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OF no less importance nor less terrifying to consider than the marvelous effects of guns are those produced with fire by powder in underground mines. These are truly not only similar to fearful natural earthquakes, but it can perhaps be said that these made by art surpass the wrath of the earth with greater effect. For if the latter shakes it happens that it causes the things on the surface to shake and sometimes to fall into ruins, but the former not only shakes but always functions and destroys-surely a marvelous effect which is almost incomprehensible, and if experience did not demonstrate it, it could scarcely be believed. Who would say that the mountains, things of such great hardness, would yield to men, easily opening their bowels? Likewise, one who had not seen it would say that it was impossible for men to have a way of administering at will fearful and destructive thunderbolts which are of such a kind that, although men make them, they cannot protect themselves against them; indeed they cannot call themselves safe from the evilness of gunpowder even in mountains composed of very hard stones or in budded structures. For, as is seen, there is no seemingly impregnable fortress that does not yield when guns are brought near it. If it happens, indeed, that guns can- not be brought near to some place because of the harshness of the site,

Jan 1, 1942

By E. J. Quinn, M. F. Fogler

In a recent paper, Rawdon and Mutchlerl gave some exceptionally interesting results on the Brinell and scratch hardness of severely cold-worked metals. In their work, they found that, on continued cold rolling, the metal hardened up to a particular point and then reversed and became softer; this was true for both Brinell and scratch hardness values. The generally reported behavior2 of metals, with respect to Brinell tests on cold-worked material, is that the metals harden up to a certain point and then, on further cold rolling, no change in Brinell hardness occurs. Jeffries and Archer3 state that there is little difference between the scratch hardness of annealed and cold-worked metals; the work of Faust and Tammann4 also indicated no difference between the hardness of annealed and cold-worked copper. Rawdon and Mutchler found, when they plotted the reduction ratio (initial thickness divided by thickness after rolling) against the hardness value for the cold-rolled material, that the hardness number increased up to a reduction ratio of about 3 and then decreased and became even smaller than that for the annealed metal. This behavior was reported for both scratch and Brinell hardness; Figs. 1 and 2 show their results for Brinell hardness on the metals for which they published data. This is an exceptionally interesting phenomenon, if it occurs under all conditions of rolling, and would have an important bearing on the practice of cold

Jan 1, 1925

"The earth is the Lord's and the fullness thereof." Science knows no national boundaries, knows no country. These views might be taken as premises for a discussion of the development of the mineral resources of the world. Yet how far man is removed from such broadminded ideals! In this day of jealousy and dread, of political machinations and statesmen's maneuverings, of rantings and crass ravings against fellow-beings, man's attitudes towards God's gifts are but the measure of the smallness of man. That the exploitation of mineral wealth should be for the common good, none will deny, but what is meant by "common"? Is it for the common good of The Pennsylvania State College, Pennsylvania, the United States of America, or the world? If man is big enough and honest enough to state categorically that by "common," as used in the context above, is meant that the utilization of the mineral wealth should be for the mutual benefit of all mankind, and that all concerned strive to see that such a viewpoint is executed, then there is brighter hope for the future. It is to be hoped that the world may have at least a few years or possibly a generation of peace. What can be done in these years to work towards the ultimate goal of human improvement? The work of statesmen in the drafting of international agreements and the easing of small frictions which appear between nations, as they

Jan 1, 1950

By H. C. Rolseth, R. H. Kohler

Jet channeling made its entry into the granite industry in 1955 and quickly gained acceptance as an economical method of quarrying. Developed by the Linde Division of Union Carbide Corp., this method employs a small rocket-jet burner with a high-temperature, high-velocity exhaust flame that causes granite to disintegrate. It can thus make continuous vertical cuts to free large blocks from granite formations. The Thermal Spalling Process The effect of a thermal device on rock depends upon the rock's spallability. In simplest terms, spalling is the decrepitation resulting from differential expansion of rock crystals due to thermally induced stresses.1 the individual rock properties influencing the spalling characteristic are so numerous and their interaction is so complex that it has so far been impossible to predict with accuracy the reaction of any particular rock to a high-temperature source of heat. Perhaps computers will eventually make such predictions possible, but for the present it is necessary to impose the thermal shock conditions on a sample of the rock to establish its spalling characteristics. The properties most favorable to a high degree of spallability are: (1) Large linear thermal expansion at temperatures below 700º C. (2) High thermal diffusivity at temperatures below 400º C. (3) Equigranular interlocking structure with little or no fine-grained clay or mica alteration products. (4) No significant amounts of soft, low-melting, or elastic minerals or materials which yield after thermal decomposition.

Jan 7, 1969

By Warren Blauvelt

IN VIEW of the enormous wastes of natural resources, of labor and of capital, due primarily to the economic environment, established by legislation, the general neglect of this phase of the problem of the elimination of waste is difficult to understand. In such a study, the engineering method of attacking a problem should be employed. The engineer does not try to solve his problem by disregarding natural laws, but by utilizing them. The successful engineer establishes an environ-ment in which forces, acting in harmony with natural laws upon an object or objects, will produce the desired results. The engineer who notices that the water level in a vessel, into which a gallon of water per minute is flowing, is two feet higher than the level in an adjacent vessel, connected therewith by a 6-in. pipe, does not assume that the law of gravity has ceased to work, or that water no longer seeks its level; he examines the connecting pipe for obstacles which prevent the free flow of water. Some editors, many reformers and most politicians tell us that the law of supply and demand no longer works; hence governmental control of commerce is necessary. Governmental control may temporarily-that is, until trial proves its futility- "insure domestic tranquility" and "promote the general welfare;" but it cannot "secure the blessings of liberty" which it cur-tails, nor can it "establish justice" which it violates.

Jan 9, 1922

By E. J. Rapperport, J. P. Pemsler

Proton irradiation of high-purity distilled berylliuwz was utilized to introduce various hydrogen contents from 0.00075 to 0.075 at. pct (0.83 to 83 ppm) in a band 0.004 cm wide. After irradiation, the specimens were heat-treated to effect hydrogen agglomeration. Observations of agglomerates in all specimens of the lowest hydrogen content indicate a hydrogen solubility of less than 0.83 ppm in the temperature range 350" to 1050°C. Estimates of the inter diffusion coefficient in the hydrogen solid solution of beryllium were obtained from measurements of the dimensions of hydrogen-depleted zones survounding agglomerated bubbles. A value of (approximately) 3 xlo-' sq cm per sec is obtained for the diffusion coefficient at 850" to 900°C. PREVIOUS investigators found that We solubility of hydrogen in beryllium is very small. Gulbransen and Andrew' state that beryllium does not react with hydrogen at 23 mm Hg between 300" and 900°C. Cotter ill et a1.' report that as-machined beryllium has an adsorbed hydrogen layer of 0.007 cu cm per sq cm of surface. No additional hydrogen is picked up in hydrogen at 0.1 mm Hg and between 200" and 80O°C, or when hydrogen is bubbled through molten beryllium. Beryllium hydride has been reported to exist in an ether solution,394 but decomposes at about 200°C; there is no substantial evidence for the existence of the hydride in the solid phase.

Jan 1, 1964

By G. C. Bateman

THE Workmen's Compensation Act of Ontario was passed in 1915 and Miners' Phthisis was added to the list of compensable industrial diseases in 1916. Under this provision of the Act only about two cases were compensated per year. In 1924, The Department of Public Health made a survey of miners in the four principal camps-Sudbury, Porcupine, Kirkland Lake and Cobalt-and the survey indicated that an alarming proportion of the men exposed to dust had silicosis in one or other of its several stages. A number of conferences were held between representatives of the Department of Mines, the Department of Public Health, the Compensa-tion Board and the mine operators. The operators were advised that in the earliest stages of silicosis there was no physical disability and if men in that stage were removed froni underground there would be little danger of permanent disability. They were further advised that if active steps were taken at once to compensate men that had some real disability and remove from the mines men in the early stages of silicosis, the first cost would be the greatest and thereafter their liability should decrease. As a result of this advice, and having at that time no reason to doubt the findings of the survey, the operators agreed to do all that was asked of them and cooperate with the Government in the steps believed neces-sary to meet the situation, and to provide compensation for the men affected.

Jan 1, 1937

RECORDING that the latest annual meeting was the largest and most successful ever held has be-come almost a habit, but when, as this year, the registration on the first day exceeded any other first day by two hundred, the annual dinner attracted nearly 1200, as compared with 750 at the previous largest one, and the number of technical sessions was larger than ever before, there seems no escape from so regarding it. In spite of the third day being a legal holiday (Washington's Birthday) no slackening, in attendance and interest was noted, and throughout the four days the greatest problem was to find enough meeting rooms and chairs to provide for the sessions, of which as many as twelve were in progress at one time. Solution of the problem would not have been possible (since the Engi-neering Societies building, was designed to provide only three general meeting rooms) except that a part of the eighth floor happened to be temporarily vacant. As these extra rooms will not be available next year, it may become necessary to adopt measures to keep the annual meeting down to the limit of facilities for handling it. The meeting opened on Monday with simultaneous sessions on iron and steel, geophysical prospecting, mine ventilation, non-metallic minerals, and milling, methods. The first four, which were continued after the usual recess for lunch, are reported in more detail elsewhere.

Jan 3, 1928

By H. Foster Bain

[Secretary's NoTE.—This paper, presented in oral abstract at the San Francisco meeting, was not at first supposed by Mr. Rain to be required for publication in the Transactions; and the excursion to Japan, in which he took part, immediately after the San Francisco meeting, delayed his presentation of the manuscript. After his return to San Francisco, Mr. Bain, in view of the importance of his paper and its discussion, kindly furnished it in full. The delay in its publication (since it was received in April last) has been due, partly to the circumstance that other contributions had meanwhile acquired the " right of way," and partly to the consideration that, the situation contemplated in Mr. Bain's paper having remained practically unchanged, the paper and its discussion would not lose force or timeliness by this lapse of time.—J. S. ] No acute observer of public affairs can have failed to observe a growing disposition on the part of the public to change emphasis in government from political equality to social justice. When our own government was founded it was felt to be sufficient to secure to each individual the fullest possible freedom of opportunity, and such a scheme was excellently adapted to the rapid development of a large territory having a small population. As the number of people in a given area increases, there are more points of contact and conflict; each must move in a smaller orbit, and there must be more regula-

Jan 1, 1913

By R. W. Waterfill

MANY existing ore deposits of valuable metals have been worked out in their upper surface levels and the continued productivity of these mines is dependent on their extension to greater depths in the earth. The maximum depths at present reached are about 6000 to 8000 ft. below the surface, with no evidence of an impoverished ore vein. These mines are widely distributed; some of the best known are in South Africa, Brazil, India and in the western sections of the United States. Among the factors which increase the difficulty of working these mines at increasing depths are hoisting, rock pressure and temperature. The manner and effectiveness with which these problems are met will, no doubt, determine in a large measure the ultimate depths to which any mine can be profitably worked. The most critical of these three factors at present is the increase in temperature with depth. The high temperature and humidity in many of these mines at present is severely detrimental to the health of the workers and greatly hampers their efficiency. Some have almost reached a condition in which the human system cannot survive. The problems involved in the cooling and ventilation of mines have all been ably analyzed and presented in previous articles. For this reason, only a resume of conditions affecting the cooling and conditioning of deep and hot mines will be given in this paper before attention is directed to possible methods of improving atmospheric conditions in the working levels.

Jan 1, 1929

By L. H. Dushak

DURING the war period of quicksilver activity there were a number of departures from what may be termed the classical quicksilver metallurgy. Attempts were made to beneficiate low-grade ores by gravity concentration and flotation; mechanical furnaces began to replace the Scott furnace and the vertical coarse-ore furnaces, and condensers of sewer tile and redwood tanks were used in place of the older brick and stone condensing chambers. Other developments that have occurred during the current period of quicksilver activity are mainly in the nature of improvement and further refinement of those started during the war period. Each period of quicksilver activity has been accompanied by the proposal of various new processes, including wet methods for the treatment of quicksilver ores and innovations in furnaces, retorts and condenser equipment. As far as the author knows, nothing of economic significance in the way of "new processes" has been developed. There is in fact no real need for any essentially new process for the treatment of quicksilver ores; the direct furnace treatment is simple and inexpensive. Moreover, with rare exceptions, the quicksilver industry has no complex or refractory ore problems corresponding to those which are receiving more and more attention from metallurgists in other branches of the nonferrous field. Under these conditions improvements in quicksilver metallurgy must be looked for through the adaptation of current developments in engineering and metallurgy generally to the particular needs of quicksilver practice rather than through the invention of new processes.

Jan 1, 1930

By L. H. Dushak

DURING the war period of quicksilver activity there were a number of departures from what may be termed the classical quicksilver metallurgy. Attempts were made to beneficiate low-grade ores by gravity concentration and flotation; mechanical furnaces began to replace the Scott furnace and the vertical coarse-ore furnaces, and condensers of sewer tile and redwood tanks were used in place of the older brick and stone condensing chambers. Other developments that have occurred during the current period of quicksilver, activity are mainly in the nature of improvement and further refinement of those started during the war period. Each period of quicksilver activity has been accompanied by the proposal of various new processes, including wet methods for the treatment of quicksilver ores and innovations in furnaces, retorts and condenser equipment. As far as the author knows, nothing of economic significance in the way of "new processes" has been developed. There is in fact no real need for any essentially new process for the treatment of quicksilver ores; the direct furnace treatment is simple and inexpensive. Moreover, with fare exceptions, the quicksilver industry has no complex or refractory ore problems corresponding to those which are receiving more and more attention from metallurgists in other branches of the nonferrous field. Under these conditions improvements in quicksilver metallurgy must be looked for through the adaptation of current developments in engineering and metallurgy generally to the particular needs of quicksilver practice rather than through the invention of new processes.

Jan 1, 1930

By Maurice Cook

A procedure of obtaining specimens of lead, tin, and cadmium with a moderately equiaxed structure and a smooth surface suitable for etching without grinding and polishing is described; the advantages of general oblique illumination (as opposed to vertical illumination) in the photomicrography of pure metals .are stated. Using these methods, a statistical study of the changes brought about in deformed lead, on annealing, has been made. The common mode of structural change was found to be recrystallization. Cases of growth of one original grain into another were rare; but if a totally recrystallized specimen was annealed above 200° C., a few large grains appeared and spread over the whole area, except for a certain number of small grains which remain unabsorbed. The temperature needed to produce structural change in lead was found to be lower, the greater the degree of deformation. With tin, an extension of 28 per cent. caused practically no recrystallization at ordinary temperatures, but recrystallization occurred if the specimen was heated to 100° C. In cadmium at low temperatures, the grain size decreased in marked manner as the deformation increased; but at high annealing temperatures, the grain size was comparatively independent of the degree of deformation. THE structural changes in metals brought about by annealing following a deformation at a low temperature has been the subject of many investigations. No less than eleven metals and alloys have been studied in some detail; namely, aluminum,1 tungsten,2 iron,3 copper,4 gold,5

Jan 11, 1924

By W. C. Ellis, M. E. Fine

WHEN certain binary Fe-Ni alloys are worked cold and then stabilized by a stress-relief anneal, their Young's moduli are nearly invariant over a substantial temperature range determined by composition and work-anneal history.' In the present investigation addition of molybdenum to such alloys (besides increasing the yield strength) was found to diminish the sensitivity of the thermal coefficient of Young's modulus to composition changes. Such alloys are of interest for applications requiring 1 a metal with controlled, low temperature coefficient of Young's modulus and substantial magnetic permeability.' Young's modulus ordinarily decreases with rising temperature. In ferromagnetic alloys a change in modulus on heating due to loss of ferromagnetism modifies the .temperature dependence. Far below the Curie temperature ferromagnetism alters the modulus in two ways: a—Addition of the energy of magnetization, a function of interatomic distance, changes the relation between interatomic energy and distance.' This lowers the modulus in the Fe-Ni and Fe-Ni-Mo alloys of this investigation. b—An applied stress changes the ferromagnetic domain arrangement so that linear magnetostriction contributes to the strain and further lowers the modulUs.~ Since in the alloys of this investigation both effects lower the modulus, loss of ferromagnetism on heating changes the slope of the modulus-temperature curve in a positive direction. With increasing temperature the slope of the modulus-temperature curve, due to progressive loss of ferromagnetism, becomes less negative, goes through zero (the modulus is minimum), becomes positive, and resumes its normal negative value above the Curie temperature.' The increase in modulus and decrease in curvature in the modulus-temperature curve occurring on work hardening have been attributed to a reduction in effect (b).'. Vn the absence of ferromagnetism work hardening through introduction of residual strains would be expected to decrease the modulus.' Alloy Preparation—Test Methods Four series of alloys having nominal molybdenum contents of 5, 7, 9, and 10 pct and containing 47 to 58 pct Fe (the analyzed compositions are given in Table I) were melted in air and cast as bars weighing from 2 to 6 lb. The charge consisted of electrolytic nickel, Armco iron, molybdenum (99+ pct) or ferromolybdenum (62 pct Mo), manganese, and aluminum as a deoxidizer. The bars were swaged cold to the desired diameters with intermediate anneals. Alloys in this composition range are reported" to be face-centered cubic and ferromagnetic at room temperature. The Curie temperatures" decrease with molybdenum. For example, keeping the Ni/Fe ratio at unity and increasing the molybdenum from 0 to 17 pct decreases the Curie tempera- ture from approximately 500°C to room temperature. (The 17 pct Mo alloy requires quenching to retain a single phase.~) Young's modulus at a series of temperatures from —50" to 100°C was determined by a dynamic method previously described.', " In this method Young's modulus is calculated from the resonant frequency (in this case approximately 50,000 cycles per second) of a rod sample (approximately 2 in. long) vibrating longitudinally in the first mode. The densities of the samples at room temperature, Table I, were determined by the standard method of weighing in air and reweighing in redistilled bromobenzene. The linear coefficients of expansion, Table I, needed to calculate the sample length and density at the temperature of measurement, were obtained by observing the change in length (22" to 100°C) of an 8 in. gage distance with a two microscope cathetometer. The values of density and coefficient of expansion in the few samples checked are independent of treatment to the accuracy reported. This was assumed to be general for all the samples. The modulus values are accurate to &0.05x101' dynes per sq cm. However, values of thermal change in modulus are accurate to 20.005~ 10" dynes per sq cm. Young's Modulus Values at 25°C: The modulus values of O', 5, and 10 pct Mo alloys at 25 °C are plotted in Fig. 1 as functions of nickel. After working cold, the samples were either recrystallized at 950" to 1000°C or given a low temperature stabilizing anneal at 400° C. The 400°C anneal does not reduce the hardness nor cause recrystallization. Annealing at 400 °C does

Jan 1, 1952

By Donald C. Myntti

INTRODUCTION A major segment in a successful heavy equipment maintenance and repair program is the provision of well-laid out and well-equipped shop and service facilities The facilities described here will be those required for a large, high tonnage hard rock open pit mine utilizing rotary drills, shovels, haulage trucks, support equipment, and service trucks. The term support equipment covers the equipment required to support the drill, shovel, and truck operations, these are crawler tractors, road graders, front-end loaders, water trucks, rollers, rubber-tired tractors, etc. Service trucks are the automotive type consisting of rubber-tired over-the- road equipment. The primary structures generally involved in the total maintenance effort are as follows. (1) the main shop with an attached warehouse (the structure could also house the tire and lube shops plus the equipment cleaning stalls), (2) a service station with bulk petroleum product storage tanks, (3) a heating plant, (4) a security station (lf this is a corporate requirement), (5) operating department and employee assembly buildings, and (6) an electrical substation. Under certain conditions, many of these facilities with the exception of the substation could be combined In one or several structures. This arrangement could have a great advantage especially in areas where the heating of the structures is extremely critical.

Jan 1, 1979

By D. B. Robinson, C. A. Macrygeorgos, G. W. Govier

Experimental data have been obtained on the volurrletric behavior of ternary mixtures of methane, hydrogen sulfide and carbon dioxide at temperalures of 40°, 100" and 160°F up to pressures of 3,000 psia. The results indicate that the compressibility factors for this system do not agree with compressibility factors for sweet natural gases at the same pseudo-reduced conditions. The deviation increases as the temperature and methane content decrease. Discrepancies of up to 35 per cent were observed. A careful analysis has been made of the existing pUrblished data on compressibility factors for binary systems containing light hydrocnrbons and hydrogen sulfide or carbon dioxide. It has been found that the deviation of actual from predicted compressibility factors for methane-acid gas mixtures is a function of the methane content and the pseudo-critical properties,.v of the mixture. The ratio between actual compressibility factors for methane-acid gas mixtures and compressibility factors for sweet natrlral gases at the same pseudo-reduced conditions has been currelated over a range of pP,, from 0 to at least 7 arid a range of pT, from about 1.15 to at 1east 2 0 with an error not exceeding 3 per cent and over most of the range within I per cent. The validity of the correlation for mixtures containing appreciable hearvier hydrocorbons has not been fully established, but it is shown to be preferable than the use of a corretation based only on hydrocarbons. INTRODUCTION Although a relatively accurate method for predicting compressibility factors of pure materials is provided by charts based on reduced properties and the assumption that the compressibility factor is a unique function of T P and z the determination of the correct values of compressibility factors for gas mixtures is somewhat difficult. Two general methods of dealing with gaseous mixtures have been proposed. The first assumes a direct or modified additivity of certain properties of the mixture in terms of the properties of the individual components. Examples of this method are based on the familiar laws of Dalton and Amagat. The second method averages the constants of an equation of state applicable to the pure components. Both of these methods are of limited value in engineering calculations because the first usually provides reliable answers only over narrow ranges of pressure and temperature and the second is cumbersome to handle. In petroleum engineering practice accurate estimations of the volumetric behavior of natural gases arc frequently required. To fulfill this need, several generalized compressibility charts have been developed.' ' Of these, the one prepared by Standing, el al is widely used at present. In the construction of charts of this type a third method for dealing with mixtures has been followed. It is based on correlation of pseudo-critical properties as outlined by Kay and calculated from the critical properties of the individual components in a mixture. Although these charts provide relatively accurate information on the compressibility of dry or wet sweet natural gases, they are less reliable when used for gases containing high concentrations of hydrogen sulfide or carbon dioxide or both. Thus, an experimental program, although time consuming, is the best means now available for the determination of the volumetric behavior of sour or acid gas mixtures. An increased interest in the behavior of these gas mixtures, particularly in connection with some of the fields in Western Canada where the acid gas concentration of the reservoirs may be as high as 55 per cent and where hydrogen sulfide alone may be as high as 36 per cent, provided the incentive for this study. It was the purpose of the investigation to determine the volumetric behavior of selected mixtures of methane, hydrogen sulfide and carbon dioxide over a range of temperature from 40" to 160°F and at pressures up to 3,000 psi. EXPERIMENTAL METHOD The apparatus used in this investigation was basically the same as that described by Lorenzo.'" The amount of each pure component used in preparing the gas mixtures was measured over mercury in a glass-windowed pressure vessel. The pure components were then transferred individually in the desired amounts to a second glass-windowed pressure vessel where the volumetric behavior of the mixture was determined. Volume was varied by mercury injection or withdrawal. The capacity of the cell was about 125 cc. Temperatures in the cells were measured with copper-constantan thermocouples and a Leeds Northrup semi-

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid's reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,' so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966

By Charles M. Cooley

DURING the last week in April, cards were sent out from New York to Institute members affiliated with the Mining, Geology, and Geophysics Div. The cards requested recipients to indicate their main technical interest, within the division, i.e., mining, or geology, or geophysics. The reason for the cards is simple. Within the Institute more than 8000 have expressed either primary or secondary interest in this division. However, there is no way to determine the technical association stimulating this interest.

Jan 6, 1953

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa.*.. *May: '71.. 1 3 2. Bethlehem, Pa Aug. '71.. 1 10 3. Troy, N. I X Nov. '71.. 1 13 4. Philadelphia, Pa Feb. '72.. 1 17 5. New York, N. Y.*.... May, '72.. 1 20 6. Pittsburgh, Pa Oct., '72.. 1 . 25 7. Boston, Mass Feb., '73 1 28 8. Philadelphia, Pa.*.... May, '73 2 3 9. Easton, Pa Oct., '73 2 7 10. New York, N. Y Feb., '74.. 2 11] [ ]

Jan 1, 1925

By C. A. Shook, W. H. W. Husband, D. B. Haas

Although previous studies l,2,3 have been made, no correlations for pressure drop have been proposed. This is probably because severe particle breakage occurred and pressure drops changed substantially with time. A quantitative statement of the relationship of pressure drop to the parameters of the system is desirable for lignite since, unlike higher rank coals, lignite slurries are thixotropic. The present investigation was undertaken to quantify the pipeline behavior and required continuous monitoring of pressure drop and size distribution.

Jan 2, 1979