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By Robert E. Cuthbertson

It is the purpose of this paper to describe in detail the laboratory development and mill application of an unusual combination of flotation reagents employed in the concentrator of the Climax Molybdenum Co., on the Continental Divide, near Leadville, Lake County, Colorado. This development originated in an ore-dressing research laboratory maintained by Climax at the experimental plant of the Colorado School of Mines, which is staffed by men directly employed by the Climax Molybdenum Co. Mill-scale testing of laboratory developments was supervised by a representative from the testing laboratory, working in close cooperation with the operating staff at the mill. General milling practice at Climax is ably described in a paper by E. J. Duggan,1 mill superintendent. Other aspects of the Climax project have been described in papers by W. J. Coulter,2 by Butler, Vanderwilt and Henderson,= by Allen Kissock,4 and by Leo H. Glanville.5 Consequently, this paper will be corfined to the metallurgical aspects of recent reagent developments, avoiding, as much as possible, repetition of material covered in these earlier publications. Brief History of Reagent Practice at Climax Prior to the year 1937, the only reagents employed at Climax for froth production and collecting action in the flotation of molybdenite were steam-distilled or destructively distilled pine oils. The only exceptions to this practice were brief periods of mill testing, when reagents of various types were tried on an experimental basis. None of these experimental runs was sufficiently encouraging to justify its continuation as regular practice. Sodium cyanide has been employed since the very early days of milling at Climax as an inhibiting agent for control of pyrite and chalcopyrite. Alkaline reagents such as lime or soda ash have been used in recent years to minimize the detrimental effect of iron salts on flotation of molybdenite. The presence of these harmful salts is attributed to the decomposition of fine metallics abraded from liners and balls in the first stage of regrinding rougher concentrate. Flint pebbles are used in subsequent regrinding, since alkaline reagents are not entirely adequate to offset the inhibiting effect of iron salts as the grind becomes progressively finer and the grade of concentrate progressively higher. Climax metallurgists were familiar at an early date with the use of petroleum products such as kerosene and gas oil as promoters of flotation of molybdenite. Charles C. Oliver6 discussed the use of pine oil and kerosene as early as 19-20, in connection with the milling practice at Dominion Molybdenite Co., Quebec. Nevertheless, the early attempts to apply this knowledge in the Climax concentrator were complete failures. In the light of recent experience, it may seem strange that the early mill tests with petroleum

Jan 1, 1947

By C. B. Clark, W. H. Bruckner

Since the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Mun-roe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research On shaped explosive charges, the following have been established concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By C. B. Clark, W. H. Bruckner

Since the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Mun-roe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research On shaped explosive charges, the following have been established concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By Willis R. Battles, William F. Cerini, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By William F. Cerini, Willis R. Battles, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By J. C. McKinnell

The appraisal of an oil lease may often be mad,? through production decline analysis, which requires description of the functional relationship between the oil production rate and either cumulative production or time. Heretofore, attempts to define the function appropriate to a given set of production data have depended to some extent on subjective procedures. The purpose here is to introduce an objective solution, obtained by combining the principle of least squares with the theory of equations. MATHEMATICAL ANALYSIS The fundamental differential equation appropriate to a general class of decline curves may be written. Solution of Eq. 1 for general boundary conditions may be written in terms of either the cumulative oil production or time: These equations constitute the mathematical expression of the so-called hyperbolic decline. Their complete description for a given set of production data requires the numerical evaluation of the three parameters1.', n, D, and (go),. For the special case of n = 0, Eq. 2 becomes q. = (q.), - DiN with the corresponding expression in terms of time being q. = (qa),e...........(5) Similarly, for the special case of n = 1, Eq. 3 becomes with the corresponding expression in terms of cumula- tive oil production being q. = (q.),e " '.......(7) Eqs. 4 and 5 constitute the mathematical description of the so-called exponential decline; Eqs. 6 and 7 are the mathematical description of the harmonic decline.',' Returning to the hyperbolic expressions, Eqs. 2 and 3 may also be written, q: = sNp + b........ (8) and where a = 1 - n; s = (n— 1)D,(q0);"; b = (go):-"; a'=-n;s/= nD,(qo);"; and b' = (go);-. Note that both Eqs. 8 and 9 are linear in either time or cumulative production with respect to an exponential function of the production rate. In other words, a straight line relationship results for both variables when associated with the appropriate power of q,. This fact is of prime importance in the application of statistical analysis. . STATISTICAL ANALYSIS For a given oil lease, the time, production rate and cumulative production are recorded records. To establish predictive formulas from Eqs. 2 and 3, it remains to determine numerical values for the three parameters [n, D, and (q,) .] through an investigation of the past history. Upon interpreting a, s and b as parameters, Eq. 8 may be expressed for every time interval of interest, i, over the past history as follows. (q,): = s(Np), + b........(10) In general, Eq. 10 will not be satisfied exactly, because of the assumptions in the expression of Eq. 1, and the errors and anomalies universally associated with production data. It will instead define the residual, s(Np), + b- CO=d......(11) Squaring both sides and summing over all the data points, m, under consideration yields

By Y. Dardel

Since the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts? then Baukloh and Oesterlen,a during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreq4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per I00 g of metal. Winterhager,6 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitze as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhausers extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per I00 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per I00 g, while that of the usual apparatus was only about 0.2 cm3 per I00 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. Table i—Amount of Adsorbed and Dissolved Hydrogen (After Eborall and Ransley) Extraction Hz Adsorbed „ h2 dissolved Temperature Calculated Extraction OCcma 500 0.057 0.050 600 0.062 o.096 Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of. Eborall and Ransley, as well as the earlier apparatus.

Jan 1, 1949

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

THERE has been little investigation of the gold-germanium binary alloys. Haughton1 does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least o.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at 12,0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke&apos;s value, was found to have a few gold dendrites in it. The eutectic temperature has been determined as 356.0 ± 0.5°C., slightly less than the temperature of 359°C reported by Einecke. The liquidus curves and the solid solubility of germanium in gold have been determined, and are shown in Fig. I. MATERIALS AND ALLOYING The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050° to 1100°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hypereutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be off composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallographic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain&apos; introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?&apos; nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?&apos; are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase&apos;s in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase&apos;s in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By H. G. Doll

An earlier paper on the general subject of the SP log has analyzed the limitations of that log, in particular when dealing with thin permeable beds enclosed in thick highly resistive ones. Under such conditions, the SP log does not give a good definition of the permeable beds. Selective SP logging is a new method which gives an accurate determination of the permeable beds; even in highly resistive formations, except when the salinity of the mud is extremely high. It also permits a close approxi. mation of the static SP to be obtained. The method consists generally in controlling the potential of auxiliary electrodes located in the drill holes in the vicinity of the measuring electrode. In this manner. the flow of SP current along the drill hole is modified to counterbalance the effect of highly resistive strata. Several procedure; and arrangements used to record selective SP curves and static SP curves are explained. Field examples illustrating these methods are given and discussed. INTRODUCTION In an earlier paper,&apos; the shape of the SP curves and the amplitude of the SP peaks were analyzed, considering how the circulation of the SP current is influenced by the subsurface media as a function of their geometrical configuration and their resistivities. It was shown, in particular. that the permeable beds situated between highly resistive formations are sometimes indistinctly indicated by the deflections of the SP log. It is the purpose of this paper to dircuss a new method now being developed, namely selective SP logging, whose principal feature is to enable a more accurate determination of the depths of the permeable beds present in highly resistive formations, such as occur in limestone fields. It will be shown also how an addi-tional curve called the static SP log can be derived from the selective SP log, or recorded directly, to facilitate the interpretation. Another purpose of the static SP log is to provide an approach toward the determination of the value of the static SP, where this value is not readily given by the SP log. This application. although less important at the present time than that mentioned above, nevertheless is of interest, inasmuch as, according to laboratory and field experiments conducted by several investigators, the determination of oil saturation of reservoirs from the data of the electric log implies the knowledge of the resistivity of the connate water,2,3 to which the static SP seems to be related.4,5,6,7 PRINCIPLE OF SELECTIVE SP LOGGING The method of selective SP logging of the formations traversed by a bore hole consists in recording two curves under the following conditions: The measuring device comprises one measuring electrode M and two additional electrodes G-G&apos;, connected to each other. located above and below

Jan 1, 1950

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.&apos; Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.&apos; Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line&apos;&apos; and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line&apos;&apos; and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.&apos; To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall&apos; determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot&apos; to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.&apos; Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer&apos; have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By N. K. Chen, R. Maddin, K. T. Aust

Lattice rotations occurring on the tension and compression sides during the bending of molybdenum single crystals at room temperature were followed in detail. Observations were also made concerning crystallite rotations and slip traces. &apos;The results indicated the participation of (110) as slip planes and the<111>as slip directions. Crystallite fragmentation during bending was also noted. EVERAL investigations have been conducted on pure bending of face-centered cubic metals.&apos;-" Structural changes as a result of "bend-gliding," and the importance of bending and constraints during conditions of axial stressing, have been noted.&apos;," It was evident that the mechanism by which the bending deformation occurs is more complex than the case of simple shear. Studies of the bending of body-centered cubic metals from the aspect of the crystallographic mechanism appear to be lacking. Molybdenum single crystals therefore were subjected to deformation by bending in order to determine the reaction of the body-centered cubic lattice to bending stresses. It might be expected for the bending of single crystals that lattice rotation as represented by the axis of compression would proceed toward the pole of the active slip plane and that rotation of the tensile stress axis should indicate the slip direction.&apos; It was believed therefore that a study of the tension and compression sides of bent molybdenum single crystals should give data concerning the operative slip system. Specific problems which are pertinent to the overall picture of plastic deformation were also investigated, e.g., whether the constraints offered by pure bending give rise to the deformation band, and also the nature of the asterism occurring on the tension and compression sides during the stages of deformation. Experimental Procedure Eight single crystal specimens were grown from sintered molybdenum rods 143 in. diameter using the method described previously.6 The purity of this material was reported as 99.9 pct as described elsewhere.&apos; The specimens were % to 1/10 in. in diameter x 7 in. long, with single crystals approximately 1 to 2 in. in length occupying the entire center sections of each specimen. The specimens were elec-trolytically polished using an electrolyte of 300 cc methyl alcohol, 60 cc H2SO4, 130 cc HCl, and a current density of 4 amp per sq in. Each specimen was then loaded in a bending apparatus similar to that used by Yen and Hibbard,&apos; as shown in Fig. 1. The load was applied by means of a spring and screw arrangement through four ball-bearing surfaces set 1.5 in. apart. Either the inner two bearings or the outer two (A, B, Fig. 1) were attached to a movable steel plate (D) through which the load was transmitted. Since the apparatus was mounted on a track of the X-ray apparatus, the tension or compression side of the specimen could

Jan 1, 1954