a $4,000,000 addition to its plant at Massena, N. Y., consisting of a large blooming mill and structural mill, gives this organization, a subsidiary of the Aluminum Company of America, the distinction of possessing the largest aluminum rolling mill in the world, as well as the first mil1 in this country to roll aluminum exclusively. The plant is located near the international boundary line between Canada and the United States, about 3 miles from the St. Lawrence River, to take advantage of the development of cheap hydroelectric power which is needed not only for the manufacture of structural shapes from the ingots, but in the reduction of alumina to the metal by the well-known Hall process as well. A power canal from the St. Lawrence River to the power house on the Grasse River at the plant provides for the waterflow, which, coupled with a drop of 47 ft. in 2% miles, generates 80,000 hp. through vertical turbines. An additional 60,000 hp. is purchased.

Jan 1, 1930

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By S. Shapiro, G. Krauss

The strutural and cr~stallo~aphic features of the plates of austenite produced by the martensite to aus-tenite or reverse martensitic tramformation have been determined in an Fe-33 wt pct Ni alloy. Micro-focus X-ray techniques and single-surface trace analysis 072 bulk samples yielded two distinct habit planes, (0.174, 0.309, 0.~35)~ and (0.375, 0.545, 0.749jM. The former plane uas the one predorninantly observed and its existence was verified by transn~ission electron microscopy. The orientation relation-ship between the reversed austenite and the parent martensite was approximately the same as the Nishiyamna and other relationships reported for the direct tramformation. Replica and thin-joil obser-vations show that both high densities of tangled dis-locations and occasional twins constitute the fine structure of the reversed austenite. Application of the phenomenological theory to a variant of the predominant habit plane defines an irrational plane and direction for the second shear in accordance with the comnplexity of the fine structure. The shear accompanying the reverse martensitic transformation is at least 0.51, the maximnum value of- the tangent oJ the tilt angle measured on surface replicas. A mechanism relating the fine transformation twins in martensite to the nucleation of reversed austenite of the predominant habit is proposed. The reversal of Fe-Ni martensite takes place both at the edges of martensite plates and in a piecewise fashion within them.' The shear-type nature of the reverse transformation is verified by the surface relief which accompanies both edge-type reversal2 and the fragmentation of plates of martensite' as a result of rapid heating above the A, (austenite start temperature). The orientation relationship between the edge-type reversal product and the parent martensite, as determined by transmission electron microscopy, is reported to be within 4 deg of either the Kurdyumov-Sachs or Nishiyama relationships,' but there is no work at present in the literature relating to the crystallography of the platelike reversed austenite. The fine structure of reversed austenite after heating to 50°C above the Af is reported4 to be composed primarily of tangled and jogged dislocations in concentrations up to 10" per sq cm. A replica investigation of partially reversed Fe-Ni martensites5 corroborates the increase in dislocation density following reversal and presents indications of other possible modes of fine structure. This paper reports on an investigation performed to examine in detail the morphology and crystallography of the plates of reversed austenite and the shear which accompanies their formation in a matrix of Fe-Ni martensite. EXPERIMENTAL PROCEDURE Discs of a high-purity Fe-32.9 wt pct Ni single crystal served as the starting material. The single crystal had been produced in the course of an earlier investigation6 and the carbon content was determined at the time to be 0.006 wt pct. The M,, and the A,, were respectively -120" and 300°C. Partial transformation to martensite was performed at -125°C and reversal of some of the martensite was accomplished by heating in the temperature range 340" to 355°C. Most samples were heated to the reversal temperature by immersion' in a salt bath for 2 min. For surface-relief studies some polished and etched Samples were heated in a tube furnace for ten min in a hydrogen atmosphere maintained over the samples throughout the heating and cooling cycles. Samples were prepared for metallographic examination by electropolishing and etching with an HC1-HNOs-H20 et~hant.~ On one of the surface-relief samples two sets of fiducial scratches were placed on the etched sample by drawing it over a slurry of 0.06 p alumina on a "microclothJ'. The orientations of individual plates of martensite were determined by X-ray analysis. A Rigaku-Denki microbeam X-ray generator in conjunction with a Micro-Laue camera with facility for precision location of the sample in front of the beam was employed for this purpose. The collimator size was 30 p and the specimen to film distance was 5 mm. The Laue photograms were enlarged to an equivalent 3-cm specimen to film distance for analysis. The orientation of each of the plates of martensite was compared to that of the parent austenite and the relationship be -tween the two phases was, in all cases, within a few degrees of those predicted for the direct transformation. The orientation relationship between one of the larger plates of reversed austenite and its parent martensite was determined in a similar manner. The habit plane of the islands of reversed austenite in the X-rayed plates of martensite was determined by a single-surface trace analysis. Each reversal island had with the parent phase one comparatively straight boundary which was presumed to represent the habit plane trace. The pole locus technique7 was applied to traces from six different plates of martensite to determine the indices of the habit plane. A 40-cm stereographic net was employed for this analysis The morphology and fine structure of the reversed austenite were studied by electron microscopy of pre-shadowed direct carbon replicas,5 and the macroscopic shear was evaluated by a two-stage replica technique similar to that employed in electron fractog-

Jan 1, 1968

By D. L. H. Forbes

(New York Meeting, February, 1912.) Introduction.. THE application of the cyanide process to complex sulphide ores for the extraction of their bold and silver is no longer a novelty, but, as an example showing modern tendencies in this direction, the following description of the new milling process at the Lucky-Tiger mine is offered: The extraordinary richness of the ore in the upper workings of this mine made any thought of milling in its early hays seen unnecessary. Its location in an almost inaccessible part of the rugged mountains just south of the Arizona boundary-line, and 60 miles from the town of Douglas, made the expense of bringing in machinery and supplies a very serious consideration. But, after the property had been shipping high-grade ore on mule-back for a few years, there remained in the mine a considerable tonnage of vein-matter that was too low in value to ship, but which it was thought could be milled near the mine at a profit. The first milling-experiment consisted in the installation of Nissen stamps in conjunction with concentrating-tables and Frue vanners, but, as the ore from the upper workings contained most of its silver in the form of cerargyrite, this type of mill was not successful. The proximity of the mine to the great copper-concentrating mills of Cananea and Moctezuma naturally made the influence of copper-milling, ideas felt in the company's next installation. At considerable expense a stage-crushing concentrating-mill, with a capacity of 100 tons per day, was built. This mill was modeled along the lines of the most approved practice in copper-concentrators at that time, the main idea being that crushing by stages in rolls was necessary in order to prevent losses from ?sliming." Largely owing to the fact that, when the mill

Aug 1, 1912

By B. G. Klugh

In a paper before the Institute at Wilkes-Barre, Pa., June, 1911,' Mr. James Gayley discussed the application of this process to iron-bearing materials. The same author² described the results of operations at the plant at Birdsboro, Pa. The purpose of the present paper is to present further discussion of some techuical details involved in the operation of this plant, and of the theoretical and practical relations of this product to blast-furnace practice. Since Oct. 1, 1911, the Birdsboro plant has been in operation at the blast-furnace of the E. & G. Brooke Iron Co. The results have been highly satisfactory, although the material treated, being chiefly the flue-dust currently made by the furnace or taker] from the accumulated stock-pile, was excessively high, and yet not uniform, in carbon, so that the desirable control or regularity of the amount of fuel in the mixture treated could not be maintained. Nothing could more forcibly demonstrate the flexibility of the process than the fact that, under these conditions, the sinter produced was, in all cases, of excellent quality. The Dwight & Lloyd process, as such, slid its present highly-developed mechanical appliances were described by Mr. Gayley in the paper above mentioned. While the repetition of some particulars will be unavoidable in this paper, it will be confined to features bearing upon the metallurgical principles involved. According to the principle of the process, the finely-divided iron-bearing material to be sinterecl is intimately nlixed with

Jan 1, 1913

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By L. A. White

IN this paper it is proposed to follow the developments in the design of the lead blast furnace at Port Pirie from the time The Broken Hill Associated Smelters Pty. assumed control in 1915 to the present time, with special reference to the development of the system using two superimposed rows of tuyeres as is now in operation. Lead smelting operations first commenced in 1889, when the British Broken Hill Pty. Ltd. started its first furnace. This was followed by installing two more furnaces during the same year and another the following year. In 1892, Broken Hill Proprietary Co. Ltd. acquired the smelting works and combined operations with those at Broken Hill, New South Wales; by 1897, the whole of the smelting operations had been transferred to Port Pirie and thirteen blast furnaces were built to treat the Broken Hill ore production. In 1915, The Broken Hill Associated Smelters Pty. Ltd. took over from the Broken Hill Proprietary and have carried out operations since that time. From its inception, the present company started on a long range program of reconstruction, in which the development of the lead blast furnace has played a prominent part. A definite trend in plant development has been towards the simplification of plant control by a reduction in the number of operating units. The great advantages of technical control which resulted from the very simplified flowsheet established in the continuous refining process stimulated the desire to extend the principle to the smelting operation. Thus in the sequence of furnaces described here, it will be noted that the trend has been towards larger and, of course, fewer units. With each such development it is significant that the operating conditions and metallurgical results have shown steady improvement. Standard Furnace In 1920 there were seven furnaces operating, five of a type subsequently called the standard furnace and two of the original thirteen smaller furnaces, the latter type being used for the treatment of drosses, etc. produced from the refinery section, while the standard type carried out the main, lead-smelting operations. The standard furnace (figs. 1 and 2) had the dimensions given in table I.

Jan 1, 1951

By James Gayley

(Presented at the Washington meeting, May 3, 1905, and simultaneously sent to the Iron and Steel Institute, for presentation at the meeting of that Society in London, May 11, 1906.) It is to be regretted that the data respecting the use of dry-air blast, which were presented to the Iron and Steel Institute at its meeting in the United States, in October, 1904, should have been restricted to the period from August 25th to September 9th inclusive, and from September 17th to 30th inclusive. In order to present the paper at all it was found necessary to limit the record of operations to the period above stated. It appears from the reported discussion that some of those who took part felt themselves to be at a disadvantage, in considering the economies secured through the use of dry-air blast, by reason of the fact that the data presented covered so short a period. It is the purpose of this communication to present in detail the record of operations of the Isabella Furnaces from November, 1904, to March, 1905, inclusive, as shown by the furnace-records. The month of October, 1904, is not included, as the furnace using dry-air blast was stopped several times for repairs; and while the record was a very good one considering these interruptions, yet it was not a continuous one. The record for Furnace No. 1 using dry-air blast, and the comparison with Furnace No. 3 using natural air for the month of November, 1904, is set forth in Table I. By a reference to my former paper it will be noted that the month of November is the beginning in this country of the winter period, when the atmosphere decreases rapidly in humidity. The month of October being the transition month in the autumn and April in the spring, and furnaces using natu-ral air approach more closely, from November on, to the conditions obtained by the use of dry-air blast. The data given in

Jan 1, 1906

By J. P. Smith

DURING the winter of 1946 to 1947 potash operations in Germany, France and Spain were visited by the author. The U. S. Department of Commerce, through its Field Intelligence Agency Technical, sponsored the inspection of German properties by representatives of the American Potash Industry. Vast deposits of potash salts occur in the above-mentioned countries, and the production and marketing of these salts are important in their respective economies. Germany An area of some ten thousand square miles of north central Germany is underlain by lenses of potash salts interbedded with greater thicknesses of sodium chloride or common salt. These salt measures are relict deposits from the evaporation of an arm of the Zechstein (Permian) Sea which formerly covered northern Europe. During the peak year of 1940, Germany produced salts containing 1,860,000 tons of K,O and, next to coal, potash is its most important mineral raw material. The German deposits are found in the synclinal areas flanking the Flechtingen, Hartz Mountain and Thuringian uplifts, and, to the north they lie beneath the plains of Hannover. The regional dip of the salt measures is to the north, hence, lenses of potash found at depths of 500 to 1000 m* in the Two general depositional provinces of potash concentrations are recognized: (1) the main basin, and (2) the subsidiary basin. The main basin embraces the producing districts of Stassfurt, Sud Hartz, Halle, and Hannover-Braunschweig. From J. P. SMITH, Member AIME, is Clzief Geologist, U. S. Potash Co., Carlsbad, New Mexico. New York Meeting, February 1948. TP 2621 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 26, 1948. 40 to 45 pct of the German production comes from this basin. The Werra-Fulda district, producer of 50 pct or more of the German potash, lies in the subsidiary basin. Salt Stratigraphy: Five commercial potash zones or beds are recognized. The three beds present in the main basin are: The Stassfurt bed that occurs near the top of the older salt, and the Ronnenberg and Riedel beds in the younger salt occurring 200 to 300 m, respectively, above the Stassfurt bed. The Stassfurt bed is found over the entire main basin, while the Ronnenberg and Riedel are restricted to the Hannover area. Two potash beds occur in the Werra basin. These are the Thuringian, or lower bed and the Hessen or upper potash bed that occurs 60 m above. These beds lie 210 and 150 m, respectively, below the position of the Stassfurt bed, and are restricted to the Werra basin. The upper bed is 2.5 to 11.5 m in thickness, and the principal ores are hartsalz with varying thicknesses of carnallite. The lower bed averages 3 m in thickness, and contains hartsalz. The upper bed is presently being mined, and the

Jan 1, 1951

By J. P. Smith

DURING the winter of 1946 to 1947 potash operations in Germany, France and Spain were visited by the author. The U. S. Department of Commerce, through its Field Intelligence Agency Technical, sponsored the inspection of German properties by representatives of the American Potash Industry. Vast deposits of potash salts occur in the above-mentioned countries, and the production and marketing of these salts are important in their respective economies. Germany An area of some ten thousand square miles of north central Germany is underlain by lenses of potash salts interbedded with greater thicknesses of sodium chloride or common salt. These salt measures are relict deposits from the evaporation of an arm of the Zechstein (Permian) Sea which formerly covered northern Europe. During the peak year of 1940, Germany produced salts containing 1,860,000 tons of K,O and, next to coal, potash is its most important mineral raw material. The German deposits are found in the synclinal areas flanking the Flechtingen, Hartz Mountain and Thuringian uplifts, and, to the north they lie beneath the plains of Hannover. The regional dip of the salt measures is to the north, hence, lenses of potash found at depths of 500 to 1000 m* in the Two general depositional provinces of potash concentrations are recognized: (1) the main basin, and (2) the subsidiary basin. The main basin embraces the producing districts of Stassfurt, Sud Hartz, Halle, and Hannover-Braunschweig. From J. P. SMITH, Member AIME, is Clzief Geologist, U. S. Potash Co., Carlsbad, New Mexico. New York Meeting, February 1948. TP 2621 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 26, 1948. 40 to 45 pct of the German production comes from this basin. The Werra-Fulda district, producer of 50 pct or more of the German potash, lies in the subsidiary basin. Salt Stratigraphy: Five commercial potash zones or beds are recognized. The three beds present in the main basin are: The Stassfurt bed that occurs near the top of the older salt, and the Ronnenberg and Riedel beds in the younger salt occurring 200 to 300 m, respectively, above the Stassfurt bed. The Stassfurt bed is found over the entire main basin, while the Ronnenberg and Riedel are restricted to the Hannover area. Two potash beds occur in the Werra basin. These are the Thuringian, or lower bed and the Hessen or upper potash bed that occurs 60 m above. These beds lie 210 and 150 m, respectively, below the position of the Stassfurt bed, and are restricted to the Werra basin. The upper bed is 2.5 to 11.5 m in thickness, and the principal ores are hartsalz with varying thicknesses of carnallite. The lower bed averages 3 m in thickness, and contains hartsalz. The upper bed is presently being mined, and the

Jan 1, 1951

By N. Pessall, A. D. McQuillan

The phase relalionsllips in an isothernzal section of the Ti-Zr-H system at 750°Chave been investigated by measurement of hydrogen equilibrium pressures. The resulting diagram indicates that the hydride phase has an anomalously wide range of homogencity extending from 66.6 to 30 at. pct H in alloys containing about 15 al. pet Zr. Measurement of the heat of solution of hydrogen as a function of alloy composition in ß-phase alloys indicates no anomalous behavior in the region of 15 at. pet Zr, and suggests that the extensive range of homogeneity in the hydride phase at about this composition must he attributed to an enhanced stability of the, hydride phase. THE manner in which titanium and zirconium react with hydrogen and the constitutional diagrams of the two metal-hydrogen systems are qualitatively very similar,'-6 as can be seen from Fig. 1 which shows the constitutional diagrams of the two systems. Quantitatively, however, there are some differences. For example, the exothermic heat of solution of hydrogen in ß titanium is smaller than that in ß zirconium, and consequently the equilibrium hydrogen pressure of a Ti-H alloy is higher than a Zr-H alloy at the same temperature and hydrogen concentration. Other differences manifest themselves in the hydride phases which exist at high hydrogen concentrations. In the Ti-H system, above room temperature, there exists only a single hydride phase in which the metal atoms are arranged on a fee lattice, but in the zirconium system there are two hydrides, and whereas the hydride of lower hydrogen concentration has a fee structure, the higher hydride has a face-centered tetragonal structure. The tetragonal hydride retains its stability up to temperatures in excess of 450oC.7 From the foregoing, it would be expected that the constitutional diagram of the ternary Ti-Zr-H system would have a very simple form, especially as titanium and zirconium are completely miscible in both the a and ß forms.8 The present work, which consists of a study of an isothermal section of the ternary system, was carried out in order to check the assumption frequently made that the electronic structure of the two metals and the mechanism by which hydrogen is held in solution in the metals is the same for each. Although this proved largely to be true, certain inter esting and unexpected features of the ternary system emerged which must be explained before we can really say that the reactions of titanium and zirconium with hydrogen are fully understood. EXPERIMENTAL PROCEDURE The most convenient method of studying hydrogen-metal systems is by the measurement of the hydrogen pressure in equilibrium with the hydrogen dissolved in the metal as a function of hydrogen concentration and temperature. In binary systems, the results are easily interpreted in terms of alloy constitution, since two-phase regions can be recognized by the fact that the hydrogen pressure at constant temperature does not vary with the hydrogen concentration in the alloy when it is in the two-phase condition. This criterion does not apply in ternary systems, but there is usually a marked change of slope in the isothermal pressure-composition curves when a phase boundary is crossed, and with care, and a knowledge of the limiting binary systems, the phase structure of the alloys can usually be deduced. In the

Jan 1, 1962

By Arthur G. Levy, Henry M. How

The purpose of the investigation on which this paper is based is to determine whether the structural change which occurs in the slow cooling of steel below the transformation range has an important effect on its engineering properties. We recognize two distinct things which occur in steel when it is brought from above to below the transformation range, first, the transformation proper, that is, the breaking up of the austenite or solid solution of the cementite in the remainder of the iron, and the liberation of its components as undissolved cementite and as ferrite or alpha iron; and second, a structural change consisting in the gradual coalescence of the ferrite and cementite respectively into larger and larger separate masses. Let us distinguish these from each other by speaking of them as " the transformation " and " the structural change " respectively. If the cooling is at all rapid the unevenness of contraction induces severe stress; so that in a sense a slow cooling has a third influence, the prevention of such stress. This transformation from austenite to ferrite plus cementite can complete itself only below the transformation range; and, because this structural change is a change in the structural arrangement of the products of that transformation, it too can complete itself only at temperatures below that range, say below 725°; and of these temperatures it is only those between 600° and 725° that give the metal sufficient mobility to permit this structural rearrangement to progress with ally rapidity. The transformation is now known to be rapid, but the structural change is relatively slow. The transformation, the liberation of the dissolved cementite from the state of solution in the austenite to a free state, leaves the steel structurally in the

Jan 1, 1913

By W. I. Duvall

A brief review of the resonant frequency and ultrasonic pulse methods for obtaining elastic constants of rock samples shows that the equations for an iso-tropic elastic solid commonly used to calculate Young's modulus, modulus of rigidity and Poisson's ratio can result in appreciable error if the rock is even slightly anisotropic. Consideration of the equations that relate bar velocities and free medium velocities to elastic constants for orthotropic, transversely isotropic and isotropic solids shows that a combination of the two methods can be used to determine average elastic constants for a single sample of rock. The determination of elastic constants in different directions requires a large number of tests on oriented samples. The use of both the resonant frequency and ultrasonic pulse methods is recommended so that the determination of both Young's modulus and modulus of rigidity is independent of the determination of Poisson's ratio. The dynamic elastic constants of rock can be determined in the laboratory from measurements on small samples which may be in the form of right circular cylinders (diamond drill core). Either the resonant frequency6 or ultrasonic pulse method1 can be used to determine the longitudinal and shear velocities in the same specimen. The resonant frequency method provides a measure of the longitudinal bar velocity, V,, and the torsional bar velocity Vt; whereas the ultrasonic pulse method provides a measure of the free medium longitudinal velocity, Vp, and the free medium shear velocity, V, . The elastic constants (Young's modulus E, modulus of rigidity G, and Poisson's ratio v) are calculated from the density of the specimen, p, and one of the pairs of velocities by means of equations from isotropic elastic theory. For the resonant frequency method the equations are: It should be noted that Eq. 5 is derived from Eq. 4 and 6 and the relation between the elastic constants for an isotropic solid as given by the first part of Eq. 3. The in situ determination of dynamic elastic constants is accomplished by generating a complex seismic pulse in the rock and measuring the arrival times for the longitudinal and shear phases of the pulse at two distant points.5 From these travel times and the distance of the travel path both Vp and Vs are determined. The density of the rock is determined from samples in the laboratory, and Eq. 4 to 6 are used to calculate the elastic constants. These three methods involve the assumption of isotropy and perfect elasticity, and require the use of the relation v = (E/2G) - 1, which holds only if the elastic constants are the same in at least two directions. The calculation of v by means of Eq. 3 introduces considerable error, as a 1% error in V, and V, results in a 20% error in v. If frequencies for samples with a length-to-diameter ratio greater than four and a length greater than 8 in. are measured carefully, the experimental error can be kept to 1%. However, it is not unreasonable to expect that the variation in Vb and Vt with direction may exceed 1%. Thus, for even a small percentage of anisotropy the use of Eq. 3 can result in considerable error in v. The calculation of v by Eq. 5 also involves some uncertainty as a 1% error in Vs and Vp can result in a 6% error in v. By means of the pulse method both

Jan 1, 1965

By R. Van A. Mills

ONE of the most important problems facing the petroleum industry is the profitable recovery of oil that is left underground by the ordinary methods of production. It is true that vast quantities of oil are being recovered from fields previously considered depleted by the pressure restoration method, the most widely applicable -and most successful means of obtaining greater recoveries that has thus far been, developed. But notwithstanding the progress that is being made in the field applica¬tion of this method there is urgent need for a better understanding of the fundamental principles that are involved. To meet this need the Petro¬leum Experiment Station of the U. S. Bureau of Mines at Bartlesville, Okla., during the past two years has conducted a series of intensive laboratory and field investigations. The larger part of the work has been carried on in the laboratory to supply the much needed information upon fundamental principles, information which few if any of the oil companies are in a position to supply for themselves. In all of this work the Bureau is endeavoring to correlate the results of laboratory investigations with those in the field, using the results of one to guide or check the other. This paper is primarily a progress report, briefly outlining the Bureau's methods of study, the laboratory and equipment in use, the preliminary problems that had to be solved in order to attack the major problems at hand, the methods of attacking some of the major problems, and some of the results of the investigations to date.

Jan 1, 1928

By Charles Colcock Jones

In the winter of 1902, while occupying the position of mining and examining engineer for the Mountain Copper Co., Ltd., of Keswick, Cal., I had .occasion to discuss with the General Manager, among other things, the question of the enormous waste of sulphur in smelting cupriferous pyrite ore, and to cast about for means to utilize this waste or to render the fumes innocuous to vegetation. The decreasing rate of production of California farms, the consequent need of fertilizers, and the opportunity thus offered to utilize large quantities of sulphuric acid in the manufacture of superphosphates naturally brought the subject to the practical and commercial side of phosphates. I was informed that the company had made efforts to find phosphates in the West, without success. I advised as a start placing inquiries for phosphate deposits on the Pacific coast in the current mining journals. This was done, with the result that in January, 1903, from an advertisement in the Mining and Scientific Press we got track of a deposit in Rich county, Utah, through T. J. Wilson, of the Southern Pacific railroad in San Francisco. As soon as snow in the mountains would permit, in May, 1903, I undertook an examination of the property, with the result of recognizing the importance of the find, in spite of its lack of facilities for transportation at a commercial figure. On June 15, 1903, I concluded my report by saying, "This may be one of the world's deposits of phosphates." On Nov. 17, 1903, I concluded my report for the season in the following words : " I have now no hesitation in saying that I believe the Carboniferous formation so largely developed in the Wasatch mountains of Utah and the mountains of the Great Basin will prove to be one of the greatest storehouses of phosphoric acid in the world." Early History. In the summer of 1897 R. A. Pidcock, a mail carrier of Ogden, Utah, while on a prospecting trip camped on " 12 mile," a branch of

Jan 1, 1914

By Henry M. Howe

In my original paper, Piping and Segregation in Steel Ingots, I pointed out1 among other things that, in view of the slighter stretching (virtual expansion) of the crust, and greater opportunity for sagging, there should be less piping in broad than in narrow ingots, and less in slowly-cooled ingots, e.g., those cast in pre-heated sand molds, than in those which cool quickly, e.g., those cast in iron molds. A. A. Stevenson said that neither of these predictions agreed with his own experience. In particular, in a picture which he showed of a wide and of a narrow ingot cast from the same ladleful of steel: the wide ingot had certainly piped much more deeply than the narrow one. At the time I did not see the explanation of these discrepancies, but further reflection makes it evident. One of the most important elements in determining the depth of the pipe is the degree of " top-lag," that is, the degree to which the solidification of the top of the ingot lags behind that of the bottom. Through this lagging the steel of the upper part of the ingot is able to run down and fill the pipe below as fast as it forms. To the importance of this lagging I called attention in my original paper.' Sand us. Iron Molds.—If we compare two like ingots, one cast in an iron and the other in a sand mold, we see that the top-lag is much greater in the former than in the latter, because in the former the lower part of the ingot is cooling off fast while the metal is running into the upper part. It is perhaps easier to look at this as a case of the solidification of the hot-

Jan 1, 1910

By G. M. Schwartz, D. M. Davidson

THE Duluth gabbro outcrops containing sulphides of copper, nickel, and iron are located on both sides of State Highway No. 1 an airline distance of 8.5 miles southeast of Ely in northeastern Minnesota. The region of known sulphide occurrences includes parts of sections 5, T. 61 N., R. 11 W., and parts of sections 25, 26, 32, 33, and 34, T. 62 N., R. 11 W. These sections, given in Fig. 1, are all in Lake County, Minnesota. Part of the area, which lies entirely within the Superior National Forest, is shown on the topographic map of the Ely quadrangle. The original discovery was made in 1948 when a small pit was opened in weathered gabbro rubble for use on a forest access road. A shear zone had caused unusual decomposition in this glaciated area, and the resulting copper stain was noted by Fred S. Childers, Sr., an Ely prospector, who began searching the outcrops along the base of the intrusive. He was joined in further exploration by Roger V. Whiteside of Duluth. In the summer of 1951 a small diamond drill was moved into the area and a hole 188 ft deep was drilled, passing through 11 ft of glacial drift into sulphide-bearing gabbro. This paper is a preliminary report on the geology of the newly discovered ore. The Duluth gabbro is one of the largest known basic intrusives and may be defined as a lopolith.' It extends northeastward from the city of Duluth as a great crescent-shaped mass that intersects the shore of Lake Superior again near Hovland, 130 miles to the northeast, see Fig. 2. The distance around the outside of the crescent is nearly 170 miles. The form of the intrusive is simple at Duluth where it ends abruptly north of the St. Louis River; at the east end, however, the gabbro splits into two elongated, sill-like masses separated mainly by lava flows and characterized by minor irregularities. The outcrop reaches a maximum width in the central part where it is about 30 miles across, and a maximum thickness of about 50,000 ft. It may be significant that the sulphides occur at the base of the thickest part. The lopolith has segregated into rock types ranging from peridotite to granite. The most abundant types are olivine gabbro, gabbro, troctolite, anortho-site, and granite. Of lesser importance quantitatively are peridotite, norite, pyroxenite, magnetite gabbro, and titaniferous magnetite. Grout estimates that two-thirds of the gabbro at Duluth is olivine gabbro. Variations in the percentages of plagio-clase, augite, olivine, and magnetite-ilmenite constitute the only essential differences found among the basic rock types. The predominant mineral is plagioclase, mainly labradorite. Plagioclase and olivine seem to have crystallized early, and the olivine rich rocks, usually troctolite, are found in the lower part. Segregations of titaniferous magnetite are abundant near the base of the gabbro along the eastern part and also occur far above the base. These have recently been described in detail by Grout.' Near the top, segregation has produced a gradation to granite, or "red rock," as it is known locally. This consists of quartz, red feldspar, and hornblende. The red rock forms a zone with a maximum width of nearly 5 miles but is quantitatively unimportant from Duluth northward for 35 miles. In Cook county, where the gabbro splits, each of the two sill-like masses has a red rock top somewhat thicker in proportion to the gabbro below than in the main central mass. The intrusive ranges from coarse to medium in grain size and from granitoid to diabasic in texture. Throughout much of the Duluth gabbro in Minnesota banding and foliation are well developed, as Grout has emphasized.V he bands are mainly a result of variation in the percentage of minerals, as in troctolite with alternating bands high in olivine and in plagioclase. A few bands may consist largely of one mineral, as is true of some segregations of magnetite. Many of the banded rocks show a clearly developed parallelism of platy plagioclase crystals, and both banding and foliation are believed to conform to the floor of the lopolith. Throughout its extent in Minnesota the Duluth gabbro dips east and south toward Lake Superior. It is generally believed to extend beneath Lake Superior and is found as a smaller mass exposed along the north side of the Gogebic district in Wisconsin and Michigan. The dip at and near the base ranges along most of its length from 20 to 40°, but at places the internal banding dips even more steeply. The dip of the upper part is much less, and if it is assumed that the flows along the north shore of Lake Superior are a dependable indication, it does not exceed 15". The formations shown in Table I which are intruded by the gabbro range from Keewatin to Middle Keweenawan in age. They present a significant picture. At the top, the gabbro and its accompanying

Jan 1, 1953