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By Henry M. Howe

IN discussing the classification of iron to-day, we are to leave out of consideration the general division into non-malleable or cast iron and malleable iron, as to the adequacy of which no question has been raised; and to confine ourselves to the subdivisions of malleable iron. This has been classified, according to the extent to which the properties imparted by carbon are present (viz., resilience, hardness, strength„ and, above all, the capacity for being hardened by sudden cooling from a high temperature), into (1) wrought iron which cannot be hardened, and (2) steel which can be hardened; and this classification I shall, for briefness, term the carbon classification. Until within a few years all authorities, both metallurgical and general,, have concurred in explicitly recognizing the carbon-given qualities, and preeminently the capacity for being hardened, as the essential qualities of steel ; this is laid down with clearness by every writer on the subject. For several years this old classification has not been sufficient to, meet all our needs, since the genius of Bessemer, Siemens, and, I may add, Holley, has produced wrought iron which has been perfectly melted, and thus freed from certain mechanical adhering impurities. This causes what we call homogeneousness for want of a better word, and gives rise to many important qualities which the old wrought iron had not;. qualities universally recognized, though not readily described. I shall, for briefness, style them the fusion qualities, and a classification based on them., a fusion classification. These qualities render the new product so vastly superior, for most purposes, to the wrought iron formerly known, that it is neces- * This paper was read in opening the discussion on the motion to adopt the report of the International Committee on the Nomenclature of Iron and Steel. At the conclusion of the discussion the resolutions on page 44 were adopted.

Jan 1, 1877

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-'. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.' For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-'. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.' For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

By A. J. Langhammer

Broadly speaking, it may be said that the engineer has two major responsibilities: One is to recommend the choosing of proper machinery and equipment; the other, to assist in the simplification of design, determination of method, and advise about the most suitable material to be used. The products of powder metallurgy enter broadly into both these fields. The oil-cushion, self-lubricating bearing surface on a machine part makes for better machinery and factory equipment, often proves a life-saver in curing difficulties where bearings are overloaded or inaccessible for lubrication, or on installations that with normal practice constitute a problem entailing frequent repairs. On the other hand, other parts may require low porosity approaching solidity. In the second field, powder metallurgy provides many possibilities for improved products, improved performance, solving of technical problems, saving of weight, quiet operation, higher factors of safety, greater flexibility, attractive economies, and so on. Parts We of the automotive industries are making many powdered-metal war-machine parts, both ferrous and nonferrous, including gears, external and internal; ratchets, both external and internal; levers; pillow blocks; sliding blocks; cams; gibs; hubs with external and internal splines, and similar units. Powdered metals play an important part in our war work, as they did in peacetime in the manufacturing of passenger cars and trucks. The art of powder metallurgy is not a panacea. Although on certain parts such operations as turning, boring, facing, reaming, counterboring, milling, countersinking. chamfering, broaching, hobbing, profiling. trepanning, gear cutting, grinding, etc., can be eliminated, there will always be the need for machine tools. Advantages of Powder Metallurgy Simple machining operations often are eliminated by using powdered metal, and also many other intricate operations, some of which are of the type impossible to perform on the most modern production equipment; for instance, an external spline on a flange hub, where the spline must continue to the flange face and at full depth. Another important feature is that some of the machine parts may require a self-lubricating surface at one or more points; for example, proper lubrication of a sliding splined spool, while ordinarily most digcuit, is accomplished automatically with a self-lubricating powdered-metal bearing. Frequently machine parts are made with physical, mechanical and technological advantages unobtainable from cast or forged metals of similar analysis. Thus powder metallurgy offers the designing engineer broader latitude. Similarly, the engineer may take advantage of powder metallurgy in his teamwork with other departments. Another important advantage in powder metallurgy for machine parts is the relatively short time required for tool-up.

Jan 1, 1945

By W. L. Mamme, G. Y. Chin

The problem of selection of the active slip systems for a crystal undergoing an arbitrary strain was analyzed by Taylor and by Bishop and Hill in terms of a minimum (internal) and a maximum (external) work criterion, respectively. These two criteria have now been generalized to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (noncrystallographic) pencil glide. The generalized treatment also takes into account the possibility of a Bauschinger effect and of unequal hardening among the shear systems, which were considered in the Bishop and Hill work. Optimization techniques of linear and nonlinear programming are shown to be applicable for the numerical calculation of the minimum or maximum work. In the case of crystallographic shear, the constraint functions are linear and hence the optimal work is obtained as the saddle value of the lagrangian function Wi(y) e minimum and W,(u) + (a) for the maximum, where Wi is the (internal) work, We is the (external) work, Y is the crystallographic shear strain, u is the applied stress, and and are constraints. It is shown that the Lagrangians are functionally the same and the saddle value of one problem is identical to the saddle value of the other, proving that the two analyses are completely equivalent. In the case of pencil glide, although the constraint functions are nonlinear and neither convex nor concave, the equivalence of the optimal values to the saddle value of the Lagrangian (which is again identical for both problems) is still valid. WHEN a crystal deforms plastically by crystallographic shear, five independent shears are generally required to accommodate five independent strain components specifying the deformation. Assuming slip as the only shear mechanism, Taylor1 in 1938 analyzed the deformation in terms of a minimum work criterion. He hypothesized that of all combinations of five slip systems which are capable of accommodating the deformation, the active combination is that one for which the internal work C is a minimum, where 1 TI is the critical resolved shear stress for slip on the 1-th slip system and is the corresponding simple shear. By further assuming equal 72 for all equivalent slip systems and no Bauschinger effect, Taylor re- duced the minimum work problem to one of minimum and applied the analysis to the case of axisym- Metric flow by {111}(110) slip in fcc crystals. However, he did not consider the question of whether the resolved shear stress has in fact attained the critical value for slip on the newly found active systems without exceeding it on the inactive systems. In 1951 Bishop and ill' put forth the maximum work analysis in which slip is again assumed as the only deformation mechanism. In this analysis, the work o1 done in a given strain ij by a stress ujj not violating the yield condition is maximized. In addition, the analysis takes into account the possibility that the critical resolved shear stress for slip may not be equal among the slip systems and that the slip behavior may exhibit the Bauschinger effect. As with Taylor, a single set of slip systems—{111)(110) — was analyzed numerically. It thus appears that the Bishop and Hill treatment is on a more sound physical basis than the Taylor treatment. However, Bishop and Hill showed that where there is equal hardening among all slip systems and when there is no Bauschinger effect, Eq. [11 ] of Ref. 2, as assumed by Taylor, the results of their maximum work analysis are the same as those of Taylor's minimum work analysis. Hence at least under those conditions there is an implication that the Taylor analysis does lead to a critical resolved shear stress for slip on the predicted active systems without violating the yield condition on the inactive systems. Recently, the Taylor analysis was applied for numerical solutions of the axisymmetric flow problem, for slip on {110}(111), {112}(111). {123)(111) systems as well as a mixture of all three sets of svstems."1 Computational techniques based on the optimization theories of linear and nonlinear programming4 were employed in these solutions. The same techniques were employed in the solutions of an axisymmetric flow problem of deformation by slip on (111) (110) systems and twinning on (111)(112) systems5 which had been considered theoretically from a modified Taylor approach. The utilization of these techniques has led to the realization that the solutions of Taylor's minimum work problem imply the solutions of Bishop and Hill's maximum work problem. The two problems turn out to be dual problems in the well known sense of mathematical programming. It is thus the purpose of this paper to first generalize the minimum and maximum work analyses to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (non-crystallographic) pencil glide, as well as the possibility of a Bauschinger effect and of unequal hardening

Jan 1, 1970

By Nicholas Kowall, K. L. Clark

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By K. L. Clark, Nicholas Kowall

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By J. H. Richards, G. Derge, W. Peifer

A WIDE Variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware, They have been related to hydrogen largely by circumstantiat evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British committee on the Heterogeneity of Steel Ingots,' and current approaches to the problem were reviewed in a recent symposium of the AIME.I2 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principal object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem, The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow in However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross-section large enough to develop cracks, Yet small enough for convenient handling and sampling. Rails were also selected because they arc made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitat~s early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion, (2) Vacuum extraction (without melting), (3) Total combustion.

Jan 1, 1949

By G. Derge, W. Peifer, J. H. Richards

A WIDE Variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware, They have been related to hydrogen largely by circumstantiat evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British committee on the Heterogeneity of Steel Ingots,' and current approaches to the problem were reviewed in a recent symposium of the AIME.I2 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principal object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem, The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow in However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross-section large enough to develop cracks, Yet small enough for convenient handling and sampling. Rails were also selected because they arc made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitat~s early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion, (2) Vacuum extraction (without melting), (3) Total combustion.

Jan 1, 1949

By H. H. Uhlig

IN our study of the mechanism of and the prevention of corrosion in stainless steels, it was considered of fundamental importance to obtain knowledge of the surface structure of such alloys. If corrosion resistance is due to a self-healing oxide layer, which like a paint film protects the underlying metal, it would be obviously relevant were the effort made to make the film less permeable and more adherent; for example, the surface might be expected to respond to an anodizing process, which is found successful in increasing the film thickness and corrosion resistance of aluminum. However, if passivity and corrosion resistance of stainless steels are due to another cause, the attack of the problem would follow another path. One of the most effective techniques for studying passivity and corrosion tendency is the measurement of the electrochemical potential. Not only can one determine by potential measurements whether a metal is active or passive, but also one can determine the degree of passivity and rate of transformation of passivity with time. Chemical media that build up or destroy passivity when in contact with the steel can also be classified by potential measurements. Something can be learned, too, of the effect of alloy additions such as molybdenum to 18-8, known to decrease corrosion of the alloy in chloride solutions. A study of alloys in previous investigations has sometimes included data on the electrochemical potentials. Tammann and Sotter1 measured the electrochemical potentials of alloys of iron-molybdenum and iron-chromium and reported the critical concentration of molybdenum or chromium at which passivity initiates. Strauss2 made similar measure-ments for the iron-chromium system. The electrochemical potential' has also been used to indicate carbide precipitated 18-8. In 18-8, heat-treated to precipitate carbide, active metal exists at the region of the grain boundaries, contrasted with passive metal within the grains, the active metal accounting for a resultant active potential. Several

Jan 1, 1939

By G. E. Keller

In connection with the work of Committee D5, Coal and Coke, of the American Society for Testing and Materials in developing new standards and improving old standards, series of tests were made to check the variance of sample preparation and analysis of American coals. Table I in the "Tentative Method of Preparing Coal Samples for Analysis - 02013-62T" is rather complicated, and the tests were designed to develop data for the simplification of this table. An allowance of 20% of the total variance of sampling and analysis for the sample preparation and analysis steps was used. Also, instead of coals being grouped into ash ranges, they were grouped as washed and raw (unwashed) coals. As a result of these tests, a simplified Table I for Tentative Standard 02013 has been proposed. A standard test for laboratories to check their variance of sample preparation and analysis has been developed. Committee D5 on Coal and Coke of the American Society for Testing and Materials has been making a study of all standards applying to coal for the purpose of improving and bringing them up to date and for breaking some of the existing standards covering a number of tests into single standards. As an illustration, sample preparation is now partly covered in ASTM Designation D492-48, Sampling Coals Classified According to Ash Content, and partly in ASTM Designation D271-58, Laboratory Sampling and Analysis of Coal and Coke. The latter contains, in addition to parts of sample preparation, methods for determining Moisture, Ash, Volatile Matter, etc. Although revision of sampling methods and sample preparation methods are now assigned separately, it is possible that they may end up as one standard. One of the first new Tentative Standards developed as the result of these studies was ASTM Designation D2013, Tentative Method of Preparing Coal Samples for Analysis. Although this method is quite an im- provement over that in the old standards and gives very specific instructions, Table I (attached) is quite complicated and rather hard to understand. In order to take advantage of reduced quantities or weights, it is necessary to know the ash content within rather narrow limits before sample preparation and no distinction is made as to whether the coal is cleaned or uncleaned. No limits of accuracy are assigned to the sample preparation and analysis. The total over-all accuracy of sampling, preparation and ash determination as given in D492-48 has been specified for commercial sampling procedure as follows: "This procedure is intended for an accuracy such that if a large number of samples were taken from a single lot of coal, the test results in 95 out of 100 cases would fall within ? 10 per cent of the average ash content of the sample." Although Appendix 11, Method for Determining the Over-All Variance of Reduction and Analysis in the Tentative Methods for Mechanical Sampling of Coal, ASTM Designation D2234-63T, does give a method for determing the over-all accuracy of preparation and analysis expressed as variance and also the F test, it does not permit the determination of the variance at the various stages of reduction or of the ash determination. It was decided in 1961 to ask a number of laboratories to run a series of tests for the purpose of determining the variance at various stages of reduction and analysis with the view of simplifying Table I of the Tentative Standard D2013-62-T. This paper is a record of this series of tests with recommendations which resulted from the tests. At the same time and preceding these tests the International Organization for Standardization under Committee TC/27 WG 7 was studying the same problem. Tomlinson1 of England and Dr. paul2 of West Germany had made studies giving quite a bit of information. Also Schwerd and coryel13 published some information which was the main basis for the Mechanical Division provision in ASTM Tentative Standard D2013-62T, Table I. In checking with the various laboratories which offered to cooperate in these tests, none was found which used mechanical division through the entire preparation procedure. It was then decided to use riffles at all stages with the thought that if riffles gave satisfactory variances, approved mechanical

Jan 1, 1965

By Robin P. Gardner

A radioisotope tracer method combined with a suitable back-calculation method is proposed and evaluated for the determination of model simulation parameters in open-circuit continuous ball mills. The method essentially consists of using impulse and/or step injections of short-lived radioisotopes of the naturally occurring trace elements manganese and sodium. It is evaluated here on the basis of the minimum standard deviations of the product weight-size distributions. These minimum standard deviations are taken as those predicted by a Poisson distribution of the number of particles present in size fractions of the samples taken for analysis. Previously developed tanks-in-series lumped parameter models are used in the evaluation. The results indicate that the method is very promising.

Jan 1, 1976

By G. W. White

Over the past several years, the steady progress of gas lift from a mysterious art into a developing science has been traceable through the many fine papers that have appeared in Journal of Petroleum Technology. Consequently, this magazine has rightly become a standard for the serious students of gas lift all over the world. The following discussion is offered in a sincere attempt to accurately present certain topics covered in the subject paper in the light of acknowledged state of the art procedures. INSTALLATION DESIGN The first point to be questioned is the author's installation design, beginning with Eq. 6. The use of 1,200 psi in the spacing equation instead of the 1,275 psi noted as available seems, at first glance, to be a simple arithmetic error. Upon further examination, it appears evident that both this 75 psi plus the 100-psi safety factor must be subtracted from available kickoff pressure because of conditions imposed by the characteristics of the ASC valve (see Fig. B-1). Pressure-charged valve design is incorrectly penalized by spacing the first valve using only 1,100 psi. The use of such a high back-pressure makes it appear that a typical ASC installation would require no more valves than a comparable conventional valve installation. Using a value of 100-psi tree pressure, the well could be valved to 11,000 ft very conservatively with seven pressure-operated valves, but would still require 11 ASC valves. The use of 400-B/D spacing gradient for a 140-B/D rate is not an accepted practice using precharged valves. The author would have done well to note the advantages to be gained by reducing the 500-psi tree pressure, which is clearly explained by Beadle, Harlan and Brown.' In Step 1 of Part III of the continuous flow discussion, the author incorrectly applies the Poettmann and Carpenter curves.2 Item 2 is an incorrect statement. An excellent reference on this point is the paper by Baxen-dell and Thomas.' VALVE MECHANICS The next topic relates to the mechanics of precharged valves. Eq. 2 for the ASC valve can be used to describe the condition of equilibrium, wherein the valve is closed with opening pending. When this equation is used to determine relative values of casing, dome and tubing pressure with conditions approaching the transition value, some strange results are obtained. The following uses the author's symbols and values given on page 689. Fig. B-1 shows the condition that exists at the moment an ASC valve has been uncovered during the unloading process (Condition I). The obvious result is a locked condition. The basis for the curve is shown on the figure which includes 1,000 psig casing pressure to uncover the valve. If injection gas is not bled off the casing until the pressure is decreased by an amount exceeding the stabilizer discharging valve pressure, upward adjustment of the casing pressure is mandatory for the valve to open and unloading operations to continue. In Condition I the dome pressure exceeds the casing pressure by 20 psi, and the tubing pressure required to open the valve is 1,212 psig. This tubing pressure would not exist under the assumed conditions. In Condition I1 the casing pressure is increased to the dome pressure, and the tubing pressure required to open the valve is 1,102 psig. It is apparent that the casing pressure must be increased to a value exceeding the dome pressure before unloading operations could continue. In Condition I11 a maximum casing pressure of 100 psi (stabilizer charging valve set pressure) above the dome pressure is reached, and the tubing pressure required to open the valve is 549 psig. The author's statement after Eq. 5 that "the minimum tubing pressure required to open an ASC valve is equal to the casing pressure at depth less the transition pressure of the valve" is incorrect except for Condition I11 only. Otherwise, the equation is invalid.

Jan 1, 1965

By Richard F. Hinds, F. O. Reudelhuber

Application of the conventional depletion drive calculation methods to volatile oil reservoirs results in erroneous estimates of ultimate recovery. In view of the increasing number and importance of volatile oil reservoirs, a special technique has been developed which will result in more realistic predictions using laboratory data obtained from reservoir fluid studies of a specific type. The experimental data are designed to permit continuous material accounting and, therefrom, provide the hy-clrocarbon composition of both the flowing oil and gas phases. The resultant well-stream composition data are then used directly in surface recovery calculations utilizing equilibrium ratios. A step by step procedure, specifically designed for routine use by the practicing reservoir engineer, is presented in an appendix. An actual study performed on a deep Mid-Continent reservoir is used ay an il-lustrathe example. INTRODUCTION It has been a practice for many years to utilize the conventional ma- terial balance methods in conjunction with relative permeability concepts for the prediction of recovery from solution gas drive reservoirs.' Those who have performed such calculations recognize that compromises of several types are necessary in order to reduce the calculations to a reasonable degree of complexity. The most serious assumption involved results from the necessity of treating the produced oil and gas as separate fluids, independent of each other in their behavior. It is further assumed that the gas which is evolved in the reservoir as a result of pressure decline will not yield liquid upon the reduction of pressure and temperature resulting from production through surface equipment. Although these shortcomings have been recognized,' it has been difficult to attempt refinement of calculation procedures since the laboratory data available normally were not of the proper type or extent to permit such calculations. Three general procedures have been available for depletion drive calculations when laboratory fluid data are of the conventional type. Differential Procedure The most simple, and most widely used, method requires use of the formation volume factor and gas sol- ubility data obtained from a differential liberation performed at reservoir temperature. This procedure ignores the differences existing between the fluid behavior in the reservoir and its behavior as it is produced through surface separation equipment. The errors introduced are not serious when dealing with very low volatility fluids and this method may be utilized if the laboratory data indicate only slight differences between the differential data and the flash data obtained from separator tests. Modified Differential Procedure This method was developed when it became apparent that medium volatility fluids evidenced a wide difference between the flash and differential data. The differential data are adjusted by changing from a residual oil basis to a stock tank oil basis. All that is required is multiplication of the differential data by the ratio of residual oil to stock tank oil relative volumes existing for the original reservoir fluid at the determined saturation pressure. This procedure generally results in increased calculated ul-timate recovery; however, such results should be viewed critically. Upon examination it may become apparent that the results are influenced by errors in reservoir liquid

Jan 1, 1958

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By A. E. Back, W. Wyman, K. E. Tame, S. F. Ravitz

In 1940, when it appeared that the United States soon might be cut off from foreign sources of high-grade manganese ore, the Bureau of Mines began an extensive series of investigations on the production of ferro-grade products from low-grade domestic ores by ore-dressing, pyrometal-lurgical, and hydrometallurgical methods. Among the hydrometallurgical processes for oxide ores investigated was a sulphur dioxide process in which the manganese was recovered from solution by precipitation with lime;' this process is essentially as follows: The ground ore is suspended in water and leached with SO2 gas to extract the manganese as manganese sulphate. Calcium chloride is then added to the slurry to precipitate calcium sulphate and form manganous chloride solution, and the resultant slurry is filtered to remove the calcium sulphate together with the insoluble portion of the ore. Calcium hydroxide is added to the filtrate and the mixture is agitated with air to precipitate hydrated oxides of manganese and regenerate calcium chloride. The precipitate is calcined, and the calcium chloride is recycled. To determine manganese extraction, reagent consumption, grade of product, and similar data for this process, a labora- tory investigation was started. Two minor modifications in the process were soon made: (I) the ore was suspended in calcium chloride solution instead of in water in order to extract the manganese and precipitate the calcium sulphate in one step, and (2) the agitation with air after the addition of slaked lime to the filtrate was omitted because manganese hydroxide is readily precipitated without air agitation and can be nodulized or sintered to a satisfactory product. When the process was carried through a series of cyclic tests, it was noted that the concentration of dithionate ion (which is one of the products of oxidation of SO2 by MnO2) in the cycled solution gradually increased; at the same time the chloride content of the solution gradually decreased, owing to soluble losses in the leach residue and in the precipitate. After a number of cycles, the calcium chloride became virtually completely replaced by calcium dithionate, the quantity of dithionate ion formed during the leach being more than enough to make up for the losses of dithionate in filtering. The calcium chloride process thus developed into a calcium dithionate process. Since the latter eliminated the need for make-up calcium chloride, and the dithionate solutions appeared much less corrosive than the chloride solutions, work on the calcium chloride process was dropped in favor of the calcium dithionate process. Acknowledgments The dithionate process was developed by the Bureau of Mines as part of a

Jan 1, 1949

By C. S. Herzig

In the Engineering and Mining Journal of Jan. 27, 1900, there appeared an article by Fred T. Greene, describing a method of measuring stopes by the use of strings, a clinometer and a tape. In the early part of 1899 I had occasion to use a somewhat similar method, for the purpose of accurately ascertaining the volume of a very irregular drift connecting two mines. This drift was an important factor in a lawsuit for $150,000, in which it was necessary to determine accurately the volume originally occupied by the material extracted from the drift. While it is unnecessary to give all details of the controversy, some explanation of the conditions is required for a clear understanding of the following description. This drift was started by the a E." Co. from its workings, in about 7 ft. of ore, and headed toward the " G " property, the plan being to extract all the ore between foot- and hanging-walls, but to take out nothing but ore. As the " G." workings were approached; the ore-body became very irregular and much thinner. It was, however, very closely followed, and where the drift broke through into the " G." workings, the hole was only 11 inches high by 14 inches wide, or just about the size of a man-hole in a boiler.. Thus, this connection-drift tapered sharply; and the very irregular foot-wall sloped toward the " G." workings, and entered them at a place where the stope was only about 3 ft. high, and the ground had already commenced to cave. It may be added that the ore-body was a nearly flat deposit of lead carbonate in limestone, the ore and gangue being quite soft. I was called upon by the " G." people to make the survey

Jan 1, 1901

By M. S. Azun

M.S. Azun I have many objections to the content of the author's paper. Before discussing it, however, I would like to repeat the property of semivariogram function. Second order stationary properties of regionalized variables (ReV's) such as semivariogram function ?(h) are perfectly known in geostatistics. Also, the kriging equations in the language of mathematical statistics using second order stationary properties are well understood. However, the way to use the sample (estimated) semivariogram function in any one of the kriging procedures is vague. The sample semivariogram function is given as follows: [1 N-hy*(h) = 2(N h) i21 {Xi-Xi+h}Z, h=0, 1, N-1] where N is the total number of samples, Xi is the sample value at the i - th location, X i+h is the sample value at the i +h - th location, and h is the distance among the samples. An estimation variance of sample semivariogram function of first lag is smaller than that of higher order lag. The theoretical semivariogram function reaches the variance of samples asymptotically. But this is not easily observable because of the larger variation involved in the estimate of semivariogram function. In general, an estimation procedure is done for h = 0, 1, 2,…., up to the greatest integer less than N/2, even though sample semivariogram function can be computable through N-1. After estimating semivariogram function, the critical question of how to model sample semivariogram function arises. As seen in the above equation, sample semivariogram function is discrete and can be smoothed by the model being selected. Therefore, modeling of sample semivariogram function is the most important step in geostatistics. It not only smoothes a discrete function but also affects the results of the kriging procedure. When the only aim is to model the semivariogram function, which is the basic point of the author's paper, one can employ any fitting techniques, such as curve fitting, or any ar¬bitrary functions, which are called submodels in the paper. The term "arbitrary function" is used rather than "submodel" because there is no basic understanding of developing them. The author suggests that the sum of those submodels can also be used for the modeling of sample semivariogram function. The combination of any arbitrary functions brings many problems instead of giving an insight of the domain structure considered. The author used two arbitrary functions and the nugget effect in response to sample semivariogram function (Fig. 10). For the same example, he stated that the parameters involved in the mixed arbitrary function model can be accepted when the discrepancy between sample semivariogram function and the model is small visually. For verifying the fitting behavior of any selected model, one should not be contented with the visual satisfactory. Some statistical measure such as goodness of fit has to be used. The author's practice is no more than an exercise in curve fitting without any fundamental understanding or conceptualization of the underlying physical mechanism. Furthermore, the selection of any model is not an easy task if the purpose is the search for the "best" response to the observed second order properties of ReV's. I suggest that the Markovian model (Azun, 1983), on the basis of a theoretical understanding of underlying mechanism, which gives more information about the occurrence of regionalized variables, is used to respond all properties of ReV's. There are a lot of problems for modeling of onedimensional sample semivariogram function. Thus, it is not appropriate to go to higher order dimensional sample semivariogram function modeling. In the meantime, I would recommend that one can connect the values of standardized sample semivariogram function rather than simple values of semivariogram function in the two-dimensional estimation. The standardized values can be computed in dividing the semivariogram function value by the number of sample pairs involved in each lag regardless of the directions. In conclusion, geostatistics is an interdisciplinary area in mining that uses the principles of mathematical statistics. Thus, it should not violate any probabilistic and statistical rules. When Matheron was developing the theory of geostatistical study in the early years of geostatistics, many mining people had a reservation accepting the geostatistical tools. However, this does not mean that we, the geostatisticians, might try to convince those people using some "strange" tools or rules as some authors implied (Baafi and Kim, 1984). Instead, we have to develop and explain the geostatistical tools staying only in the framework of statistical concepts and properties. ? References Azun, M.S., 1983, "Stochastic Process Modeling of Spatially Distributed Geostatistical Data," Columbia University, Ph.D. Thesis. Baafi, E.Y., and Kim, Y.C., 1984, "Discussion - Comparison of Different Ore Reserve Estimation Methods Using Conditional Simulation," Mining Engineering, Vol. 36, No. 3, p. 280. Reply by J.M. Rendu The interactive method proposed by Rendu allows practitioners to develop semivariogram models that take into account not only the numerical information obtained by sampling, but also highly significant additional information that often cannot be quantified. The geology of the deposit - including hypotheses concerning its genesis, sampling methods, assaying methods, and mathematical methods used to calculate the semivariograms - all have an influence on the numerical results obtained and on how these results should be interpreted. If all the information concerning the spatial distribution of values in a mineral deposit was contained in the sample values, it could be argued that statistical techniques alone would produce optimum models. However, this is rarely, if ever, the case. Methods that allow the user to take into account his experience and his geologic understanding of the deposit should not be rejected for the sake of theoretical statistical purity. ?

Jan 1, 1986

By R. A. Stauffer

The chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper1 has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000ºC in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating-to about 1000ºC in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. The Replacement of Li2O in Spodumene A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide Present in the Ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh' Analysis of the spodumene was as follows: PCT SiO2......................... 62.7 Al2O3........................ 29.9 Li2o......................... 4.9 Na2O........................ 0.89 CaO......................... 0.75 MgO........................ 0.49 K2O......................... 0.44 Lime (cp —200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000ºC in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1949

By E. P. Whittemore

Experience with the ASC multipoint gas lift system was obtained in Colonia zone of the West Montalvo field near Oxnard, Calif. The wells in this pool produce from depths varying from 10,500 to 12,000 ft. Oil gravity is generally 14 to 15' API with a few extremes of 12 and 20" API. Some salt water is produced which causes some very viscous emulsions. Viscosities at 150F (which is the approximate wellhead temperature) vary from 5,000 to 100,000 SSU. Most of the production is by gas lift, although a few wells are produced by rod and hydraulic pump. About half of the gas-lift wells are on continuous flow and the remainder are on intermittent lift using large, ported, pilot-operated valves for single-point transfer of gas from casing to tubing. Gas-liquid ratios vary from about 6 to 10 Mcf/bbl of gross fluid lifted. Wells are produced to a 450-psi trap system. The following remarks will be confined to intermittent lift only, since this is the type of lift which has been achieved with the ASC valve system. The maximum gross fluid which has been produced by single-point intermittent lift is about 350 B/D in 3-in. tubing and 200 B/D in 21/2-in. tubing with gas-liquid ratios of approximately 7 to 9 Mcf/bbl. Some design changes could reduce this ratio. The ASC multipoint system has provided production as high as 480 BOPD in 21/2-in. tubing with gas-liquid ratios just under 4 Mcf/bbl. To be able to apply the multipoint system, it is recommended that a detailed explanation be obtained concerning transition-point pressure and stabilizer setting—what its significance is to the string design, how it may work for or against the operation of the well, how it is related to tubing sensitivity and how it affects the unloading operation. The unloading operation may only be of academic interest in a technical paper, but to the production foreman, unloading and setting the valves in operation is a very real problem and should be understood in detail. One item touched lightly in the paper was the unloading valve. This valve controls the maximum pressure at which the well can be operated. When lifting heavy viscous fluids, it is most important to set this valve for the maximum possible realistic operating pressure at the surface. If the well lifts easily, it is simple to set the ASC valves at a lower operating pressure and the unloading valve will remain closed; but if the well happens to be heavier to lift than anticipated, it may be desirable to operate on the unloading valve itself and use all the energy obtainable at the bottom of the hole. In the Colonia pool very heavy wet-gas gradients are experienced due to the viscosity of the liquid and the dense mist which is left behind a slug of fluid. There are many combination strings of 3- and 21/2-in. tubing. This aggravates the wet-gas gradient problem and provides wet-gas gradients of about 50 to 70 psi/1,000. An advantage which multipoint lift has provided is increased slug efficiency through better maintenance of pressure under the slug and decreased fall back as the slug passes up the tubing. By using multipoint injection, wet-gas gradients have been reduced to about 30 psi/1,000. This has reduced bottom-hole operating pressure and given a production increase. The ASC valve is not a simple device. It's operation is difficult to understand, and it must be understood to be used efficiently in gas-lift design. Operating problems are difficult to diagnose—whether they be caused by the fluid lifted, valve malfunction, lift gas rate, or operating pressure. Calculations and reasoning are required to find out what is causing the problem. Inherent in the ASC valve is the inability to create large pressure differentials across a slug. Large differentials may be required to overcome the inertia of very viscous fluid as it is being accelerated in the bottom of the hole. This is tied back to the design of the unloading valve and is one reason for the importance of setting the unloading valve for the highest possible operating pressure. ~u; to the narrow spread the ASC valves provide, it is impossible to cycle slower than about 24 cycles/day on choke control. If small production of 150 BOPD and less is expected, a surface time-cycle controller will be required if the most economical operation is to be achieved. To achieve a satisfactory operation, the operator must keep a record of any changes made in the operating pressure of the ASC valves. Anything which may cause changes in casing pressure in excess of the stabilizer setting will change the valve operating pressure, and if this is not noted from daily inspection of the well casing-tubing pressure recorder charts, the operator will lose control of the well. Significant results can be achieved using ASC valves; however, considerable knowledge is required to design with them, and attention to detail is required for satisfactory field operation.

Jan 1, 1965