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By J. P. Timmons, J. H. Moran, G. K. Miller, M. A. Coufleau

A prototype equipment has been designed and built for the digital recording of well logs on magnetic tape at the same time that the regular film recording is made. The format of the digital tape produced is such that it can be used directly at the input of the ZBM 704, 7090 or other models of ZBM computers which accept digital magnetic tape. This apparatus has been used for the experimental field recording of dipmeter tape logs which were subsequently computed by means of an ZBM 704 or 7090. In this paper the equipment and the digital tape are described briefly, and their application to the computer-interpretation of dipmeter data is discussed. A principal element in the interpretation of the dipmeter log is the correlation of the three microresirtivity dipmeter curves to determine the depth displacements between them. Several correlation methods for computer use are considered, with particular attention to their sensitivity to error and their consumption of computer time. The tape data were used to compute information content of the dipmeter microresistivity curves in terms of their frequency spectra. The results show that the sampling rate used in recording the digital information is quite adequate and illustrate a use of the digital tape in evaluating the characteristics of new tools. Some examples of field results are shown. It can be foreseen that, when digital tape recording becomes available for general field use, a whole new realm of possibilities will be opened up for the processing of other well logs through computations, which hitherto were not feasible because they were too laborious and time-con.sunzing. INTRODUCTION The last few years have seen a revolution in the design and production of data-processing equipment. Stored-pro-gram digital computers have progressed from a research curiosity to the basis of a major industry. There are now hundreds of such machines in daily use in the United States. With the acceptance of a technique that was, in fact, already clearly described by John von Neumann in 1945, the last decade has seen great strides in the development'of components, reliability, programming systems and, most spectacularly, in the sheer number of machines built and in use. In 1957 there were enough digital computers available to the oil industry to justify the suggestion that it would be worthwhile to investigate the possibility of using these machines in processing well log data.' The first result of this investigation was the appearance of what may be referred to as the input-output bottleneck. Well logs are customarily recorded on film. To get these data into a machine required then (and still does): a time-consuming semi-automatic reading of the film; conversion of the log data to digital form; and recording these digital data in some medium acceptable for computer input, such as cards, magnetic tape, or punched paper tape. However, the recording, reading, and re-recording could only result in deterioration of the data. Therefore, it was concluded that the fist step should be the development of a new, more direct recording technique supplemental to the film recording, which would provide easy access to the digital computer. There are many solutions to the problem of recording log data in an easily recoverable form. After careful consideration it was decided to adopt the boldest solution which, it was felt, was also the most elegant. It was decided to record well logs directly, in the field, on magnetic tape in such a way that this tape could be used without further modification as an input to the IBM 704 or 7090 computer. To realize practical field recording of magnetic tape logs, it became necessary to develop in a rather small package, an analog-to-digital converter, a tape recorder, and the necessary multiplexing and control circuits to allow the simultaneous recording of a multiplicity of logging signals. The magnetic tape recording was to be made simultaneously with the conventional logging operation in such a way as not to interfere with it. Along with the development of hardware, it was necessary to begin development of interpretation techniques and machine programs that would exploit the power of the digital computer. Here, again, there is a long list of possible applications. After much consideration it was decided to concentrate on the interpretation of the dipmeter log as a first application. It is the object of this paper to describe in some detail the developments sketched in the last three paragraphs.

By L. S. Chabot

The bibliography of mining methods in the past few years has contained many articles dealing with the use of the diamond drill for blasthole drilling. In the Canadian mines, this method has been used with great success in stoping at Noranda, Aldermac, Waite Amulet, East Malartic and Sladen Malartic mines in the Province of Quebec. It has also been used at the Dorchester and Beattie gold mines in Duparquet, Quebec. The method has found useful application at Copper Mountain mine, British Colombia, and at Flin Flon mine in Manitoba. In the United States, the diamond drill blasthole method has been used at Cornwall Iron Ore Mines in Pennsylvania and at the Republic Steel Corporation magnetite properties in the Port Henry district of northern New York. In the Lake Superior iron district, the method has been used at the Anvil-Palms mine of Pickands, Mather and Co. at Bessemer, Mich., and is also used at the Book mine of the North Range Mining Co. at Alpha, Mich. Other companies in the district have also experimented in some degree with the method at some of their properties. This Paper is being offered as a prelimi- nary report on the use of the diamond drill method of stoping at the Book mine. Sufficient work has been done with it to prove its worth and it is the purpose of the article to present some results, operational details, equipment ideas and recommendstions which we have found in its use at our mine. Location and Description The Book mine is situated about a mile north of the village of Alpha, in the NE-NE1/4 and the SE-NE1/4 of set 12-42-33, between the Dunn mine and the Balkan-~~d~~~ mine, and about four miles southwest of the village of Crystal Falls, on the menominee Range of Michigan, The property was found to have ore near surface in sufficient quantities for open-pit operations and stripping was begun in the latter part of 1942 to prepare it for ore production in 1943. During 1943, 288,447 tons of direct shipping ore were produced from the open pit and 382,933 tons in 1944 While the mine was being operated as an open pit some 350,000 tons of lean ore were stockpiled for later treatment. This material is beilng treated in a washing and jig plant and concentrates are produced during the shipping season. The ore bodies at the Book mine are characteristic of the Menominee Range. They are found on the flanks of sharply folded anticlines which have a fairly steep pitch to the northwest. The open-pit operatiOns in 1943 and 1944 revealed two of these anticlinal structures. A detailed study and classification of the old diamond drill records, coupled with the information of some new holes drilled, has established the

Jan 1, 1949

By James Harding

THE usual method of sampling mineral deposits is to drill holes and assay the sludge or core. Though the results thus obtained may not represent the true average value of the deposit, it is on these results that estimates of practically all large orebodies are made. In a large number of cases, the results of exploitation fall far short of the estimated value of the orebody. The standard method of making these estimates is to find the cubic contents of triangular prisms, in the apexes of which the drill holes are placed, .by multiplying the surface area by the average depth of the ore in the three drill holes and then multiplying the cubic contents by the specific gravity of the ore or rock to find the tonnage. The assay value is found by dividing the sum of the products of the depth of ore in each hole and the corresponding assay value by the sum of the depths of the ore in the three holes. As the latter part of this method is subject to many mathematical errors, it should not be depended on.. Some engineers, therefore, use a discount factor, but as this factor is either arbitrarily selected or is obtained by obscure methods, the results are no better than guesswork. The standard method is correct when the drill holes are so laid out that the triangular prisms are equilateral in cross-section. But as ore deposits cannot always be drilled into at regular intervals and because of the human factor, if many holes are drilled, triangular prisms of all degrees of angularity are produced. In such cases, it is necessary to assume that the influence of the different holes is not the same in all directions, which assumption of course is absurd.

Jan 1, 1921

By Walter Crafts

STRUCTURAL steels containing chromium have become widely used in the last 20 years. In the earlier part of this period the major applications were in chromium-molybdenum aircraft tubing and similar special high-strength steels. During the past 10 years there has been a notable expansion in the use of chromium-bearing steel for structural purposes when welding was utilized for fabrication. The chromium-bearing steels introduced by Saklatwalla1 (chromium-copper), Kinzel2 (chromium-manganese-silicon), and Schultz3 (chromium-copper) are being extensively used at the present time.

Jan 1, 1939

By H. DeWitt Smith, W. H. Sirdevan

The mine operated by the United Verde Copper Co. is situated near Jerome, Ariz., on the eastern flank of the Black Hills, at an elevation of approximately 5500 ft. (1676 m.) above sea level. The mine and the town of Jerome are located on a steep hillside, which slopes rapidly to the valley of the Verde River. The smelter town of Clarkdale is situated in the Verde valley 4.1 mi. (6.5 km.) distant in an air line from Jerome, and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel & Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 mi. long and has a compensated 4 per cent. grade. At Clarkdale, it connects with the Verde Valley branch of the Santa Fe R. R. The narrow-gage (36-in.) line of the United Verde & Pacific Ry. was, until 1919, Jerome's only rail connection with a main trunk line. This road connects with a branch line of the Santa Fe system at Jerome Junction, after traversing 26 mi. of mountainous country. From the time of its location, in 1876, until its purchase by Senator W. A. Clark, of Montana, in 1889, the United Verde mine was worked on a small scale and shipments of high-grade gold-silver ore were made from the surface workings. Until 1894, when the narrow-gage railroad to Jerome Junction was completed, all supplies for the mine and smelter

Jan 1, 1922

By Robert Wamsley, W. E. Jones

One of the earliest problems in the life of any community is the provision of an adequate supply of water sufficiently free from all types of contamination to be suitable for domestic purposes. Generally speaking, the location of most communities is determined to a great extent by the availability of an adequate supply of satisfactory water. For a mining camp, that consideration cannot be foremost. Here, the ore takes first place, and the men who mine it must do the best they can under the existing conditions. If there is no local source of water, it must be brought from some distant source or must be found by sinking shafts or drilling wells. Fortunate indeed is the mining company that discovers a commercially valuable ore deposit beside a never failing creek full of pure water, with sufficient water rights available. because the acquisition of water in any other manner nearly always involves not only a considerable period of time but the expenditure of considerable money. The experience of Climax Molybdenum Co. demonstrates the measures that sometimes are necessary in order to provide a suitable supply of water. The Climax mine and mill are on the Continental Divide! about 13 miles northeast of Leadville. The elevation of the domestic part of the camp varies from a minimum of 11,320 ft. to a maximum of approximately 11,550 ft. above sea level, and, as is common at such altitudes, the near-by streams that might be suitable for a water supply are small and intermittent, usually flowing only during the summer months. The only streams of any size in the immediate vicinity of Climax are the Ten Mile and Arkansas Rivers The headwaters of Ten Mile River are on the Company's property, and its water has been used for the domestic supply. The headwaters of the Arkansas River are about 2 miles distant and have not been used as a source of supply by the company. During the past 11 years of the production of molybdenum at Climax, the number of families living there has increased from about 45 to 283, and the population has increased from about 200 to 1200 persons. Consequently, the capacity of the water-treatment facilities, and the amount of water available, had to be increased to meet the requirements of the camp. As early as 1932 it was recognized that the water in Ten Mile River would not continue to be adequate for domestic purposes and after considerable discussion it was decided to drive a drift through the major fault in an effort to find additional water. This drift was completed in 1935 and tapped sufficient water to make the supply adequate. This water was treated in a tank underground, where lime was added, and was then piped into the domestic supply lines. At about the time this line was completed, the presence of fluorine in harmful concentrations was discovered in the water. This problem was submitted to the International Filter Co. and in November 1937 a plant of its design was put in operation for treating the water to remove the fluorine. This plant proved entirely successful,

Jan 1, 1946

By H. E. Elliott, R. S. Busk, A. T. Peters

ONE of the problems of the fabricator of metals and alloys is the propensity of some composition ranges toward abnormal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, o per cent Al, 2 per cent Zn, 0.2 per cent Mn) and G alloy (Mg, i0 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other metals. Jeffries and Archer' have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. of abnormal local grain growth was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. r) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The Dow Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germination," since this term has been defined' as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.' (Compare the electron band picture in Hume-Rothery.' Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By E. S. Bardwell, Roy H. Miller

During the period extending from May, 1922, to September, 1923, the copper-refining furnaces of the Great Falls Reduction Department of the Anaconda Copper Mining Co. at Great Falls, Mont., were operated exclusively with pulverized coal as fuel. The installation was made first as an experiment. It proved successful from the start and was abandoned solely because fuel oil from the Sunburst field became available at a price sufficiently low to be more desirable from an economic standpoint. The equipment required for pulverized coal has, however, been kept intact and is available for immediate use should the oil supply fail. Inasmuch as pulverized coal had been used on two large reverbera-tory smelting furnaces and was, at the time we were considering its application-to the copper-refining furnaces, being used on the Wedge furnaces roasting zinc concentrate for the electrolytic zinc plant, we were equipped with a coal-pulverizing plant of ample capacity to supply pulverized coal for the furnace refinery. The only problem was to devise suitable means for transporting pulverized coal from the pulverizer plant, located in the smelter building, to the refinery about 3000 ft. distant and about 150 ft. above the level of the pulverizer plant. When studying this installation, it should be borne in mind that the layout represents an adaptation suited to the existing conditions at this particular plant. The installation was entirely satisfactory and uniformly dependable but might be modified to advantage from an operating point of view if an entirely new installation were being planned. Fuel Supply The use of the local coals, high in ash and sulfur, was abandoned some time before coal-dust firing was attempted. Local coals from the Great Falls field carrying an average of 4 per cent. sulfur and 22 per cent, ash were used with fair success in the small furnaces in use prior to 1916. In the 250-ton furnaces, however, the time lost in grating and removing clinker from the fireboxes, as well as the difficulties incident to the high-sulfur content of the fuel, became serious and recourse was had to the

Jan 1, 1927

By Herbert H. Kellogg, Hugo Vasquez- Rosas

Recently the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authorsl-5-l8 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, laurylamine hydro-chloride, as a collector for the flotation of galena-sphalerite ores. The results show that laurylamine hydrochloride (LAmHCl), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. Contact-angle Tests The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-coverkd glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the clean surface to air or any other source of contamination.

Jan 1, 1947

By Herbert H. Kellogg, Hugo Vasquez- Rosas

Recently the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authorsl-5-l8 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, laurylamine hydro-chloride, as a collector for the flotation of galena-sphalerite ores. The results show that laurylamine hydrochloride (LAmHCl), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. Contact-angle Tests The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-coverkd glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the clean surface to air or any other source of contamination.

Jan 1, 1947

By Clyde Orr

INTRODUCTION Cracks, crevices, holes, and fissures -- here collectively termed pores -- occur in all manner of substances in sizes from those evident to the unaided eye to those well below electron microscopic levels of detection. Naturally occurring materials having varying degrees of porosity are represented by wood, rock, soil, and mineral formations. Man-made materials that are porous include ceramics, sintered metals, catalysts, adsorbents, filters, and various compacted objects. The extent of their porosity greatly influences the hardness, rigidity, integrity, and general usefulness of such materials, and assessing both their pore volume and size is becoming increasingly necessary. Means by which this pore information can be obtained is the subject here. No attempt will be made to include all techniques and variations of them that have been suggested, but, hopefully, those of most general applicability will be described in sufficient detail to enable a potential user to judge their merit for a particular need. The results of pore measurements are made useful by relating them through other tests to performance criteria such as weatherability, water penetration, frost damage, oil recovery, strength, or thermal or electrical conductivity. These tests, of course, are outside the bounds for inclusion here. A pore is variously defined in dictionaries as "a minute opening", "a small interstice admitting passage of liquid", and "an interspace between particles". Clearly any object through which it is possible to find a continuous path from one side to the other either for a liquid or a gas must be regarded as porous. Passageways are not necessary for porosity to exist, however. There are so-called blind

Jan 1, 1980

By N. O. Gray, John Henderson

Hydrogen-reduction data for naturally occurring single crystals and Prepared polycrystals of dense hematite have been presented. Results cover the temperature range 400o to 1000oC, for particles from ten sources, ranging in size from 0.07 to 10 mm and in shape from spheres to cylinders, cubes, and thin slabs. A consistent pattern of behavior has been demonstrated for single crystals and the reduction mechanism shown to be temperature-dependent. Below 579oC reduction is a simple topochemical process but at higher temperatuves it is complex and occurs in two distinct stages. Prepared particles from these laboratories behave in a similar manner to the single crystals. Data from two investigators showing topochernical reduction of Prepared particles above 575°C are inconsistent with that for other dense hematites. It is concluded that topochenzical reaction should not be used as a model for generalized rate expressions for dense hematites. SINCE 1958, McKewan1-6 has brought to prominence a simple concept of dense hematite reduction. This model is that oxygen is lost from a hematite particle undergoing reduction only from an oxide-iron interface that recedes in such a way that the oxide remaining retains the original shape of the particle, i.e., reduction occurs topochemically. An adjunct to this concept is that any intermediate oxides in the transition from hematite to iron only form thin layers so that oxygen cannot be lost from the particle without movement of the oxide-iron interface. Further, the rate of oxygen loss from the particle is said to be proportional to the area of the receding interface so that the iron layer grows linearly with time and the over-all reduction process can be described by the equation where ro and do are the initial particle radius and density, respectively, R is the fraction of the original oxygen lost, i.e., the fractional reduction, at time t, and K is the rate constant. The idea of an underlying simplicity in hematite reduction is attractive because it gives a tractable basis from which general theories of hematite reduction can be developed and it has received wide support,7-14 based mainly on the large amount of data13 that can be fitted to Eq. [I]. However, despite the fact that this equation has been derived for dense materials, the bulk of the data that have been used to test it13 have been for materials of only about 90 pct of theoretical density (5.26 g cm-3) or less, so that its generality for dense hematites has not been demonstrated. In any case, as will be seen, adherence of reduction data to Eq. [1] does not necessarily imply that reaction occurs topochemically. In this work only data for hematites approaching theoretical density are considered and it will be shown that in only one study besides McKewan's is topochemical behavior observed over the whole range of temperature investigated. For the majority of materials a linear rate of interface advance is observed to complete reduction only when wustite is not a stable intermediate phase in the transition of hematite to iron, i.e., at temperatures below about 575°C. Above this temperature, reduction is an exceedingly complex series of reactions that takes place in two distinct stages and it is only in the first stage that reaction in any way resembles a topochemical process. This means then that, far from representing general behavior as has commonly been supposed, topochemical reaction for dense hematites is only a particular behavior that may be observed under some circumstances. EXPERIMENTAL Hydrogen-reduction data have been collected and cross-checked in these laboratories by three techniques, weight loss, collection of water evolved in the reduction reactions, and direct metallographic examination. Details of these techniques are discussed elsewhere," where it is shown that results obtained by the three methods are in close agreement. The weight-loss method, by which most of the results were obtained, consisted of hanging the sample in a platinum mesh basket from an Ainsworth Model AV-AU-1 vacuum recording balance inside a vertical l 1/4-in.-ID alumina tube furnace. Dry deoxidized hydrogen was flowed downwards through the tube at 2 to 4 liters min-1 (stp). Single crystals from two sources and artificial oxides from three sources have been examined. The single crystals were from hematite deposits at Yampi Sound, Western Australia, and Brazil, the latter being obtained from Gregory, Bottley and Co., London, U.K. The "Yampi Blue" crystals were hand-picked from washed, magnetically concentrated, sized fractions, -200 mesh BSS (mean diameter ca 0.07 mm) and —36 + 44 mesh BSS (mean diameter ca 0.4 mm) while 10-mm cubes were cut from the Brazilian crystals with a diamond saw. The starting materials for the prepared particles were hematites designated, respectively, "Specpure Iron Oxide", Laboratory No. S639 from Johnson Matthey & Co. Ltd., London, U.K., "Calcined Ferric Oxide" from B.D.H. Laboratory Chemicals Division, Poole, U.K., and "Pigment Grade Oxide", EPR-50, from C. K. Williams & Co., Easton, Pa., U.S.A. Approximately spherical particles were prepared from the artificial oxides by rolling the material, moistened if necessary, in a glass jar, and cylindrical compacts approximately 10 mm in diam and of approximately equal height were pressed in a steel die at 200 psi. These spheres and cylinders were subsequently fired in oxygen for 20 to 100 hr at 1370°C. The

Jan 1, 1967

By Charles C. Russell, Glenn C. South

A primary factor in the selection of coals for making coke at high temperatures is the amount of pressure the coal will exert upon the oven walls when carbonized in modem by-product ovens.l-3 This factor has become increasingly important in recent years because of demands for increased throughput and higher coke yields. As a result of the increasing necessity for assessing coals in regard to their carbonization pressures, more and more research work is being directed toward developing labora-tory-scale tests for predicting carbonization pressures and for showing how blends of coking coals may be modified to eliminate pressures liable to damage coke-oven walls. The specific reasons have never been defined as to why some blends of coking coals develop dangerous carbonization pressures and others do not, therefore specific procedures to eliminate dangerous pressures could not be prescribed. It is true that the major processes occurring during carbonization have been described by many writers,4 and there is a general agreement on the ideas of the changes that occur as coal is transformed into coke. However, there is little evidence relating the processes occurring during carbonization to the pressure developed and the available evidence is very incomplete and often contradictory. This deficiency arises in part from the fact that the fundamental causes of pressure development have not been defined, at least from experimental data, and in turn this is the result of the lack of satisfactory testing equipment for studying the problem. Operating experience has shown several ways of reducing or eliminating dangerous pressures,5 but probably none of these ways is applicable to all blends of coking coals, and such empirical methods often lead to production of inferior coke. They are trial-and-error methods, not designed to remedy specific causes of pressure development. The number of laboratory-scale testing devices designed to estimate the carbonization pressures that result when coals are carbonized in commercial ovens is probably well over a hundred.6 Few of these instruments have remained in use for any length of time, either because the predictions were not sufficiently accurate or, more often, because too many exceptions were found. Often testing devices are operated without any attempt at duplication of conditions in commercial ovens and erroneous and contradictory results are frequently obtained. Therefore, it has seemed desirable to study the properties of coal itself and to determine any relationships between the properties of the coal and the carbonization pressures developed. Relationship between Properties of Coal and Carbonization Pressure Attempts to determine relationships between various properties of coal and carbonization pressures, for the most parti have been indirect because no satisfactory and reliable laboratory testing device has

Jan 1, 1944

By Glenn C. South, Charles C. Russell

A primary factor in the selection of coals for making coke at high temperatures is the amount of pressure the coal will exert upon the oven walls when carbonized in modem by-product ovens.l-3 This factor has become increasingly important in recent years because of demands for increased throughput and higher coke yields. As a result of the increasing necessity for assessing coals in regard to their carbonization pressures, more and more research work is being directed toward developing labora-tory-scale tests for predicting carbonization pressures and for showing how blends of coking coals may be modified to eliminate pressures liable to damage coke-oven walls. The specific reasons have never been defined as to why some blends of coking coals develop dangerous carbonization pressures and others do not, therefore specific procedures to eliminate dangerous pressures could not be prescribed. It is true that the major processes occurring during carbonization have been described by many writers,4 and there is a general agreement on the ideas of the changes that occur as coal is transformed into coke. However, there is little evidence relating the processes occurring during carbonization to the pressure developed and the available evidence is very incomplete and often contradictory. This deficiency arises in part from the fact that the fundamental causes of pressure development have not been defined, at least from experimental data, and in turn this is the result of the lack of satisfactory testing equipment for studying the problem. Operating experience has shown several ways of reducing or eliminating dangerous pressures,5 but probably none of these ways is applicable to all blends of coking coals, and such empirical methods often lead to production of inferior coke. They are trial-and-error methods, not designed to remedy specific causes of pressure development. The number of laboratory-scale testing devices designed to estimate the carbonization pressures that result when coals are carbonized in commercial ovens is probably well over a hundred.6 Few of these instruments have remained in use for any length of time, either because the predictions were not sufficiently accurate or, more often, because too many exceptions were found. Often testing devices are operated without any attempt at duplication of conditions in commercial ovens and erroneous and contradictory results are frequently obtained. Therefore, it has seemed desirable to study the properties of coal itself and to determine any relationships between the properties of the coal and the carbonization pressures developed. Relationship between Properties of Coal and Carbonization Pressure Attempts to determine relationships between various properties of coal and carbonization pressures, for the most parti have been indirect because no satisfactory and reliable laboratory testing device has

Jan 1, 1944

By R. R. Nash, W. F. Sheely

Experiments were conducted on magnesium monocrystals in order to collect quantitative information on the mechanisms which limit the rate of basal slip. Using critical shear stress and creep data, activation energies for creep at low aid at high temperatures were derived. The activation energy at low temperatures is the same as that for jog formation and the activation energy at high temperatures agrees with that for climb. COTTRELL has suggested that at low temperatures, the expansion of dislocation loops under stresses near the yield strength is limited by the rate at____ which the expanding loops can cut the "forest" of dislocations passing through the glide planes.' On the basis of this mechanism, seeger2 has derived expressions for low-temperature creep and for the relation of flow stress of single crystals to temperature. In the work reported here, the authors have performed experiments designed to obtain quantitative data on the physical properties of the dislocation intersection mechanisms operating during basal slip in pure magnesium monocrystals. Above a critical temperature, dislocations thread-

Jan 1, 1961

By Frank Fahrenwald

INTRODUCTORY A COMPLETE list of the elements as given for 1915 includes 18 that melt above 1,700° C. There does not exist one complete thermal equilibrium diagram for any pair of these 18 elements. Several of these elements have been combined, in relatively small proportions, with metals of lower melting point: e.g., tungsten, molybdenum, and vanadium, in steels, or with nickel and cobalt; but of this refractory group, platinum is the only one that has been extensively studied in this connection. When one considers that, with few exceptions, the industries have made use of alloys to the exclusion of pure .metals, it is reasonable to expect that alloys of this refractory group will invade fields in which the pure metals have found little application. The past neglect of this class of metals has, no doubt, been partly due to the rarity of some of them, for even though alloys of very valuable properties should be developed, their cost, unless in exceptional applications, would be prohibitive. There is also a well-founded reluctance to undertake research involving very high temperatures which, in the case of most of these elements, must be accompanied by an inert atmosphere as well. This combination of high temperatures* and control of atmosphere within the heating chamber of any furnace of present design is a difficult problem. It is the purpose of this paper to give results,1 of an investigation of one binary series of this group, in which methods were employed that avoided the usual difficulties accompanying high-temperature alloy investigation.

Jan 6, 1916

By L. G. Jones, A. S. Odeh

A theoretical developtment is presented which provides a straightforward method of handling the drawdown analysis for both oil and gas wells flowing at variable rates. In the past our inability to analyze variable-rate drawdowns has been a major obstacle in using them for formation evaluation. This method should permit wider use of these tests in the future. INTRODUCTION Pressure build-up analyses are widely used to obtain reservoir data such as the effective flow capacity of the formation. On the other hand. although pressure drawdowns have been run for a long time, they have not been used extensively to evaluate reservoirs because they are difficult to analyze. One of the difficulties in analyzing pressure drawdowns has been that the theory developed until now has required the test to be run at a constant rate. For both oil and gas wells this is a difficult requirement to satisfy. especially during the early period of a well's life when drawdown tests are usually run. In spite of this limitation, drawdown tests are often run with build-ups as a check. In this paper a theory, which handles the drawdown analysis for variable rates, is presented for both oil and gas wells. Thus, one of the biggest deterrents to running drawdowns is removed, and they should become a much more useful engineering tool in the future. THEORETICAL CONSIDERATIONS 011, RESERVOIRS The general equation used for describing the unsteady-state radial flow of slightly compressible fluids in homogeneous porous media can be written in cylindrical coordinates as where r is the radial distance in cm, t is the time in seconds, p is the pressure at r and t in atmospheres, + is the fractional porosity, p is the viscosity in cp, c is the compressibility in vol/vol/atm, and k is the permeability in darcies. There are a number of solutions of Eq. 1 for various boundary conditions. One of these is the so-called "point-source" solution, which approximates the case of an infinite oil reservoir with a well located at r = 0 and produced at a constant rate. The point-source solution of Eq. 1 is

Jan 1, 1966

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By G. Thodos, R. B. Grieves

A method has been developed For predicting the critical temperatures and critical pressures of binary mixtures of carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen with the normal paraffin hydrocarbons. For carbon-dioxide and hydrogen-sulfide systems, relations are presented that take into account the peculiar behavior of mixtures with closely boiling components, such as carbon dioxide-ethane and hydrogen sulfide-propane mixtures which exhibit minimum critical temperature points. For hydrogen, nitrogen and carbon-monoxide systems, the extreme critical behavior caused by wide differences in pure component properties is established In addition, those fixed gas-paraffin systems which resemble paraffin-paraffin systems are also accounted for. For a mixture of known composition, the pure component critical temperatures, critical pressures and normal boiling points are all that are required to determine its critical point. Graphical relations are presented relating Tc and PC , of the mixture to the pure component properties. From the treatment of 12 carbon-dioxide and hydrogen-sulfide systems reported in the literature (74 mixtures), the expected error lor the critical temperature is approximately 1.5 per cent, and for the critical pressure, approximately 2 per cent. From the treatment of six hydrogen, nitrogen and carbon-monoxide systems reported in the literature (30 mixtures), the expected error for both the critical temperature and critical pressure is approximately 2.5 per cent. The relationships, which have been developed with only normal paraffins as the hydrocarbon components, may be extended to those isoparaffins and olefins which fall within the allowable volatility ranges. INTRODUCTION Many of the fixed gases — carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen — occur in natural mixtures with hydrocarbons. Carbon dioxide and hydrogen sulfide are frequent components of the fluids produced from underground petroleum reservoirs. Nitrogen, carbon dioxide and hydrogen sulfide are present in varying quantities in most natural gases and gas-condensate well effluents. Hydrogen mixtures are of considerable interest in many phases of refining processes of petroleum. The determination of the critical temperatures and critical pressures of such mixtures is of value in vapor-liquid equilibrium studies, for the prediction of the characteristics of underground reservoirs, and for reduced-state correlations of PVT, transport and thermodynamic properties. The accurate estimation of the critical point for binary mixtures is an important initial step toward a complete analysis for the establishment of the critical temperatures and pressures of multi-component mixtures. Methods for predicting the critical temperatures and critical pressures of binary hydrocarbon systems have already been presented in the literature.8 It is possible to apply these existing methods to fixed gas-paraffin mixtures, but due to their unusual critical behavior, values calculated deviate considerably from experimental values. For systems containing trace quantities of the fixed gases, these methods are acceptable; however, for systems containing more than 5 mol per cent of the fixed gases, these utterly fail to produce reasonable critical values. Consequently, in this study a method has been developed for handling such binary mixtures over the entire composition range. CARBON-DIOXIDE AND HYDROGEN-SULFIDE SYSTEMS The critical behavior and the vapor pressure behavior of mixtures of carbon dioxide and hydrogen sulfide with paraffinic hydrocarbons may be quite similar or quite dissimilar to that of paraffin-paraffin mixtures, depending on the volatilities of the components involved. The critical temperature and normal boiling point of carbon dioxide are very close to the corresponding values for ethane, while its critical pressure is considerably higher than that of ethane. The normal boiling point of