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By E. P. Ferrero

Analyses of 38 crude oil samples from 25 fields in Algeria, Libya, and Nigeria are presented in this report. The 38 crude oils are listed alphabetically by country and field. Also shown are the geographic and geologic sources of the samples analyzed, the companies that supplied the samples, the general characteristics and analytical and computed data, and the production for the fields from which the samples were obtained.

Jan 1, 1966

By James A. West

COUNTRIES of the Near East, with the world's largest and insist prolific petroleum resources, produced nearly 277 percent of the world's estimated total output of crude& oil in 1964 and accounted for about 60 percent of world exports of this commodity. Although petroleum largely dominated the mineral industry of tine area, production of antimony, chromium, copper, mercury, boron, potash, and phosphate rock was of world significance. Production of crude oil in Near East countries reached a record high of 7,520,000 barrels per day in 1964, an increase of nearly 11 percent over that of 1963. Kuwait maintained its position as the leading producer, accounting for almost 28 percent of the area's output. Saudi Arabia, Iran, and Iraq followed with 22.5, 22.2, and 16.5 percent of total area output, respectively. Despite record production, the Near East, proved crude oil reserve remained in excess of 211 billion barrels, or more than two-thirds of the estimated world proved crude oil reserve.

Jan 1, 1966

As far as is known at the present time, important ore occurrences at Mount Isa are restricted to the Urquhart Shale. These occur at Mount Isa itself, and some 13 miles north along strike at the Northern Leases.The primary silver-lead-zinc and copper orebodies occur as adjacent but discretc entities in lithologieally distinct host rocks. The copper orebodies occur in an envelope of "Silica Dolomite", whereas the silver-lead zinc orebodies occur in shale typical of the Urquhart Shale in general.At both Mount Isa and the Northern Leases, secondary lead orebodies occur at thc surface representing primary stratiform silver-lead-zinc sulphide accumulations in the fresh rocks at depth.Secondary copper orebodies are known only at Mount Isa, where they have formed in favourable environments, but unlike the secondary lead orebodies, not in the positions of the former primary mineralization that gave rise to them. The secondary copper is localized in shale remote from the point where the copper was released into solution by weathering. It was derived from very low grade fracture fillings and disseminations of chalcopyrite in the outcropping or suboutcropping crest of the "Silica Dolomite".Primary silver-lead-zinc orebodies arc oxidized without significant transport or secondary enrichment, but secondary copper orebodies arc characterized by considerable transport and extreme secondary enrichment.The original water table stood at approximately 1,150 ft (mine datum) and for the majority of the mine area controlled the base of complete oxidation fairly closely.An oxidized zone approximately 175 ft deep is general in the Urquhart Shale.Structures affecting ground conditions have influenced oxidation and leaching of the silver-lcad-zinc orebodies, and have had effects vital to the formation of secondary copper orebodies.

Jan 1, 1966

By Norman G. Foster

The mass spectra of four tertiary butyl substituted thiophenes are reported. A comparison and contrast with earlier structure correlations made by API-RP48 mass spectroscopists is presented. The fragmentation routes of these types of molecules are discussed and explained in terms of existing theories in mass spectrometry. Low ionization voltage data are presented to support the mechanistic picture developed. Structures are inferred about some of the ions, and these are correlated with existing theories. Metastable peaks in the spectra are used to support the fragmentation paths. The presence of doubly charged ions in the spectra is noted and the possible implications toward mechanisms discussed. The general picture of simple, small fragments leaving the ion moiety upon further fragmentation is developed in detail. Some suggestions are presented for further work utilizing isotopically labeled molecules to establish firmly the general picture of fragmentations of the alkylthiophenes.

Jan 1, 1966

By Harry R. Johnson

Laboratory experiments were conducted to study the carbon deposition characteristics of a high-gravity, paraffin-base crude oil. The results of these experiments indicate that a fuel supply adequate to initiate a combustion wave can be deposited in high-gravity-oil reservoirs. These results are significant because there has been considerable doubt whether oils over 35° API gravity are able to deposit sufficient fuel. Considered in these studies were the effects of air flux, temperature, initial oil saturation, and time on carbon deposition. Conditions that maximized carbon deposition in the laboratory and an understanding of the nature of carbon formation are shown by graphical interpretation of the data. Statistical techniques were used to design and analyze the results of the retort tests. For the same amount of laboratory work, this approach yields more information about the systems that were studied than the classical method of research presently used in many laboratories. In addition, the accuracy of calculating the effect of each variable on carbon deposition is twice that of the classical approach. This paper develops the statistical approach to research without complex mathematics, thus enabling the reader to grasp the concept of how statistics can be applied to study many complicated problems.

Jan 1, 1966

With the exhaustion of orebodies close to the main haulage shaft of the Emperor mine, an increased rate of development, aimed at earlier investigation of values disclosed by exploration drill holes has been attained with an overall reduction in unit costs.This paper describes the techniques used in rates of advance up to and exceeding 1,000 ft per 28-day period.

Jan 1, 1966

Boundary and general corrosio~z rates for higkpurity alutninum were ~rzeasured irz 16 pct HC1 at sJmllow penetrations (< 25 p). The rates for several high-angle random tilt boundaries, several [001] synzmetrical tilt boundaries, a 54-deg [010] twist, and a 15-deg randorn tw~st boundary were one-fourth to one-third higher than that of the (001) surface used as reference. Boundary attack was slower for 23 and 37-deg [001] tilt boundaries and a 16-deg [010] twist boundary. The corrosion rate for a (111) surface was roughly om-third higher than for (001) and was thus about as high as the corrosion rate of the fastest boundaries. The boundary attack did ?lot appear to parallel the variatiorz of boundavy energy. The signvicance of the anisotropy of corrosion was discussed.

Jan 1, 1966

By Lester G. Rollins

Coal today enjoys a dominant position, serving the energy and metallurgical marketed The measure of success in the market place is, and will continue to be, the price per million BTUs or price per ton delivered to the user. The Coal Industry&apos;s remarkable record of price stability since World War II is well known. The next twenty years promise to be equally as challenging. This challenge will be met our president, Mr. Drain, has often stated that, ?The Joy Manufacturing Company is betting that coal will meet the challenge.? To this end, the resources of Joy have been committed to doing its part. Joy&apos;s efforts are directed toward a target which has been defined as: 1. Deliver coal to the user at a price of $.15/MBTU or less. or; 2. Deliver coal to the mine portal at a cost of $1.00 or less.

Jan 1, 1966

By J. P. Morris

A diphenyl ether calorimeter for measuring high-temperature heat contents of ferrous alloys and iron-and steelmaking slags was constructed and calibrated with specimens of molybdenum, alumina, and platinum that were heated to temperatures ranging from 1,720° to 1,875° K. The standard deviation of the calibration measurements was 0.37 percent. By measurements of the enthalpy of delta and liquid iron, the heat of fusion of iron was found to be 3,298 ±100 cal per mole.

Jan 1, 1966

By S. F. Featherby

"This paper traces briefly the historical development of coal handling systems to meet the needs of a rapidly developing thermal power generation technology. The wide range of operating requirements is demonstrated by comparing and contrasting the Wabamun GS of Calgary Power Ltd. and a typical modern Ontario-Hydro thermal plant. The problems of safe storage of large tonnages of coal in stockpiles are discussed, together with recommendations for stockpile management. The development of coal bunkers and their management is discussed in detail, together with future trends in the industry."

Jan 1, 1966

By R. L. Benner

The Bureau of Mines investigated the ZnO-Fe2O3-Fe3O4 system at 1,000°, 1,300°, and 1,400° C, with oxygen pressures between 1.0 and lx10-4 atmospheres. The results, divided into the thermodynamic properties as related to the spinel structure, and the thermodynamic properties as related to zinc concentrate roasting, were used to calculate the activities of ZnO, Fe2O4, and Fe3O4 within the spinel solid solution region of the ternary system, and the pseudo-binary activities of ZnFe2O4 and Fe304. The activities of both systems show large positive deviations from Raoult&apos;s Law, especially at high Fe3O4 concentrations. The free energies, the enthalpies, and the entropies of mixing for the binary system were calculated from the binary activities, and the entropies of mixing were compared with two statistical models, one representing an ideal solution, and one representing the mixing of a normal with an inverse spinel. The binary entropy of mixing seemed to be better represented by the latter statistical model, indicating that the tetrahedral and octahedral cations of the reactants tend to remain in the product, even at the high temperatures of the study. This comparison also indicated that the cations of the components are the major contributing factors to the thermodynamic properties.

Jan 1, 1966

By F. M. Swain

High-calcium limestones occur in the upper part of the New Market Formation, of Lower Middle Ordovician age, in Franklin and Cumberland Counties, Pennsylvania. The high-calcium facies of the New Market Formation is represented by sublithographic limestone or vaughanite, which probably formed in quiet water; low-energy environments such as intershoal lagoons, or in protected bays similar to the present-day Florida Bay environment. Rapid facies changes are characteristic of the strata. The better grade of stone lies in the upper 100 to 125 feet of the New Market Formation and averages 95-97% calcium carbonate. Silica and magnesia are about equal in amount as impurities. One high-calcium belt extends from the Maryland state line through Chambersburg and Newville to beyond Carlisle. The strata in this belt are structurally complex, which requires careful field study&apos; and core-drilling prior to exploitation. Stone suitable for blast-furnace flux is present in relatively large amounts, but stone for open-hearth use or portland cement requires more selective quarrying.

Jan 1, 1966

By H. C. H. Darley

The influence of particle size and concentration on the development of chip hold-down pressure (CHDP) was studied in an apparatus designed to measure the change of filtration rate during the first second of the filtration process. CHDP is controlled by the "bridging" particles (i.e., particles in the 50 to 0.2 micron range), whereas filter loss is controlled by the colloid fraction. The results indicated that a fast drilling fluid with a low filter loss could be obtained if the concentration of bridging solids and the viscosity were kept very low. A novel group of drilling fluids, which we have named colloid emulsions, was developed to meet the above requirements. These colloid emulsions are made by dispersing art oleophilic colloid in oil and emulsifying about 5 per cent of this dispersion in water or a dense brine. Good results have been obtained in field trials with emulsions which use asphalt as the oleophilic colloid. INTRODUCTION In recent years it has been found that fast rates of penetration can be maintained in hard formations by using "clear" water as a drilling fluid. In some cases, however, water cannot be used because the very high down-hole filter loss creates various difficulties in drilling, in logging, or in producing the well. It then becomes necessary to "mud up", which results in a decrease in drilling rate. The reason that mud decreases drilling rates is a complex subject which has been well covered by such authors as Garnier and van Lingen, Cunningham and Eenink,&apos; and van Lingen.3 One of the principal factors involved is the tendency of the drilling fluid to develop a filter cake on the bottom of the hole. The pressure differential which develops across this filter cake opposes the action of the bit in dislodging chips from the rock. This pressure differential is referred to by Garnier and van Lingen&apos; as the chip hold-down pressure, which is denoted by the initials CHDP in this paper. The work described in this paper was undertaken to develop a drilling fluid which would minimize CHDP but which would still have a low filter loss—in other words, a fluid which would deposit a filter cake on the sides but would lay little or no filter cake on the bottom of the hole. EVALUATION OF CHDP EXPERIMENTAL Conditions governing the growth of filter cake on the sides of the hole are obviously different from those on the bottom of the hole. On the sides of the hole, cake will form continuously but at a decreasing rate, until eventually the rate of growth will equal the rate of cake erosion by the mud stream.&apos; On the bottom of the hole, each time a bit tooth dislodges a chip the cake is removed, a fresh rock surface is exposed, and the filtration process must start over again. Thus the CHDP is determined by the amount of cake which can form in the interval between successive tooth strikes at a particular spot, normally a fraction of a second. Our first step therefore was to study filtration rates over the first second or so of the filtration process. These tests were conducted in the simple type of dynamic filter cell shown in Figs. 1 and 2. In this cell the mud was filtered through a train of rock cores while rotating blades kept the mud flowing over the surface of the core. The procedure was to evacuate the cores to 0.05 mm of mercury, saturate with brine, and assemble in the holder under brine. The permeability of the core train was then determined. A plastic seal was placed on the face of the core train, and a rip cord was attached from the seal to one of the blades. At the start of the test, 500 psi was applied to the mud, and the meniscus in the capillary measuring tube was adjusted to zero. When the blades were started, t,he seal was ripped from the face of the core, and filtration began. The filtration rate was at first measured by photographing the advance of the meniscus in the capillary tube. Using

Jan 1, 1966

By Jr. Taylor

The following heats of solution have been measured in 1.160 molal H2SO4 at 25° C: AH298, kcal./mole Be(c) + 77.44(H2SO4?47.849 H2O) H2(g) + BeSO4 (soln) -92.83 ± 0.11 BeSO4 ?(c) + 77.44 (H2SO4?47.849 H2O) BeSO4(soln) -16.45 ± 0.02 BeSO4?2H2O(c) + 77.44(H2SO4?47.849 H2O) BeSO4?2H2O(soln) -5.395 ± 0.019 BeSO4?4H2O(c) + 77.44 (H2SO4?47.849 H2O) BeSO4?4H2O(soln) 1.513 ± 0.010 Combining these data with other experimental results and data taken from National Bureau of Standards information yielded the following heats of formation at 298° K:

Jan 1, 1966

By Henry N. Doyle

One can hardly discuss coal pneumoconiosis unless it is placed in the context of the total pneumoconiosis problem in the mining industry. However, it might be well if first we defined a few terms, since it has been my experience that the use of the word pneumoconiosis frequently causes con- fusion among those who are not familiar with the term. Pneumoconiosis comes from two Greek words meaning lung and dust. Hence, the word pneumoconiosis simply means dusty lung, or dust on the lung. There are many forms of the disease, some of which are disabling and some are not. Among the many dusts which cause pneumoconiosis might be included silica, asbestos, coal, talc, iron ore, and many other mineral dusts. Silicosis is a specific form of pneumoconiosis. It is caused by the inhalation of excessive amounts of silicon dioxide in the form of crystalline quartz. The disease is manifested by nodulation of the lungs which is apparent on an X-ray film. Continued exposure to silicon dioxide causes the nodules to grow and ultimately large areas of the lung become scar tissue which pre- vents the lung from performing its physiologic function. In its more advanced stages, there is a significant loss of pulmonary function which accounts for

Jan 1, 1966

By W. L. Falke

Procedures in which manganese compounds are reduced and the metal is volatilized and selectively condensed, a hitherto neglected area, were investigated. More than 95 percent of the manganese was recovered from high-melting-point ores whether vacuum volatilization or atmospheric pressure volatilization was used, but neither process is economically attractive under present price-cost conditions.

Jan 1, 1966

By R. E. Cumings

The Bureau of Mines made electrorefining tests in inert-atmosphere, molten salt cells to develop methods for the preparation of high-purity molybdenum. Seven of the electrolytes investigated were suitable for the preparation of refined metal. The electrolytes were composed of molybdenum chloride in alkali chlorides or mixtures of alkali and alkaline-earth chlorides. An electrolyte composed of potassium chloride and potassium hexachloro-molybdate was selected for a larger scale, more detailed study on the basis of its ease of preparation, its ability to retain the molybdenum salt, and the type of deposits obtained. High-purity molybdenum in the 99.99-percent-purity range was successfully prepared as dense plate up to 80 mils thick and as dendritic crystals. The temperature of electrolysis and the current density were major factors in determining whether plate or dendritic crystals of molybdenum were obtained.

Jan 1, 1966

By Raymond S. Shrode

Limestone and dolomite production is of significant importance to the Baltimore and Ohio Railroad. Except for coal, more tons of limestone and dolomite are moved by the Railroad than any other mineral raw material. In the territory served by the Railroad, these materials are produced from every geologic system from Cambrian through Pennsylvanian. Some of the operations produce premium stone acceptable for high-specification steel and chemical use; at others, the stone finds application as aggregate materials and for cement manufacture. The Railroad is interested in seeing continued production from the operations it now serves, and in serving operations in a way mutually beneficial to the Railroad and to the producer. In working with producers, the importance of geologic knowledge in prospecting and development of deposits has been clearly recognized. In turn, knowledge of the economic and technological facets of production and consumption is needed for the geologists to participate with maximum efficiency.

Jan 1, 1966

By Erik Q. Dahl

The strength of green and sintered pellets during reduction under various conditions in a laboratory kiln has been investigated. Equipment and test methods are described, together with the results obtained. The strength of sintered pellets drops sharply when the reduction starts, and goes through a minimum at the 70 per cent oxidation level. At more advanced reduction, the strength increases with increasing metallization. Successful use of green pellets as kiln feed requires that more attention be paid to the pellet preparation than is necessary when producing pellets for separate sintering. In particular, the ores have to be ground to a greater fineness. The initial strength of green pellets is low. Below the 70 per cent oxidation level, however, the strength of these pellets is about the same as the strength of sintered ones. Additions of such materials as silica, limestone and anthracite coal; within reasonable limits, affect the strength only slightly.

Jan 1, 1966

By L. J. E. Hofer

THIS BULLETIN analyzes and summarizes research at the Bureau of Mines dealing with the preparation, properties, and reactions of iron carbides in the period 1948-60, part of which was sponsored by Wright Air Development Laboratories. The objective was to develop better catalysts for the synthesis of methane and higher hydrocarbons from hydrogen and carbon monoxide. The investigations resulted in the first adequate characterization of epsilon iron carbide, which later proved to be an important intermediate in the tempering of martensite in steel. At temperatures near 170° C, the carbon in carbon monoxide reacts nearly quantitatively with finely divided alpha iron to form an iron carbide in which the metal atoms occupy the positions of the close packed hexagonal arrangement with lattice parameters of ao=2.754 A and co=4.349 A. The carbide has a composition within 2 atomic percent of that required for the formula Fe2C, a Curie point of about 370° C, a specific magnetization of 160.4 ergs per gauss-gram Fe at 50° C, and a ferromagnetic moment of 1.70 Bohr magnetons. Epsilon iron carbide can be converted to chi iron carbide by thermal treatment at 343° C for about 70 hours. The chi iron carbide so formed has a Curie point of 247° C, a specific magnetization of 142.5 ergs per gauss-gram Fe at 50° C, a ferromagnetic moment of 1.72 Bohr magnetons per iron atom, and a paramagnetic moment of 5.5 Bohr rnagnetons per iron atom. Direct synthesis of this carbide from carbon monoxide at 240° C indicates a composition within 7 atomic percent of that required for Fe2C. Chi iron carbide can be converted to cementite at 550° C in about 315 minutes. The theta iron carbide so prepared has a Curie point of 210° C, a specific magnetization of 147.3 ergs per gauss gram Fe at 50° C, a ferromagnetic moment of 1.72 Bohr magnetons per iron atom, and a paramagnetic moment of 3.9 Bohr magnetons per iron atom. Pure chi iron carbide reacts to form theta iron carbide by the elimination of free carbon. In the presence of an excess of free iron in intimate contact with the carbide, chi iron carbide reacts with the free iron to form theta iron carbide. The second reaction proceeds at an appreciable rate at 320° C and can be used to snythesize finely divided theta iron carbide with no free-carbon impurity at low temperatures. The ease of the reaction in the presence of free iron suggests that chi iron carbide is an intermediate in the tempering of epsilon iron carbide to theta iron carbide as it proceeds in steels. Experiments on carbon steel show that the magnetic moment of the iron atoms in martensite is about 2.2 Bohr magnetons per atom, a value approximately the same as that of the iron atoms in alpha iron. The Curie points of epsilon iron carbide, chi iron carbide, and theta iron carbide were found -in various specimens of tempered steel to be 10° to 20° C lower than normal values. This shift is probably the result of manganese in solid solution. Preparations of various compositions of epsilon iron carbonitrides show many effects of extensive isomorphism between epsilon iron carbide and epsilon iron nitride. The action of carbon monoxide on finely divided alpha iron at 400° C results in free carbon deposits containing filaments about 0.1 micron in diameter and several times as long. The filaments are characterized by nuclei of dense material located midway from each end of the filament. Although carbiding to near completion at 240° C over periods of about 300 hours produces a preparation containing no appreciable percentage of epsilon iron carbide, very brief periods of carbiding of the order of a minute result in the formation of detectable epsilon iron carbide even at temperatures as high as 325° C. The data indicate that epsilon iron carbide is an intermediate in the formation of chi iron carbide during its formation from carbon monoxide in the gas phase. Attempts to convert cementite to chi iron carbide by cold work increased the Curie point but did not change the X-ray powder diffraction pattern.

Jan 1, 1966