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By Samuel Storchheim

IT was noted that variations existed in the magnetic properties, namely, coercive force, He, and rema-nence, Br, of 18/8 stainless steel wires of the same analysis when these wires were given the same percentage of reductiori of area at different rates of reduction. In order to determine the extent of these variations, a program was initiated whereby commercial 302 and 304 stainless steels were drawn with a wide variation of speeds. Ultimate tensile strengths and specific resistances, as well as the Hc-BT measurements, were determined. If variations of considerable magnitude were found, it was thought that the knowledge accrued from the investigation could probably aid in determining the particular drawing speed required to obtain desired properties for a given specification for a particular analysis of wire. Drawing Procedure Two specimens (set I, No. 302 and No. 304), the chemical analyses of which are given in Table I, were drawn at different speeds, namely, 45 to 3900 ft per min, directly from 0.016 in. diam wire to 0.004 in. diam wire, a 93.7 pct reduction of area. To obtain this high percentage of reduction, the wire at 0.016 in. was softened by annealing at 1150°C. It was then strung in a No. 16CF variable speed Vaughn drawing unit and passed through 13 B.&S. gage dies of successively smaller diameter, as shown in the accompanying table. Following this step, several hundred feet of the wire was drawn, at a particular speed, through the dies and wound upon a spool. Once the sample of wire was drawn at the desired speed, the spool with the finished sample was removed, tagged for later identification, and an empty spool was placed in the machine. Another wire sample was drawn at a different speed, after making the necessary adjustments upon the Vaughn unit. At the greater speeds, several thousand feet of sample were drawn to insure that the wire to be used for testing would be uniform. This was done because the desired speed was not reached instantly; the wire taking a short while to attain the required drawing rate. All speed measurements were made by placing a tachometer against one of the machine's pulleys during the actual drawing of the specimens. 84.4 pct reduction of area. The 0.072 in. diameter wire was also annealed at 1150°C. The process of obtaining samples was the same as described above. The only difference between the two was that the rates involved were not as extensive, set II covering a range of 625 to 1150 ft per min. Tensile tests were carried out for the 0.004 in. diam wires on a horizontal Scott Tensile Tester, while tensile tests for the 0.028 in. diam wires were made on a vertical Scott Tensile Tester. Each value listed in the tables represented the average of five samples with a maximum deviation of approximately 3 pct among the samples. Resistance per foot of the wires was determined by use of standard bridges accurate to the nearest hundreth of an ohm for the 0.004 in. wire, and to the nearest thousandth of an ohm for the 0.028 in. wire. The resistances per foot were then converted to resistivities by use of the following equation: P = RxCM where R is the resistance per ft in ohms per ft; CM, the area in circular mils; and P, the resistivity in ohms—CM. The values listed in the tables likewise

Jan 1, 1952

By W. McA. Johnson

THE work of J. E. Johnson, Jr., on the effect of small amounts of oxygen in cast iron in increasing its strength and resistance to shock, is of interest from the technical and scientific standpoints. The following exposition of the theory carries Mr. Johnson's explanation further and, in my opinion, will disclose certain related phenomena and perhaps shed further light on the subject. Some facts, so novel in character as to excite incredulity, have been accepted finally by many metallurgical authorities. One of these is that oxygen to the amount of 0.060 per cent. in cast iron gives it a breaking strength of 3,500 lb. per square inch, compared with a breaking strength 2,500 lb. per square inch in cast iron of the same composition with re-ect to elements other than oxygen, but having only 0.010 per cent. oxygen. The "oxygenated" cast iron, even if made in a coke furnace, has properties equivalent to the best charcoal pig iron. Mr. Johnson has also established the fact that the variations in combined carbon cannot account for the results. By microphotographic evidence he has shown that in oxygenated cast iron the graphite particles are dense and spherical, while in well-deoxidized cast iron the graphite particles are flaky and leaf-like. It is just a matter of common sense that iron of the latter structure is much weaker than the former. The analytical and microscopical work has been done with care and there is no doubt in my mind about the accuracy of the, experimental results. In this paper then, we shall consider it as accepted that small amounts (0.060 per cent.) of oxygen increase the strength of cast iron by producing a structure in which the round and solid particles of graphite are surrounded firmly by a principal matrix of ferrite. The purpose of this paper is to show that the reason why the graphite particles are round is founded on the fact that the particles of any precipitate are made denser and harder by the presence of a reagent having a solvent action on the precipitate. This can be stated as a law, although I have never seen it so given in any textbook.

Jan 2, 1916

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By J. R. Thoenen

If asked whether limestone production was a mining problem I would not hesitate to answer emphatically in the affirmative. The question, "When is a quarry a mine?" is familiar. The immediate mental picture induced by the thought of limestone production is that of an open quarry. All are familiar with the open pit in the iron-producing districts of Minnesota and Michigan and the open cuts of the so-called "porphyry" coppers of the West. If these are mines, they differ little from limestone quarries in general mode of operation; if quarries, why do they need the attention of mining engineers? During 1923, the United States produced in round numbers 70,000,000 tons of iron ore. The limestone production of the United States for the same period was something over 100,000,000 tons. In tons, it about equals the oil production of the United States. The uses of limestone are legion. A paper read by a prominent engineer of Chicago, at the meeting of the National Crushed Stone Association held last February in St. Louis says: "There is no industry in the United States today that is more basic in its operation or by itself controls more industries. There is hardly a chemical operation, hardly a metallurgical operation or building operation that a crushed-stone man does not control if he will jump in and make the full utilization of it." Some of the many uses are for road metal, concrete, railway ballast, building stone: riprap, and rubble, the manufacture of iron and steel, alkalies, calcium carbide, magnesia, carbolic and carbonic acids, asphalt filler, mineral wool, poultry grit, sulfuric acid, phosphates, nitrates, soap, baking powder, the purification of copper and prevention of coal-mine explosions, to say nothing of the quantities used in the making of lime and cement. It has been said that without iron we would revert to the Stone Age; how much iron would we have without limestone? From the point of view of the mining engineer, using the term in its broad sense to include geologists and metallurgists, the production of limestone is important because of its occurrence, volume, commercial importance, and the problems presented by its recovery and treatment.

Jan 1, 1925

By Ralph Sweetser

AT the joint session of Blast Furnace and Open Hearth Committees, April 7, 1937, at Birmingham, the subject of the quality of basic open-hearth pig iron was so well presented and discussed from so many different viewpoints that it was the general opinion that progress had been made and that such meetings were conducive to the advancement of the art of making pig iron of the right quality for the open-hearth man to produce the most satisfactory quality of steel. It was agreed that there is a decided differentiation between the chemical analysis of pig iron and the "quality" of pig iron. Paul J. McKim said that open-hearth furnace operators frequently make refer-ence to certain types of iron as "bad iron," "dirty iron," "cold metal,' etc., claiming that when using these irons, although they are within specified chemical analysis, it is impossible to produce quality steel. Mr. McKim gave a list of the suggested causes of those "certain types" of bad irons that have a thoroughly respectable analysis but a thoroughly disreputable character. Another open-hearth man, P. A. Maclsaac, of Nova Scotia, said that: The effects of iron flint is below standard in analysis or in that mysterious property called quality, are well known to all open-hearth operators. It has been shown that iron of this type results in the production of steels on which the rejections of finished product, run high. What is to be done about it? I would say that the burden of producing high-quality iron should be placed squarely on the shoulders of the blast-furnace man, even as that of making good steel is shouldered by the open-hearth luau. It is the purpose of this paper to bring out into the open this 'mysteri-ous property called quality"; that is, in those "certain types" of basic pig iron that make it impossible to produce quality steels; and at the same time to point the way for the blast-furnace man to be able to shoulder the burden that Mr. MacIsaac and all other open-hearth men and foundry-men have placed upon him.

Jan 1, 1938

By W. J. Locher

One important means of reducing steel consumption in grinding mills is not mentioned in S.G. Malghan's paper. It is simply to reduce the oxygen content in the mill and pulp. While oxygen dissolved in pulp is not readily reduced without additives, reduced aeration and reduced ventilation of grinding mills are often feasible. It is not necessary to completely eliminate the oxygen to achieve substantial benefits, since corrosion rates vary with oxygen content in a manner analogous to combustion rates as oxygen content increases. It is difficult to generate indisputable quantitative data on the relationship of oxygen reduction in a milling system to changes in consumption of grinding steel. Perhaps this accounts for the absence of technical papers on the effects of reducing oxygen content in grinding mills by reducing aeration of pulp and ventilation of grinding mills. One qualitative observation is that mills operating at a lower percent of critical speed will tend to have lower media consumption for similar fineness of grind without necessarily having an equivalent reduction in power consumption per ton of product. Reduced mill speed would also tend to reduce both ventilation of the mill and entrainment of air in the pulp. Larger grinding mills tend to be more media efficient because they operate at a greater ratio of charge volume to pulp surface area, which will tend to reduce the aeration per unit of pulp volume. The mechanical steps required to reduce aeration of grinding mill pulps depend on the configuration of the grinding circuit and related process. Reply by S.G. Malghan Mr. Locher stated that my paper did not mention the reduction of oxygen content of the pulp as a potential method of decreasing the steel consumption. I would like to bring to the attention of Mr. Locher that an indirect reference was made to the fact that pulp oxidation potential controls the corrosion wear of steel. Though dissolved oxygen is one of the factors that controls oxidation potential, additional discussion was deliberately avoided for the reasons mentioned by Mr. Locher. The most important reason being the difficulty of decreasing and controlling the oxygen concentration of the pulp in a commercial mill.

Jan 1, 1984

IN discussing the art of the goldsmith, it is apparent that it is an art requiring skill. He who wishes to be acclaimed a good master therein must be a good universal master in several arts, for the different kinds of work that come to his hands to be done are infinite. Those who work in gold and silver must outdistance all other craftsmen in learning and achievement to the same degree that their materials outdistance other metals in nobility. Therefore, it is necessary first of all to be a good designer, because design is the key that opens the doors not only to the goldsmith's craft but to all others. Then it is necessary that he understand melting and that he know well how to work with a hammer and how to use flat gravers and burins in engraving, as well as files and chisels. He must also possess certain secrets that are needful to the art, which in truth are parts of alchemy, such as softening gold when it is brittle and raw, coloring it when it has little color, soldering, enameling, working in niello, blanching, gilding, and an infinite number of things which must all be known in detail. But above all he who wishes to do this art well must be very patient in working, must know how to mould and how to proceed with the melt and with the file, hammer, chisel, or other implements for bringing his gold or silver work to the final state which he plans. He must also have good judgment in gems and know well how to recognize every [134v] good or defective quality they possess, and to distinguish the false gem from the true, either when set or when unmounted, as there is need; also how to value them both in buying or selling and in satisfying others who seek his appraisal. He should also be experienced not only in the technique of melting but also in the methods of assaying, parting, refining, cementing, and the like, and still many others. But if I wished to tell you of every part

Jan 1, 1942

By S. R. Elliott

THE principles of the caving system, as they apply to mining of soft iron-ore deposits, are well known, as this method has been in use for many years. It is, however, necessary to give a general description of it before describing the Athens method. The shaft and surface equipment should be placed at a sufficient distance from the orebody, so that the caving and pulling of the surface will not disturb the operations of the mine. Levels are started at the proper intervals, and when raises are completed, slicing commences at the top of the orebody and progresses downward. The necessary precautions are taken to avoid the occurrence of large open rooms and it is customary to break sufficient capping to form a mat to prevent heavy falls of ground from crushing through to the lower sublevels and endangering the lives of the workmen. Slicing is continued, and when sufficient width and length are undercut, the capping commences to cave, and in time a settlement occurs at the surface. As soon as this caving commences, the pressure on the timber naturally increases; after it extends to the surface, the amount of pressure has a certain relation to the depth. In other words, the pressure increases with the depth, but not in direct proportion. At great depths, such as that found at the Athens, 2500 ft. (760 m.), the pressure might be so excessive that the cost of keeping working places open would be prohibitive. The actual caving of the surface in a deep mine, with a great thickness of capping, is slow and often takes years to accomplish. After sufficient width and depth -have been undercut, the capping starts to break away, but through arching large masses of rock-.fill the opening, support the capping, and retard the continuation of caving. Caving to the surface is, therefore, retarded until either a sufficient thickness of the orebody is removed, or the width and length of the undercut part have been greatly increased. I wish to emphasize this fact of slow caving, for it is on, this principle that the success of the Athens system. largely depends.

Jan 8, 1920

By A. F. Lucas

EACH day, the fact becomes more evident that the ever-growing demand for oil is farther outstripping production, regardless of the increase in output throughout the past twenty years. The development of known oil fields and the prospecting for new ones along present lines are not resulting, in, and cannot bring forth, supplies large enough adequately to meet the oil needs of the country. The usual methods of prospecting-for new supplies are insufficient to meet the exigencies of the situation which threatens, in the not distant future, to reach a critical stage. Were it not that within the last two years new and prolific oil fields have been discovered in northern Louisiana, central Texas, and California, this crisis would undoubtedly be now at our door. Stocks are being exhausted in spite of the rapid growth of imports. The time is therefore fast approaching when some radical departures must be made in the method of prospecting and developing old and new fields in order to increase our oil supplies. Methods and chances, that have seemed unwarranted will not only be given serious consideration, but, according to the results promised, will be put to the test. Meanwhile, however, nearly all the oil fields are responding to the stimulus of higher prices, whereby enormously growing capital is attracted to this important industry, both here and abroad; the increase in our petroleum production at the present time is due to this circumstance. Yet, although a most active search is being made for possible sources of additional supply, one section of our country is not yielding the results that, in my opinion, it is capable of producing: I allude to the coastal dome belt of Texas, Louisiana, and Mexico. The United States Geological Survey has estimated that three-fourths of a billion barrels are available in the ground in the Coastal Plain of the two states just mentioned. Numerous papers have been written on the subject of the salt domes of the Coastal Plain and more or less attractive theories have been advocated by leading geologists to account for their origin and the presence of the oil, sulfur, and salt associated in them. However, owing in part to the generally monotonously level country in which the coastal

Jan 9, 1920

By J. T. Duce

There were no important changes in the producing situation in Colombia in 1930, because the emergency bill passed by the Colombian Congress in 1927 is still in effect, and therefore no change has taken place in the law governing petroleum. At the close of 1930 the Colombian Congress began to consider a new petroleum bill. This measure is an improvement on the preceding bills which had been the subject of so much debate in the Congress. However, it cannot by any means be regarded as perfect, and a number of criticisms may be justly leveled at it. The most substantial one probably is that the royalties on public lands, and the taxes on private lands, while apparently low, are deliverable at seaboard, or payable based on seaboard price at the option of the government. If the government exercises its option to take the oil at the mouth of the well, the cost of the transportation figured back into oil is also deliverable to the government. This phase of the law has the effect of making seemingly low royalties a burden on the operator. The fact that taxes on private properties are deliverable in kind is also an unusual provision for which there is no good precedent. The pipe line provisions are also noteworthy, and the government has authority to fix rates and also to deny permits to construct pipe lines for reasons affecting national economy. There are also clauses enforcing unit operation on both public and private lands, and collecting a tax of 1 c. per 1000 ft. of gas wasted. It remains to be seen whether this bill will be enacted, or whether it will be substantially modified. This much may be said, however, that unless it is modified, it will defeat its own purpose; i. e., promotion of petroleum development in Colombia. Company Activities The South American Gulf Oil Co. shut down its operations during the year, and now employs only watchmen at its camps, Las Monas and El Tigre. The Standard Oil Co. of California continued operations on the Coast at Repelon and Gualapa. At the close of the year Repelon

Jan 1, 1931

By Nelson W. Taylor

With the extensive deposits of potash minerals which have been discovered in the southwestern states, and their rapid development, a permanent American supply of potassium compounds is now assured. The 325-year history of the potash industry in this country has been told by H. I. Smith1, of the U.S. Geological Survey, and the more recent activities of the Survey and of American potash companies were described last year by the same author2. In fact, it may be stated that so great is the productive capacity that two mines in New Mexico and one in California are able to supply more than half a million tons of crude and refined salts over and above that produced for agricultural purposes. The era of scarcity has given way to an era of superabundance. This situatiori makes it desirable for the potash producer to look for other applications for his product, and it is with this in mind that the writer presents some information pertaining to present and possible future uses for potassium compounds in the ceramic industry. Ceramic Products Ceramic products are essentially solid materials containing one or more oxides such as SiO2, Al2O3, CaO, MgO, FeO, K2O, Na2O, TiO2, which are the oxides of greatest abundance in the earth's crust. The typical ceramic process is that of firing or burning the batch, and the product may be glassy, crystalline or mixed. In the glassy or vitreous group come glass, porcelain enamel and glazes; in the crystalline group, refractory materials such as silica brick, or chromite or magnesia; and in the mixed group, porcelain, chinaware, stoneware, tile, brick, etc., which contain both a vitreous and a crystalline phase, in variable proportions. The ceramic industry of the United States is a billion dollar industry, and is important not only because of its magnitude but also because of the key position occupied by certain ceramic products in the whole manufacturing structure. From the standpoint of use of potash, the field of refractories is of no great interest, since K2O lowers the melting point of a refractory oxide and

Jan 1, 1938

By J. R. Thoenen

IF ASKED whether limestone production was a mining problem I would; not hesitate to answer emphatically in the affirmative. The question, "When is a quarry a mine?" is familiar. The immediate mental picture induced by the thought of limestone production is that of an open quarry. All are familiar with the open pit in the iron-producing districts of Minnesota and Michigan and the open cuts of the so-called "porphyry" coppers of the West. If these are mines, they differ little from limestone quarries in general mode of operation; if quarries, why do they need the attention of mining engineers? During 1923, the United States produced in round numbers 70,000,000, tons of ore. The limestone production of the United States for the same period was something over 100,000,000 tons. In tons, it about equals the oil production of the United States. The uses of limestone are legion. A paper read by a prominent engineer of Chicago, at the meeting of the National. Crushed Stone Association held last February in St. Louis says: "There is no industry in the United States today that is more basic in its operation or by itself controls. more industries. There is hardly a chemical operation, hardly a metallurgical operation or building operation that a crushed-stone man does not control if he will jump in and make the full utilization of it." Some of the many uses are for road metal, concrete, railway ballast, building stone, riprap, and rubble, the manufacture of iron and steel, alkalies, calcium carbide, magnesia, carbolic and carbonic acids, asphalt filler, mineral wool, poultry grit, sulfuric acid, phosphates, nitrates, soap, baking powder, the purification of copper and prevention of coal-mine explosions, to say nothing of the quantities used in the making of lime and cement. It has been said that without iron we would revert to the Stone Age; how much iron would we have without limestone? From the point. of view of the mining engineer, using the term in its broad sense to include geologists and metallurgists, the production of limestone is important because of its occurrence, volume, commercial importance, and the problems presented by its recovery and treatment.

Jan 2, 1925

By Nelson W. Taylor

With the extensive deposits of potash minerals which have been discovered in the southwestern states, and their rapid development, a permanent American supply of potassium compounds is now assured. The 325-year history of the potash industry in this country has been told by H. I. Smith1, of the U.S. Geological Survey, and the more recent activities of the Survey and of American potash companies were described last year by the same author2. In fact, it may be stated that so great is the productive capacity that two mines in New Mexico and one in California are able to supply more than half a million tons of crude and refined salts over and above that produced for agricultural purposes. The era of scarcity has given way to an era of superabundance. This situatiori makes it desirable for the potash producer to look for other applications for his product, and it is with this in mind that the writer presents some information pertaining to present and possible future uses for potassium compounds in the ceramic industry. Ceramic Products Ceramic products are essentially solid materials containing one or more oxides such as SiO2, Al2O3, CaO, MgO, FeO, K2O, Na2O, TiO2, which are the oxides of greatest abundance in the earth's crust. The typical ceramic process is that of firing or burning the batch, and the product may be glassy, crystalline or mixed. In the glassy or vitreous group come glass, porcelain enamel and glazes; in the crystalline group, refractory materials such as silica brick, or chromite or magnesia; and in the mixed group, porcelain, chinaware, stoneware, tile, brick, etc., which contain both a vitreous and a crystalline phase, in variable proportions. The ceramic industry of the United States is a billion dollar industry, and is important not only because of its magnitude but also because of the key position occupied by certain ceramic products in the whole manufacturing structure. From the standpoint of use of potash, the field of refractories is of no great interest, since K2O lowers the melting point of a refractory oxide and

Jan 1, 1938

By N. Mungan

A study was made of the effects of wettability and interfacial tension on the immiscible displacement of a Iiquid by another Iiquid from porous media. The influence of viscosity ratio was also investigated. Porous media used were polytetrafluoroethylene (TFE) cores prepared by compressing TFE powder under different pressures. lt is shown that displacement of a wetting by a nonwetting Iiquid is always less efficient than the displacement of a nonwetting by a wetting fluid, all other things being equal. In the former case, the recovery efficiency can be increased substantially by either reducing the interfacial tension or increasing the viscosity of the displacing fluid. A qualitative discussion is given on the implications of this work to the recovery of crude oil by water flooding. INTRODUCTION The high cost of oil exploration and new recovery schemes makes it imperative that waterflooding be conducted under conditions favoring most efficient oil recovery. To improve oil recovery by waterflooding, it is essential that the role played by interfacial forces in the entrapment of residual oil be studied and understood. Interfacial phenomena in natural rock, connate water and crude oil systems are very complicated because of the complexity of the natural liquids found in petroleum reservoirs, because of our inability to adequately describe the geometrical structure of the porous media and because of a lack of understanding of physical and chemical interactions between the liquids and surface of the pores. The problem becomes further complicated when one tries to elucidate the role of interfacial phenomena in fluid flow. Numerous studies of the displacement of oil by water under different interfacial tension or wet-tability conditions have been made.lm3 These studies have been performed in silica, alundum or sandstone systems using water and paraffin oil and also some surface active material to control the interfacial tension s and the contact angle 0. Unfortunately, the high energies of various interfaces involved favor adsorption and orientation of the surface active material at the interfaces. Also the surface active material concentration at the interfaces exceeds that in the bulk of the liquid phases. Such surface excess may cause the surfactant distribution, the contact angle and the interfacial tension to differ from their measured static equilibrium values and makes interpretation of the displacement experiments difficult. Furthermore, as changes in s also lead to changes in cos 0, the role played individually by one of these parameters in the displacement becomes obscured by the effect of the other. To circumvent these difficulties, a low surface energy solid and true solutions or pure liquids should be used. Use of a low surface energy solid minimizes adsorption and orientation effects at the solid-liquid interfaces. By controlling s and cos 0 through use of selected pairs of pure liquids or true solutions rather than by surfactants, the adsorption effects at liquid-liquid interfaces are eliminated. In the present study TFE cores were used as the porous media. Liquids used were water, sucrose solutions, paraffin oils and benzyl, n-butyl and isobutyl alcohols. The interfacial tension was varied from 40 to 1.1 dynes/cm by suitably choosing the liquid pair. A surface active material was added to the water-oil system only in the case where interfacial tension of 0.5 dyne/ cm was desired. No precise changes of cos 0 were attempted. However, either the displaced or the displacing liquid could be made the one which preferentially wets the TFE surface. Using sucrose solutions and blends of paraffin oils proved to be a convenient way of changing the viscosity ratio between the displaced and displacing liquids. The present investigation examines the effect of interfacial tension, wettability and viscosity ratio on the immiscible liquid-liquid displacement from porous media. Observed data permit a

Jan 1, 1967

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By G. C. Bernard, L. W. Bernard, L. W. Holm, W. L. Jacobs

The effect of loam on the permeability of porous media to water was studied as a {unction of foaming agent concentration, specific permeability, pressure gradient, length of a porous medium and its oil saturation. At a given fluid saturation in a porous medium, the permeability to water was found to be the same whether loam was present or not. Foam decreases the permeability to water by developing a higher trapped gas saturation than that obtained by water flooding without loam present, increasing the concentration of foaming agent increased the trapped gas saturation and thereby decreased the permeability to water. The presence of oil reduced the capability of most foaming agents to decrease the permeability of a porous medium to water. A few surfactants were found to be effective loaming agents even in the presence of oil. These results are similar to those reported in a previous paper on the effect of loam on the permeability of porous media to gas. The effect of loam was found to persist in long porous media at moderately high reservoir temperatures and during the passage of many pore volumes of surfactant-free water. INTRODUCTION This paper describes part of a study on a novel approach in the use of surfactants for oil recovery; the use of foam rather than water to displace oil. Previously it was found that foam can displace oil which normally is not displaced by water.4 The foam is formed by successively injecting a suitable surfactant solution and gas into a porous medium. Foam appears to have at least two uses in the field: (1) it shows promise as a superior oil recovery agent, and (2) it shows promise as a selective permeability reducing agent. Foam may be very useful in water floods, or in other oil recovery processes, where highly permeable streaks or unfavorable mobility ratios are a problem. A previous paper reported the effect of foam on the permeability of porous media to gas.1 In the present study the effect of foam on the permeability of porous media to water is reported. The specific objectives of the study were to determine: (1) the effect of foam on the permeability to water in porous media of various specific permeabilities, (2) the effect of foam on the permeability to water in the presence of oil, (3) the effect of foam and crude oil on the trapped gas saturation, (4) the effect of foam on permeability to water at trapped gas saturation, (5) the effect of pressure gradient on the permeability to water under foaming conditions, (6) the persistence of foam during the passage of surfactant-free water through the porous medium, and (7) the effect of various foaming agents, length of the porous medium and temperature on the permeability reduction caused by foam. EXPERIMENTAL PROCEDURES EQUIPMENT AND MATERIALS The experimental apparatus consisted of consolidated and unco n soli dated porous media, wet test meters and constant delivery pumps. The porous media consisted of consolidated sandstone cores (6 to 36 in. long), and unconsolidated sand packs (3 to 30 ft long). The consolidated cores had permeabilities of 32 and 1,000 md and porosities of about 20 per cent. The sand packs had permeabilities of 3,500 to 211,000 md and porosities of about 40 per cent. (Throughout this report a term such as 100 md sand" is used. This term means that the porous medium had a dry, nitrogen permeability of 100 md.) Fluids used in the experiments were distilled water, 1 per cent NaCl solution, aqueous solutions of foaming agents, nitrogen gas, air and crude oil.

Jan 1, 1966

By R. F. Krueger, L. C. Vogel, P. W. Fischer

Previous studies have shown that the permeabilities of sandstone cores are markedly reduced following exposure to drilling fluid and subsequent clean-up with oil at high-pressure gradients. Laboratory experiments reported in this paper indicate that permeability damage from drilling mud or water can be substantially avoided through use of an initial low-pressure gradient followed by gradually increasing gradients during clean-up by reverse oil flow. On the other hand, attempts to improve the permeability of damaged Berea and oil formation cores with high-rate oil backflush (simulated well stimulation) and low-rate clean-up gave erratic results. Essentfully complete permeability repair was achieved in most of the fresh water-damaged cores from Miocene and Pliocene oil-producing formations; only minor improvement was noted generally in tests with both water-and mud-damaged Berea sandstone. Field well stimulation treatments using high-rate back-flush resulted in long-term productivity improvement when production was brought in at gradually increasing production rates and then restricted to a steady value less than the maximum possible rate. Wellbore plugging at high production rates correlated with increasing solids content in the produced oil. Observations and results from these tests agree with current concepts that formation damage in water-sensitive rocks results from movement and bridging of formation fines, rather than from clay swelling alone. INTRODUCTION Many laboratory studies1-g have shown that the permeabilities of sandstone cores are often markedly reduced following exposure to fresh water or water-base drilling mud filtrate. However, work with cores in the restored state has demonstrated that, although permeabilities to water may be very low for sandstones containing hy-dratable clays, flow of oil can often restore a substantial portion of the effective permeabilities to oi1.Neverthe- less, water invasion into water-sensitive sandstone cores results in varying degrees of permanent reduction in permeability to oil.24' Based on field data, Wade's statistical study" of well completion effectiveness also indicated a correlation between productivity damage and water invasion during completion. Similar damage can result from fluid invasion during workover. Nowak and Krueger' and Bertness4 observed in their early work (1951-53) that formation damage in water-sensitive sandstones was associated not only with swelling of expandable clays but also with movement of dispersed particles. Subsequent work by Monaghan et al." (1959), Atwood'' (19641, Mungan" (1965) and Gray and Rex'" (1965) has led to general acceptance of the hypothesis that permeability damage in water-sensitive formations is caused by migration of finely dispersed minerals and bridging in "brush heap" arrangements at pore constructions. In laboratory studies, Monaghan et al.' found the use of chemicals to be of only minor value for repairing formation damage. Atwood? however, was successful in substantially repairing damage in a number of low-permeability cores using an n-hexanol flush. In the field, except for treatments with acids, the use of chemical washes to reduce wellbore damage has had limited and sporadic success and generally is unpredictable. A statistical analysis of stimulation treatments in silt-blocked wells has shown that physical manipulation of wash materials is more important than chemical composition." The recent work reported on formation damage in water-sensitive sands brings to mind the results of some unpublished exploratory work done in 1954 in connection with drilling fluid studies.' This laboratory work and subsequent field stimulation treatments indicated a beneficial effect of controlled pressure drawdown and the associated production rate on formation clean-up. This paper reports the results of this work and more recent supplemental experiments on the clean-up of water-sensitive sandstones damaged by water or filtrate invasion. PERMEABILITY RECOVERY AFTER DAMAGE BY DRILLING MUD APPARATUS AND TEST SAMPLES A drilling mud circulating system was used to expose cores to simulated wellbore conditions. The mud flow system is the same as that described by Krueger and Voge17 except that no provision was made for scraping

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Willard C. Lacy

Rather than attempting to present a summary of the many and highly varied papers that have been presented at this symposium on sampling and grade control, I will attempt to extract the general philosophy of analysis and approach, and attempt to identify the trend of future developments. First, the term "sampling" is used with its broadest connotations. A sample consists of a representative portion of a larger mass, and must represent the mass not only in the grade of contained metals or minerals, but also in all other respects in terms of mineralogy and mineral quality (1, 5), deleterious materials, recoverability of economic components, physical behavior, geophysical response (I), and even archaeological and environmental aspects (7, 11). The sample must be taken from a locality and in such a manner and quantity that it is representative of the larger rock mass. This calls for complete and accurate geological control and an understanding of the nature and distribution of the contained chemical and physical elements and a record of the effectiveness of the different sampling methods. Second, value of a given mass of ore material is based upon its profitability - the difference between recoverable value and costs to achieve recovery, beneficiation and sale. There is a strong movement in mining geology control toward more complete analysis in determining cutoff grades and in grade control, as illustrated by the kriging of metallurgical recovery factors as well as grade at the Mercur Mine (8). To achieve a "profit- ability factor" as a guide for economic mining practice requires further integration of: 1) the value of contained metal or mineral, 2) percentage recovery of values, 3) dilution of ore with waste rock, 4) addition to, or loss of value as a consequence of by-product materials or deleterious components, 5) cost of producing a saleable product plus mini- mum profit to justify the effort (cutoff), and 6) cost of land restoration (7, 11). All these parameters vary with the rock type, rock structure, mineralogy, depth, geometry, mining and metallurgical methods, but they must be sampled and analyzed if sampling and grade control are to reflect profitability. A wide variety of deposits has been presented at this symposium; each deposit with its own problems and special solutions. Deposits containing high unit-value components, e.g. precious metals and diamonds, present special problems in the obtaining of accurate samples and generally require statistical analysis control methods or may disregard or modify occasional high or occasional low values, based upon experience (12 ) Grade control may be accurate for the long term but may vary for the short term. Bulk sampling is always essential. Deposits containing metals or minerals with low unit value are very sensitive to transport costs, and they are often very sensitive to small amounts of deleterious components or differences in physical or chemical behavior. Problems of sampling and grade control change with the genetic type of deposit, with the stage of deposit development and with the size of the information base. Precious metal epithermal deposits (2, 6, 8), because of rapid vertical zonation and erratic lateral distribution of values, have always been difficult to evaluate and maintain grade control and ore reserves. On the other hand, evaluation and grade control are relatively easy in bulk-low- grade deposits (4, 13). However, these deposits generally have a low margin of profit and are sensitive to mining and beneficiaton costs, price fluctuations and political costs. Industrial mineral deposits (5) often must be evaluated on the basis of their behavior, rather than by chemical analysis. Environmental impact generally increases with the scale of the operation, but certain elements or minerals have especially high impact effects (7, 11). In the exploration phase there is no production control of sampling procedures and careful geological observations are particularly essential. The greatest number of problems is related to the oxidized outcrop where the chemical environment of the ore body has changed and the contained values may have been enriched, depleted or values left unchanged (2, 6). Present evidence suggests that gold values may be very mobile under certain conditions (2, 6) and stable under others. Everything must be sampled in detail. Principal values and by-product or deleterious elements may vary dependent upon their position within the soil profile. Such factors as geomorphic position, erosion rate, vegetation, climate, etc., may affect the interpretation (1, 3). During the development phase it is equally easy to overtest, to have "paralysis by analysis," as to undertest (3, 6). Bulk samplng and testing are

Jan 1, 1985