Search Documents

By Charles Hardy

ACTIVATED alumina is an aluminous material which may be 1 classified chemically as a partially dehydrated aluminum trihydrate having a high porosity and a perma¬nent physical structure. In general, it may be employed effectively and economically for the complete removal of water vapor from gases and vapors; for the selective adsorption of certain as especially those of the higher boiling points, and as a catalyst or catalyst carrier. Other forms of alumna are available and may be employed similarly but not so effectively nor can reactivation be accomplished with uniformity over many cycles without deterioration. The adsorption-reactivation cycle of activated alumina can be repeated many times without any apparent depreciation ill

Jan 1, 1934

By H. R. Stahl

FIVE mills are operated in Southeast Missouri by the St. Joseph Lead Co.; these have a total rated capacity of 24,300 tons per day divided as follows: Federal, 12,000 tons; Leadwood, 4800 tons; Desloge, 3600 tons; Bonne Terre, 2400 tons; and Mine La Motte, 1500 tons. These concentrators are similar in a general way, differing mainly in size and type of equipment and in minor variations in flow sheet. No attempt is made rigidly to standardize procedure in the various mills in spite of a general similarity in the ores. Each mill may be regarded as a separate laboratory in which new ideas and changes may be tried. A generalized description of the process is given, noting important differences in procedure at the various plants. The concentration process may be divided into five main stages: dry crushing, wet grinding, desliming and classification, tabling, and flotation.

Jan 1, 1947

By Philip E. LaMoreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride.

Jan 1, 1950

By William J. Coulter

WITHIN the past thirty years the United States has been involved in two tragic, vicious, and costly world wars. To make the world safe for democracy was the reason given for our participation, but the confusion and misunderstanding that prevails all over the world today suggests that war is not the proper approach to the attainment of that utopia. These conflicts were conceived and prosecuted by nations far advanced in civilization and culture. Their best manhood was sacrificed, a staggering tax burden was saddled on their peoples, huge financial losses were incurred, destruction of property was appalling, and cultural and peaceful scientific advancement received a setback that may require centuries to retrieve. Therefore, some basis is established for the conclusion that progress in the past fifty years has been most outstanding in the development of instruments used for death and destruction, and that progress in this direction between the two World Wars would indicate that the next war will go far toward total destruction of world civilization.

Jan 1, 1946

Willet G. Miller, Toronto, Canada (communication to the Secretary): In his interesting paper Mr. Lindgren says: " As to ultimate results, it would seem as if we should be justified in concluding, with Prof. Suess, that the gold-supply of the world will gradually decrease if no further important improvements are made in the processes for the extraction of this metal; but regarding events so far distant no predictions may safely be made." It seems to the writer that no very important improvements require to be made in order at least to keep up the present production for many years to come. In many parts of the world there are large deposits of auriferous material which can be worked if present conditions are slightly changed. In the territory occupied by the Archean protaxis of the Province of

Jan 1, 1903

By Joseph Hartshorne

EVER since the introduction of the Siemens regenerative furnace, it has been recognized that a certain amount of gas is lost each time the furnace-action is reversed. This loss comes, first, from the gas which passes through the free connection between the stack and the gas-main, which exists during the time the reversing-valve is turning over; and, secondly, from the gas which is in the chamber and flues, from the hearth to the reversing-valve, and which flows back into the stack when the valve is reversed. The amount lost each time is, of course, small; but, since a furnace is reversed from four to six times every hour for, say, 300 days in the year, the aggregate is large enough to be well worth attention. The estimate has been published' that, in Germany alone, the loss from the first of the above causes amounts to 500,000 marks per year. The loss from the second cause is, of course, much greater. A process for saving this entire loss, in use at Teplitz, Bohemia, for about three years, would seem to be of value even in this country, where coal is cheaper and where the small economies are not watched as closely as they are in Europe. This process, invented by Mr. Adelbert Kurzwernhart, late Technical Director of the Teplitzer Walzwerk, has been worked out with thoroughness. The loss from each cause can be calculated very closely for any particular furnace, and the results to be expected from the process ascertained. It can easily be decided, therefore, whether it is worthwhile to adopt it under any given conditions. The amount of chamber-gas lost depends upon,-(1), the cubic contents of the chamber, ports and flues upon one side of the furnace, up to the reversing-valve (deducting, of course,

Mar 1, 1906

By Gordon B. Brox, Joseph F. Mcaleer, Charles C. Goddard, Edward P. Shea, Robert G. Ingersoll, Lester G. Zeihen, George J. Burns, John M. Guilbert, Richard N. Miller, Charles Meyer

The Boulder batholith is a composite intrusive in which the Butte quartz monzonite is the dominant rock type. Quartz porphyry dikes intruded the quartz monzonite in directions which were subsequently followed by the eastwest- striking Anaconda system of veins, the earliest major veins in the district. Anaconda veins are faulted by northwest-striking veins of the Blue system, which are most prominent in the central third of the district. Anaconda veins are the major producers in the western third of the district and also in the eastern third, where the "horsetail" zones break off from them. Individual oreshoots are thousands of feet long as well as deep on both systems of veins, but they are generally more persistent and thicker on the Anaconda veins. Viewed broadly, the mineralization in the big veins is arranged in crudely concentric zones of zinc and manganese around a central zone of copper. Only slightly offset from these zones, but earlier structurally, is a zone in which quartz-molybdenite veinlets are prominent. This zone tops at about the 2800 level and widens downward. The pattern of distribution of Cu-Fe-S series minerals in the large veins of the copper zone is not symmetrical with respect to the metal zones. There is a fringe of chalcopyrite-bornite all around the copper front. However, within the copper zone, pyrite-chalcocite-enargitecovellite- digenite assemblages are prevalent near its eastern edge from the 3800 level to the surface, whereas deep on the large Anaconda veins in the western part of the copper zone, chalcopyrite is dominant. Here the chalcopyrite grades upward into bornite-chalcocite ores and eastward into the high-sulfur assemblages of the Leonard mine. Sericite-biotite-K-feldspar alteration envelopes, containing up to about 2 per cent copper as chalcopyrite, are present on some of the quartz-molybdenite veinlets at deep mine levels in the molybdenite zone. These envelopes contrast sharply mineralogically and chemically with the later sericitic and argillic alteration envelopes around Main Stage veins. K'0-Ar'0 ratios indicate that they may be older by about 4 m.y. Secondarily enriched copper ores are mined in the Berkeley pit in the southeastern part of the district. At the present time they account for about half of Butte's production of copper.

Jan 1, 1968

By T. E. Leontis

Several publications1-7 during the past few years have demonstrated the markedly greater effect of cerium, as compared to all other alloying elements, in enhancing the strength and creep resistance of magnesium at elevated temperature either with or without the presence of other elements. In the work reported in Ref. 1-6, the cerium was added in the form of Mischmetal, which contains all the rare earth elements in essentially the same proportions as they occur in monazite sand, the principal ore of these metals. Mellor and Ridley7 have presented the creep characteristics at 200°C of magnesium alloys prepared both with pure cerium and with Mischmetal. Up to the present time, however, no comprehensive study of the effect of the various component elements of Mischmetal on the properties of sand-cast magnesium has been made. This hiatus in magnesium technology undoubtedly is associated with the difficulty in obtaining the rare earth metals separately. This investigation provides such a survey, the object of which was to determine which of the elements present in Mischmetal contributes the greatest effect in developing high strength and high resistance to creep at elevated temperatures. Toward this end the compositional variation of these properties has been determined as a function of temperature in the following alloy systems: 1. Magnesium-Mischmetal 2. Magnesium-cerium-free Misch- metal 3. Magnesium-didymiuin 4. Magnesium-praseodymium- lanthanum 5. Magnesium-cerium 6. Magnesium-lanthanum This designation, based on the names of the metals as furnished by the producer, is used throughout the paper in order to avoid the complicated system of listing all the elements present in the more complex alloys. The composition of the metals and the alloys is discussed in detail below. Preparation of Alloys ALLOYING INGREDIENTS The chemical composition of each of the six alloying ingredients used to prepare the alloys reported in this paper is given in Table 1. In each case, the percent total rare earths, percent cerium, percent neodymium, percent praseodymium, and percent thorium were determined in addition to the listed impurities. The percent lanthanum was determined by difference from the total rare earth content and consequently includes the other elements (samarium, terbium, yttrium, etc.) present in Mischmetal. These additional elements, however, seldom amount to more than 1 to 2 pet of the total rare earth content of Mischmetal. The iron content of the Mischmetal is considerably lower than that of the other metals. This grade of Mischmetal is now readily available. The metals are listed in the order of decreasing complexity. Elimination of the cerium from Mischmetal results in what the trade calls "Cerium-free Mischmetal." Carrying the separation a step further by eliminating the lantha-

Jan 1, 1950

By J. W. Taylor, E. G. Zukas

THE results of shock-loading studies on copper were reported several years ago by smith. In his experiments, Smith found that there was a correlation between the shock direction and the orientation of twins which the shock produced. By using free-surface-type shots in which the free surface of the specimen was not normal to the shock direction, he showed conclusively that twinning of copper in impulsive loading was caused by the rarefaction wave. Similar tests with iron, however, showed that it twinned during compression. More recent studies of iron2 and on Fe-Si single crystals3 have shown that twinning can be suppressed in these materials by shock loading at pressures high enough so that the velocity of the shock wave exceeds the elastic-wave velocity. From these observations, it appeared that twinning was caused by the shear stresses present in the zone undergoing adjustment from one-dimensional to three-dimensional loading. At high pressures, such a zone becomes so thin that there is insufficient time for the relatively ordered motion of atoms involved in twinning to occur. Twinning in copper, therefore, cannot be produced by a single compressive shock wave because resolved shear stress large enough to create twins exists only for a very short time (0.01 psec or less) before the pressure increases suddenly and loading becomes essentially hydrostatic. (A typical pressure vs time record for a copper shot, illustrating the short rise time of the compression wave, is shown in Fig. 1.) If, on the other hand, a second shock wave can be created in a precompressed sample, then the new elastic limit is several kilobars,4 and a resolved shear stress sufficient to cause twinning should be maintained for an adequate time period (0.1 psec or more). This experimental situation can, in fact, be realized. The experimental arrangement used to do so is shown in Fig. 2. By utilizing the pressure transformation in Fe-V alloys, it was possible to shock-load the copper in compression while the copper was already precompressed. In the first test, an 8 wt pct V-Fe sample was used as a driver for loading the copper, and the copper was exposed to the following series of compressive shocks: 1) an elastic wave of about 8 kbars, which is usually ignored in shock studies; 2) the pressure transformation wave for the driver of 200 kbars; and 3) the driving shock wave of 270 kbars pressure. Metallurgical determination of the angular twin distribution, shown in Fig. 3, with respect to the shock direction and the shock rarefaction direction (which was 23 deg from the shock direction) showed that twinning took place

Jan 1, 1965

By J. L. Lummus, Frank O. Jones

A field procedure for determining graphite in drilling mud is presented which is sensitive to 0.25 lbs/bbl and accurate to 20 per cent. The method, utilizing oil flotation principles, is suitable for use in all oil-free water base muds except those containing ligno-sulfonates, lignites, or surface active agents. INTRODUCTION Graphite was proposed as a drilling lubricant as early as 1940, but has not been used extensively until recently.' Graphite has been substituted for oil in certain instances to avoid oil contamination of core samples since it has been found that graphite does not interfere with routine core analysis. A major difficulty in using graphite is the lack of a satisfactory field test for determining the concentration of graphite in mud. DISCUSSION OF METHOD Several possible methods of analysis were investigated, including chemical separation, density fractionation, radioactive tracers, and oil flotation.', ' The investigation indicated that a satisfactory method for field use could be devised using an oil flotation method. It was found that toluene shaken with a highly diluted mud sample would recover sufficient graphite to be apparent in the oil phase. Refinement and standardization of technique made it possible to detect as little as 0.25 lb/bbl graphite and to estimate graphite content to within 20 per cent by using a visual comparison method. The test is limited to oil-free water base muds. Quebracho, phosphates, or barytes in the mud do not interfere with the test but surface active agents, lignosulfonates' and lignites evidently render !he graphite water-wet so that none may be recovered by oil-flotation. PROCEDURE Instructions for determining graphite in mud: 1. Collect representative one gallon sample.- from mud stream. Transfer immediately 350 ml portions of this Sample into four mixing cans labeled A, B, C, and D. Measure out graphite (same as is used to treat mud) for addition to cans as indicated below, using either a specially designed scoop or a balance. Can: A B C D Grams Graphite to Add: none 2 4 6 Stir samples B, C, and D for 15 minutes with propeller type mixer. 2. Clean and rinse well with water four 250 ml volumetric flasks labeled I, 11, 111, and IV. Using a 5 ml hypodermic syringe, transfer the indicated volume of samples from cans A, B, C, and D into designated flasks as follows: From Can: A B C D To Flask: I II III IV Add This Volume of Mud: 4 ml 2 ml 2 ml 2 ml 3. Measure 100 ml fresh or distilled water to each flask and swirl gently to disperse mud. Add exactly 5 ml toluene to each flask. Stopper and shake each

Jan 1, 1953

DeLamar, the largest silver mine in the United States outside the Coeur d’Alene District in Idaho, came into production in April 1977. It is a joint venture of Earth Resources Company and Canadian Superior Oil Co., with Earth Resources being the operator. The property is a consolidation of several old operations dating back to the 1800s; the better known of these are the DeLamar and Sommer-camp mines. DeLamar is situated in southwestern Idaho near the Oregon border in the Owyhee Mountains, 88 km (55 miles) southwest of Boise, Idaho. Heavy snowfalls and very low temperatures are common in the wintertime. Planned production was 77,500 kg (2.5, million oz) of silver and 5 13 kg (16,500 oz) of gold per year. Expected life at a milling rate of 1,540 mtpd (1,700 stpd) was 20 years, with an ore grade of 144 g Ag and 1.58 g Au per mt (4.2 oz Ag and 0.046 oz Au per st). Present production is at the rate of 1,900 mtpd (2,100 .stpd). The total cost to bring the mine into production was reported to be approximately $22 million, and the mill was reported to have cost about $10,000 per daily ton of design capacity. At DeLamar, naurnanite (Ag2Se) is the principal silver .mineral occurring with acanthite (Ag2S) disseminated through quartz veins and a silicified rhyolitic ash-flow tuff of Miocene age. The mineralization is relatively iron and manganese free and is readily amenable to cyanidation giving recoveries of 85% silver and 92% gold, which occurs free. When the plant was started, considerable difficulties were encountered in handling the wet sticky ore because of the high clay content. Following primary crushing, the ore is stockpiled. Due to the sticky nature of the ore, the vibrating feeders initially installed under the stockpile were replaced by a reclaim hopper and an apron feeder which was fed 24 hours a day by a front-end loader. The minus 200 mm (8 in.) ore is fed to a 5.5 m by 2.75 m (18 ft by 9 ft) autogenous mill followed by a 2.75 m by 4.57 m (9 ft by 15 ft) ball mill and cyclones. The mills are equipped with 750 kw and 520 kw (1,000 hp and 700 hp) motors. Both mills discharge to the same cyclone feed sump and a portion of the cyclone underflow is returned to the autogenous mill. Cyclone overflow, which is 20% plus 74 microns (200 mesh), is leached in four agitators in series for 72 hours (45 hours at the 2,100

Jan 1, 1981

By H. B. Northrup

Mineral Industries Extension instruction was pioneered by The Pennsylvania State Colleges Extension work was organized in 1893 and constituted what is believed to be the first vocational adult educational effort in that field in America. From 1894 to 1899, twenty-seven extension bulletins were printed and distributed free for the benefit of classes in the coal-mining industry and the records show that free lectures wore delivered by a corps of teachers of the mining department of the College "to the mining employees at their customary lace of assembly upon matters of interest to them in their occupation." In 1899, the State Legislature reduced the appropriation to the College and therefore the extension pamphlets and lectures were discontinued. Several sporadic attempts were made to resume the extension services in mining through industrial grants for travel and publications, and through voluntary contributions by members of the resident staff. The work. consisted mainly of lectures and demonstrations and served the purpose of creating the desire for more training and information of a more formal character. In 1928, the nave of the school was changed, by trustee action, from School of Mines and Metallurgy to the School of Mineral Industries and the working structure of the school was organized under the three functional collaborating headings: Resident Instruction, Correspondence and Extension Instruction, and Mineral Industries Research. The three functional bodies are separate, yet interdependent. The Federal Smith-Hughes law, passed in 1917, made Federal and State funds available for vocational educational work. Mining extension was revived in 1919 and the College employed one full-time extension professor to reorganize the work and instruct the classes. In 1923, the State Department of Mines and the State Department of Public Instruction entered into, a formal agreement with the School of Mineral Industries to assist the College in its extension program.. Classes were organized to study the State mining laws and State Department of Mines' previous examination questions and answers, in preparation for coming state examinations for certification of competency as underground officials. Mimeographed lesson material was used at first, and in 1947 and 1929 mining instruction and mining teacher-training lessons were printed. In 1931, the extension activities of the school were placed on an organized basis compatible with the newly formed school organization and a director was appointed to tale full charge of the work. During that year, at a conference in Harrisburg, an agreement was consummated between the State Departments of Public. Instruction, Mines, Labor and. Industry, and the College whereby extension classes in the field of the, mineral industries could be organized by the College, throughout the State, under "public supervision and. control," in close cooperation with the State Department.

Jan 1, 1941

By Richard M. Foose

FIVE miles southwest of Mt. Holly Springs, Cumberland County, Pennsylvania, the Philadelphia Clay Co. has been mining and milling a white clay since 1896; for use in white cement, as a filler in rubber, pigment and paper, in the manufacture of insecticides, and for other minor purposes. Until late in 1942, when the mine was abandoned because of labor shortage, combined underground mining and surface stripping produced approximately 30,000 tons of clay a year, of which 10,000 tons were refined in the mill. GEOLOGY Lower Cambrian Antietam quartzite and the Montalto quartzite, stratigraphically older, trend N.55°E. and make a sharp 1600-ft. anticlinal ridge of the South Mountains. The Tomstown dolomite overlies the Antietam quartzite on the southeast flank of the anticline, which is displaced near its crest by a steeply dipping oblique fault. Erosion of the less resistant Tomstown formation has resulted in a narrow valley at an elevation of 700 ft. Directly on top of the Antietam quartzite and at the base of the Tomstown formation is a zone of sandy white clay, lenticular along the strike of the formations, ranging in thickness from 10 to 300 ft. within a mile. All of the formations dip steeply to the southeast, from 65° to vertical. The clay crops out at an elevation of about 1000 feet. ORIGIN AND CHARACTER The uppermost part of the Antietam formation is sericitic and schistose at many places, and at all these places weathering is in an advanced stage. The clay is the residual product of weathering of this sericitic quartzite or sandy schist. The crude clay has the physical aspect of a sandy kaolin, but there are large areas in the clay formation that are low in free silica, and commonly the 30 ft. adjacent to the Antietam quartzite is notably free of silica. The overlying Tomstown dolomite has been weathered almost completely to a mixed yellow and brown clay, which carries a zone of nodular and chunky limonite and manganese ore, 4 to 12 ft. thick, about l00 ft. from the contact with the white clay. In mining, this zone is an important "marker," indicating where the white clay may be expected in an advancing tunnel. The contact of the white clay formation with the yellow and brown clay of the Tomstown formation is relatively sharp, although the line of contact is irregular and therefore responsible for the lenticular character of the white clay formation. Following is an analysis of the refined clay containing less than one per cent of moisture when dried at 212°F.: Si02, 67.05 per cent; A1203, 22.27; Fe203, 0.40; CaO, 0.00; Ti02, 1.05; MgO, 0.52; Na20, 0.04; K20, 0.88; ignition loss, 7.65; total, 99.86.

Jan 1, 1944

TO THE BOARD OF DIRECTORS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS Gentlemen -The Institute was founded 54 years ago "with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained" At least once a year it is well to take stock of our assets, review our performance and determine how well we are now carrying out the purposes of our Founders There can be no question as to the work the Institute has done and is doing in promoting the arts and sciences in the fields of mining and metallurgy One needs only to contiast the methods, the labor and the costs of a half century ago with those now to visualize how far we have gone in the development of accurate technology and sound economics in mineral and metal production The great mines, mills and smelters of the present, handling individually thousands of tons per day, would have been impossible except for the accumulation of knowledge, the development of theory, and the improvement in practice that has charac¬terized the period since the foundation of the Institute The United States has prospered in the last half century greatly, and this has been due not merely to the possession of great natural resources, but to these resources being reduced to possession and put to work The absence of customs barriers and the freedom of trade across the whole width of this great continent has been an important factor in the growth of our wealth Unrestricted interchange of goods has permitted each citizen to draw on the resources of the whole country However, these are but subsidiary causes of prosperity The free interchange of scientific and technical data, by making the whole body of facts and theory available to each worker, has made this quick and unrivaled development possible In promoting this free trade in knowledge the Institute may claim a large place without fear of denial The 72 volumes of TRANSACTIONS, the special volumes, the bulletins and the other pub¬lications that have been issued, include a store of knowledge of the arts and sciences related to the pioduction and use of metals and minerals not duplicated elsewhere The large list of foreign members-1746 in number-few of whom ever have opportunity to attend meetings and all of whom derive their main benefits from membership through the pub-

Jan 1, 1923

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

By J. D. Milburn, H. J. Hill

In quantitative interpretation of electrical logs the presence of clay minerals introduces an additional variable which further complicates an already complex problern. Although recognizing the difficulties introduced as a result of the heterogeneity of natural sediments and despite the present incomplete state of knowledge regarding electrochemical behavior of shales, dissemirzated clay minerals and concentrated electrolytes, it was felt that useful empirical correlations might be obtained from experimental investigation. Six typical sandstone formations, having a wide variety of petrophysical properties, were selected for the study. Approximately 45 samples from each formation were selected to satisfactorily represent the range of pore size distribution within the particular formation, As a matter of general interest, four limestone formations were also included in the investigation. Previously proposed equations relating to resistivity, SP and interrelationship of the two phenomena have, where possible, been tested with data obtained in this investigation. These equations do not satisfactorily describe experimental behavior of samples through all degrees of shaliness or throughout the range of brine solution resistivities normally encountered in logging practice. An empirical equation has been developed which quantitatively relates formation resistivity factor to satirrnting solution resistivity, porosity, and "effective clay content." This relation is indicated to be uniformly applicable to clean or shaly reservoir rocks. It is shown that both the SP and resistivity phenomena of shaly samples are related to the sample cation exchange capacity per unit pore volume. The independent chemical determination of this parameter is thus a means of determining the "effective clay content" of samples. Some implications regarding theory and electric log interpretation of shaly sands are discussed. INTRODUCTION The use of electrical resistivity logs as a means for estimating formation porosity is based upon the original work of Archie1. It was shown by empirical methods that the resistivity of a rock, when 100 per cent saturated with brine solution, could be related to rock porosity through the equation, F = Ro/ RW = f-m.......(1) where F, the formation resistivity factor, is defined as the ratio of the resistivity of the 100 per cent water saturated rock, Ro, to the saturating solution resistivity, Rw; f is the ratio of pore volume to bulk volume; and m is the slope of the average line when the data are plotted on log-log paper. This relation was established for relatively shale-free formations containing water having high salt concentrations, and under these conditions F may be considered constant for a given rock sample. Applications of Eq. 1 to interpretation of logs of shale-free formations has been quite successful when satisfactory formation water resistivity data could be obtained. The most readily available means of estimating formation water resistivity is the self-potential log. Conventional methods of SP log interpretation involve correct.

Jan 1, 1957

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart's chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By H. Conrad Meyer

The wizardry of nucleonics has added new and greater dimensions to the almost inseparable "twins"-zirconium and hafnium. So close is their relationship that neither element is found free of the other in any presently known mineral. Although zirconium in the form of its oxide was discovered in 1789 by Klaproth, the metal in an impure, nonductile form was not isolated until 1824 by Berzelius. About 100 years later -1925-van Arkel and deBoer developed and patented a technique for the deposition in vacuo of crystalline, coherent, highly ductile metal of extreme purity on an electrically heated filament through the dissociation of gaseous zirconium tetraiodide. Within the past five years both zirconium and hafnium have been dramatized by the press and in popular science magazines. This has led to the false assumption that practically all of the world consumption of zirconium ores is used in the production of the metals. Recent statistics on the subject show that not over 15 pct of the zirconium ore consumed in 1958 went to ferrosilicon zirconium and zirconium metal. The rest was consumed in refractories, foundry sand and facings and ceramics. The importance of zirconium as a component in compact, relatively lightweight nuclear energy units, such as those now used in the submarine Nautilus,6 is well established. A rival of zirconium metal as a casing for atomic fuels is a newly developed ceramic body. It is claimed to be cheaper than zirconium-to withstand higher temperatures-and to be more resistant to corrosion. Whether such ceramic casings have the required low thermal neutron absorption cross section, high strength and easy formability of zirconium is yet to be demonstrated. Hafnium, because of its low order of abundance and its close chemical relationship to zirconium, was not definitely recognized as a new element until around 1923, despite prior claims. A study of the X-ray spectra of zirconium led to its identification. The circumstances leading to the discovery of hafnium were much less fortuitous than those surrounding zirconium. The more precise tools of arc and X-ray spectrometry lent themselves admirably to the search for elements to fill certain gaps in the periodic table. [ ] Pure, ductile hafnium-a metal similar in appearance to stainless steel-has a specific gravity of 13.3 (zirconium 6.52) and a melting point of 2,200°C. In other respects it closely resembles zirconium except in one important respect which gives it a preeminent position in nuclear energy development, namely, a high thermal-neutron absorption cross section. This explains the necessity of hafnium-free zirconium in atomic piles. The ability of hafnium to capture thermal neutrons makes it an excellent "moderator" of "governor" when used as control rods in nuclear reactors (Table 1).

Jan 1, 1960

By H. L. Gilbert, C. T. Anderson, W. J. Kroll

In a previous paper,' the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.% When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8 in. in diameter. The supply of direct current of high amperage for producing the desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flcxible tubing of the movable electrodc, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decsed to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 19oo"C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica accortling to the reaction: SiO² + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1949