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By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By N. B. Davis

I. Introduction. II. Definition of Plasticity. III. Theories of Plasticity. A. Structure of the clay particles. (1) Fineness of grain. (2) Plate structure. (3) Interlocking particles. (4) Sponge structure of particles. B. Presence of hydrous aluminum silicates. C. Molecular attraction between particles. D. Presence of colloidal gelatinous matter. (1) Review of theory of colloids. (a) Suspension colloids. (b) Emulsion colloids. (2) Experiments. IV. The Formation of Clays. A. Residual clays. B. Transported clays. V. Summary. VI. Conclusion. I. IntRodUction While working with a number of very sticky cracking clays from western Canada the writer became interested in a study of the cause of the excessive plasticity. This led to a review of the rather bulky literature on the subject and the finding that plasticity still remains to be satisfactorily explained. Most of these investigations seem to have been carried on solely from the chemical viewpoint, the geologic aspects having been ignored. In nearly every case, the investigators have worked with the higher-grade clays of low to medium plasticity, such as the kaolins, the excessively plastic ones having generally been neglected, partly because of their limited application, yet the author believes that these are

Jan 1, 1915

By J. Hunter

DuXing 1942, Louisiana attained the rank of fourth among the great oil-producing states of this country. Its present prominent position is the result of an orderly and systematic program of exploitation with emphasis on conservation. Even before the functioning of M-68, the Federal spacing order, development and production in Louisiana were regulated by various acts of legislation, the most recent of which and by far the most effective is Act 157 of 1940. Under the authority of this act, it has been possible for the Department of Conservation to hold many public hearings and thereby to secure data and evidence regarding the feasibility of issuing rules and regulations for development of various oil and gas fields in the state. As a result of information compiled at such public hearings, many orders have been issued by the Commissioner of Conservation that have in most cases provided reasonable solutions to the problems that arise in the exploitation and development of fields in this state. Probably one of the most effective powers granted the Commissioner of Conservation in the state of Louisiana has been the authority to provide for fieldwide unitiza-tion and pooling of condensate fields. This has led to the erection of huge cycling plants in Louisiana, which permit the most efficient recovery of the liquid content of the reservoirs, and further conserve most of the gas reserve that undoubtedly will be of considerable future value. Many months have passed since various orders of the Department of Conservation were put into effect, and all are accomplishing their purpose; namely, the elimination of waste. Although the effectiveness of these orders provides considerable satisfaction to the members of the Department of Conservation, it is also a tribute to the members of the oil and gas industry in Louisiana, who, in addition to providing carefully prepared technical data, have also given unstinting cooperation and have thereby enabled the Department to cope intelligently with the many problems. Production On Dec. 31, 1942, oil and/or gas was being produced in 50 parishes, or 78 per cent of all the parishes in the state. Thirty-three of the parishes produced oil and gas, 12 produced oil, and 5 produced solely gas. This is indeed an enviable record for any state. However, it is reasonable to assume that eventually all parishes in the state of Louisiana will be productive. From a geological viewpoint, there is no apparent reason to assume otherwise—a point that a11 operators seeking oil and gas production in this state may well bear in mind. Twenty new fields were found during 1942—a rate of discovery that does not compare favorably with the 30 new fields found during 1941. The record of discoveries in Louisiana during 1942 is further disappointing when it is realized that 8 of the 20 new fields discovered were gas fields. During this period of war emergency, there are, of course, many

Jan 1, 1943

By J. Hunter

DuXing 1942, Louisiana attained the rank of fourth among the great oil-producing states of this country. Its present prominent position is the result of an orderly and systematic program of exploitation with emphasis on conservation. Even before the functioning of M-68, the Federal spacing order, development and production in Louisiana were regulated by various acts of legislation, the most recent of which and by far the most effective is Act 157 of 1940. Under the authority of this act, it has been possible for the Department of Conservation to hold many public hearings and thereby to secure data and evidence regarding the feasibility of issuing rules and regulations for development of various oil and gas fields in the state. As a result of information compiled at such public hearings, many orders have been issued by the Commissioner of Conservation that have in most cases provided reasonable solutions to the problems that arise in the exploitation and development of fields in this state. Probably one of the most effective powers granted the Commissioner of Conservation in the state of Louisiana has been the authority to provide for fieldwide unitiza-tion and pooling of condensate fields. This has led to the erection of huge cycling plants in Louisiana, which permit the most efficient recovery of the liquid content of the reservoirs, and further conserve most of the gas reserve that undoubtedly will be of considerable future value. Many months have passed since various orders of the Department of Conservation were put into effect, and all are accomplishing their purpose; namely, the elimination of waste. Although the effectiveness of these orders provides considerable satisfaction to the members of the Department of Conservation, it is also a tribute to the members of the oil and gas industry in Louisiana, who, in addition to providing carefully prepared technical data, have also given unstinting cooperation and have thereby enabled the Department to cope intelligently with the many problems. Production On Dec. 31, 1942, oil and/or gas was being produced in 50 parishes, or 78 per cent of all the parishes in the state. Thirty-three of the parishes produced oil and gas, 12 produced oil, and 5 produced solely gas. This is indeed an enviable record for any state. However, it is reasonable to assume that eventually all parishes in the state of Louisiana will be productive. From a geological viewpoint, there is no apparent reason to assume otherwise—a point that a11 operators seeking oil and gas production in this state may well bear in mind. Twenty new fields were found during 1942—a rate of discovery that does not compare favorably with the 30 new fields found during 1941. The record of discoveries in Louisiana during 1942 is further disappointing when it is realized that 8 of the 20 new fields discovered were gas fields. During this period of war emergency, there are, of course, many

Jan 1, 1943

By C. M. Wayman, M. Miyagi

COMPARED to many of the binary alloys of iron, Fe-Ir alloys have received very little tud.'' Virtually nothing is known about the Fe-Ir equilibrium diagram' except for a few details concerning the liquidus-solidus positions for dilute iron-based alloys. It is reported1 that the y to a transformation temperature in Fe-Ir alloys (up to 40 wt pct Ir) is composition-dependent, varying from -900°C for pure iron to 0" to 100°C for Fe-40 pct Ir in an almost linear manner. The y to a transformation appears to be reversible,' the transformation hysteresis width increasing with increasing iridium content. In a qualitative way, the composition dependence of the y to a (and vice versa) transformations appears similar to those in the widely studied Fe-Ni system. In that the y phase (in Fe-40 pct Ir) can transform at -1000C, it

Jan 1, 1967

By Thomas F. Donnelly

The Province of San Cristobal is situated on the south side of the island of Santo Domingo about 25 miles west of Santo Domingo city, the capital of the republic. The copper mineraliza,tion is found about 8 miles north of the town of San Cristobal,. in the section known as Bucaro Hill; in San Francisco Hill; on the Nigua River; and on the Jaina River. The district is reached by automobile from Santo Domingo city over an excellent road for 25 miles to San Cristobal, and then, by horseback 6 or 8 miles up the Nigua River to what is locally known as "Camp

Jan 1, 1916

By R. E. Boni, G. Derge

SURFACE tensions of molten silicates are of metallurgical importance for many reasons. From a knowledge of their values, an insight into the problem of liquid slag structure can be gained. Also, such problems as separation of slag from metal, slag penetration of refractories, spreading of enamel coats on metals, bonding of cutting wheels, adsorption of gases, frothing of slags, and homogen-ization of slags are related to the surface tensions of the silicates. Because of the absence of a correlated review of the work that has been conducted in this field, the following survey is presented. It is not a complete summary of all the surface tension studies of silicates but only a review of the literature which is pertinent to metallurgical applications and research. Liquid Surface Tension The surface of a liquid differs from the interior in that its particles (ions, atoms, or molecules) are not

Jan 1, 1957

By Thomas A. Wright

No symposium on die-casting could be complete without consideration of the methods of formula and impurity control. No corisideration of control would be complete without discussion of that new tool of the analytical chemist and inspector, the quartz spectrograph. Just as there is an increased appreciation of the possible applications of the die-casting process and of die castings, so too is there, slowly but surely, of the spectrograph. At present the role of the instrument might well be compared with that of brass or magnesium die castings. Neither is as widely understood or known as they will be. Product specifications are increasing and are getting more explicit and often more rigid. The designer, metallurgist and production engineer or superintendent will be forced to depend more and more on the chemical laboratory. Sampling, as well as analyses, testing and inspection problems will grow. The chemical laboratory must meet its increased responsibility and use of the spectrograph will become more common. Advantages of increased precision, greater speed, lessened labor and often lower costs cannot be ignored. It will be the purpose of this paper in part to outline the respective fields of chemical and spectrographic analyses and to indicate where one may overlap the other and in part to indicate certain possible sources of contamination of zinc-base die-cast alloys in particular. Composition Aluminum.-Aluminum die die castings are expected to conform to the specifications of the Amcrican Society for Testing Materialslt and the Society of Automotive Engineers2. The A.S.T.M. has recognized seven aluminum alloys in Tentative Specification B85-33-T. TWO are straight silicon and the remainder are of the copper-silicon type of which alloys VIII and IX have in addition respectively 2 and 4 per cent of nickel, but unlike the others are not covered by S.A.E. as well. All seven call for rigid control of certain impurities. With the exception of alloy XII,

Jan 1, 1935

By Thomas A. Wright

No symposium on die-casting could be complete without consideration of the methods of formula and impurity control. No corisideration of control would be complete without discussion of that new tool of the analytical chemist and inspector, the quartz spectrograph. Just as there is an increased appreciation of the possible applications of the die-casting process and of die castings, so too is there, slowly but surely, of the spectrograph. At present the role of the instrument might well be compared with that of brass or magnesium die castings. Neither is as widely understood or known as they will be. Product specifications are increasing and are getting more explicit and often more rigid. The designer, metallurgist and production engineer or superintendent will be forced to depend more and more on the chemical laboratory. Sampling, as well as analyses, testing and inspection problems will grow. The chemical laboratory must meet its increased responsibility and use of the spectrograph will become more common. Advantages of increased precision, greater speed, lessened labor and often lower costs cannot be ignored. It will be the purpose of this paper in part to outline the respective fields of chemical and spectrographic analyses and to indicate where one may overlap the other and in part to indicate certain possible sources of contamination of zinc-base die-cast alloys in particular. Composition Aluminum.-Aluminum die die castings are expected to conform to the specifications of the Amcrican Society for Testing Materialslt and the Society of Automotive Engineers2. The A.S.T.M. has recognized seven aluminum alloys in Tentative Specification B85-33-T. TWO are straight silicon and the remainder are of the copper-silicon type of which alloys VIII and IX have in addition respectively 2 and 4 per cent of nickel, but unlike the others are not covered by S.A.E. as well. All seven call for rigid control of certain impurities. With the exception of alloy XII,

Jan 1, 1935

By T. F. Bower, M. C. Flemings

Results are reported of a study of surface dendrilic structure of an Al- Cu alloy solidified against a chill wall. Most primary and secondary "arms " in the surface dendritic structure are arranged orthogonally, giving the impression of strong preferred orientalion on the surface. However, no such preferred orientation exists and it is therefore evident the arms do not represent (100) directions. The primary arms are shown to be interseclions of a (100) plane wilh the chill plane, or, equally often. the projeclion of a (100) direction on the chill plane. Secondary dendrite arms are usually within a few degrees of 90 deg to the primary arm, independent of grain orientalion. Prirary, secondary, and higher-order surface dendrite arms almost always represenl intersections of (100) platzes with the chill surace, or pvojections of (100) direclions. Growlh of secondary arms is favored on the side of the primary arm where a (100) direclion points toward the chill surfAce a1 a Lou, angle. Surface dendrile arms are often observed to be bent. In these cases, the crystal lallice changes orientation; bending is concave to the chill surface. In a previous paper,' a technique was discussed whereby large grains can be obtained at a chill surface. The technique used involves quickly drawing superheated liquid A1-4.5 pct Cu alloy into a thin copper mold, so that the mold is full well before solidification begins. The chill surfaces employed are polished copper blocks coated with amorphous carbon. Shrinkage during solidification between dendrite arms and grains delineates both, without the need for polishing or etching of the cast surface. The grain structure of the chill surface was discussed in a previous paper;' in this paper, the dendrite arms within each grain are examined. Previous work on surface dendrites includes that of Edmunds, who studied the development of preferred orientation in zinc, cadmium, and magnesium.' In zinc and cadmium, he found that the surface region has a (0001) texture (parallel to the chill surface). Walton and Chalmers reasoned that, since the fast growth (1010) directions are in the basal plane, nuclei which have this plane parallel to the mold wall would produce larger grains than nuclei with other orientations. Hence, the texture observed is as expected.3 The same authors, in measurements on aluminum ingots, found no preferred orientation at the mold wall. However, the X-ray technique they used measured the preferred orientation in terms of grain numbers, not grain areas; larger grains were weighted equally with small ones. No preferred orientation is expected on this basis at the chill surface. In a later paper,' Edmunds stated that experiments show a random grain orientation at the surface in die cast aluminum; his technique, also used in his earlier paper, takes account of grain area. Little work has been published on the dendritic structure of metal chill grains. Recent work of Biloni and Chalmers on "predendritic growth" shows the change in morphology from spherical to dendritic during the initial stages of freezing, 5 but this work did not include detailed examination of the fully developed dendrites. Other pertinent work includes that of Lin-denmeyer, who investigated the growth of ice dendrites. 6 When growth was on a substrate, the dendrite axes were bent. The bend corresponded to a change in orientation of the crystal lattice and occurred in such a way as to align the basal plane to the substrate. DENDRITE STRUCTURE Fig. 1 shows the chill surface of a typical casting poured above the critical temperature necessary to produce coarse grains. A cursory examination of these grains shows that the surface dendrite arms within most of the grains are oriented roughly perpendicular to each other. One is tempted to assume that these are (100) directions and that, therefore, marked preferred orientation exists at the chill face. This, however, is not the case. Each of the grains in the casting of Fig. 1 was separately identified, Fig. 2, and its orientation determined by the Laue back-reflect ion method. Results are given in Fig. 3 and it is seen there that no preferred orientation exists. Even when grain area is accounted for, there is no significant preferred orientation. The relationship between surface grain structure and crystal orientation was then obtained by assigning X and Y axes to the casting surface, Fig. 1, and assigning the same axes to the stereographic projections of each grain. Thus, the visible surface structure could be compared readily with grain orientation. This was done for fifty-five of the grains of Fig. 1. Results of this study on three typical grains are described below, and some general observations given subsequently. Fig. 4 shows the structure and stereographic projection of a grain which lies near the (100) zone (with respect to the casting surface). The X and Y directions are marked on the projection, and the photomicrograph mounted with the same orientation. Poles of the stereographic projection represent crys-tallographic directions in the grain which point out of the casting, toward the chill. Two (100) directions are shown in Fig. 4. A line joining the center of the projection and a pole represents the projection of the pole onto the X-Y plane (chill surface). Two such lines are shown in Fig. 4 (solid lines). A line joining the intersection of a great circle with the circumference of the projection gives the trace of a crystallo-graphic plane in the chill surface; two such traces are shown (dashed lines).

Jan 1, 1968

By H. P. Allen

THE Achotla mill of the Cia. Minera de Pe[n]oles is of special interest in that it is one of the few still employing the chloridization process. The ore milled comes from the Suriana mine and consists of both oxide and sulphide, from neither of which can the gold or silver be extracted by a simple cyanide treatment. The mill was built in 1927, after several years of study in the development of the process1, and operated from December of that year until October 1930. Operations were resumed in February 1935, and have been continuous since, treating approximately 5000 tons per month, while the mine is getting up to full tonnage of 6500 tons per month. Transportation Of Supplies The property is in Guerrero, Mexico, some 175 km. by airline southwest of Mexico City. The mill site is at Temisco (Fig. I), 8 km. from the Balsas River and 4.8 km. by aerial tram from the mine. At Temisco are the general office, shops, warehouses and laboratory serving both mine and mill. Here sufficient water is available either from a small creek running through the property or from the Balsas River, also convenient and ample storage space for the tailings. With the exception of the mine timber and a few native building materials which may be obtained locally, all supplies for both mine and mill are brought down the Balsas River from Balsas, the terminal of a Mexican National Railway line out of Mexico City. The method of transportation on the river is interesting. Rapids with very fast water are numerous, prohibiting the use of mechanically propelled boats. Those used resemble large, flat-bottomed rowboats some 22 ft. long by 8 ft. wide (Fig. 2). They are manned by two oarsmen sitting in the bow, each handling one large oar, and usually another man in the stern who, with his oar, assists in steering the boat, especially when the rapids are run. From 3 to 7 tons of freight are carried on each boat, depending upon the stage of the water, which governs also the time

Jan 1, 1937

By J. Brian Eby

As is generally understood, the word geophysics means literally ?the physics of the Earth? and the science of geophysics is therefore that which treats of the study and measurements of the various physical properties of the Earth. The broad and general study of the elastic, the gravimetric. or the magnetic properties of the Earth as a whole belongs to the general science of geophysics. The detailed application of this science to rocks of shallow depth and in small areas for the purposes of ascertaining data on their character and structural attitude gave rise to the present well-known science of ?applied geophysics.? Since the discovery of enormous new quantities of oil, gas, and sulphur has been by far and wide the principal benefaction of geo-physics in the United States, this paper will refer only to geophysical methods employed in the search for these particular minerals. The application of methods and appliances originally used for geophysical research to the solution of the practical problems of finding new oil-fields, plus the counterflow or new and highly refined techniques and Instruments from the company and consulting geophysical research laboratories and into non-economic geophysical research, has provided another case of that gen-eral cycle of events which is familiar to all scientists. That this closed-circuit flow or scientific current has been tremendously important to the whole science of geophysics is probably well known to all members of this audience, but the gen-eral status of the exploratory geophysical arts as now used In the search for new oil-fields, the scales on which different methods are being used, the magnitude of the costs involved, and the far greater magnitude of the practical results achieved may not necessarily have come so directly to your attention. It is, I understand, for this reason that this paper has been sug-gested, and I shall seek to provide the information requested by using as case-illustrations those changes in the oil-reserve picture for the United States as a whole, and for the Gulf Coast, California, and Illinois Basin regions in particular, which have occurred in the period of the past 17 years, during which time oil-field discoveries have proceeded at a rate which served to build up known and readily-available (or proven) oil supplies to a reasonable figure, and have dispelled the fears of a serious oil shortage during any period for which valid fore-casts can be made. Not that geophysical-prospecting methods have alone been responsible for this transformation, but they have an indispensable and leading part in the picture of exploration and production-to which geophysics, geology, engineering, and general technical progress have jointly made contribution. So far as the United States as a whole is concerned, its total proven, probable, and possible oil reserves (discoverable and recoverable by then-known methods) were estimated at about nine billion barrels in 1920, whereas proven reserves alone are now com-puted at about 16 billion. In 1920 the driller in ?wild-cat? territory was faced with the knowledge that for every new oil-field opened by a successful well, from 20 to 100 unsuccessful wells would have to be drilled and, in some territories, that the chances for a discovery were really less than one in 100 for new drilling, in contrast to which may be cited the record for the past year in parts of Louisiana where the 67 wells drilled opened 16 new oil-fields, that is to say, where the score of hits to misses was increased to approximately one out of four.

Jan 1, 1940

By Horace Mann

A FEW years ago, it was generally thought that from 15 to 18 per, cent. of zinc oxide was the upper limit of a workable lead blast-furnace slag. With slags above this zinc-oxide content, the furnaces gave so much trouble because of hearth, wall, and crucible accretions that the campaign was very short. The time lost in cleaning out the frozen furnaces, for it was seldom possible to blow them out, and blowing in was so great that it was considered uneconomical to attempt the running of high-zinc slags, even if this were metallurgically possible. It is true that there are, references to one or two slags much higher in zinc than the foregoing,1 but the average smelterman regarded these, as freaks and not to be considered for regular furnace work. One or two plants, notably the plant of the United States Smelting Co, at Canyon City, Colo., ran charges, higher in zinc. At this plant, the zinc-oxide content of the charge was frequently 20 per cent. and higher but the slags from these furnace's seldom ran over 10 to 12 per. cent. zinc oxide. The furnaces were run with a large volume of air under a relatively low pressure, a low smelting column, and a very hot top; as a result, a large amount of zinc was volatilized. Even with the low smelting column and hot top, accretions caused much trouble and barring, down was a daily occurrence. At the time most of the theories on lead blast-furnace work were promulgated or worked out, it was necessary to run a furnace with a cold top in order to avoid an excessive loss due to fines and fume. At the same time, the smelting conditions had to be such that the lead and silver would be reduced and would enter the bullion. The slag had to be liquid but the charge must not give excessive accretions either in the hearth or on the walls of the furnace. This forced the operators to run the furnaces with a comparatively low blast, which, in turn, caused a small fuel consumption per unit of time with the accompanying result of a low working temperature.

Jan 8, 1925

By W. C. Roberts-Austin

The subject with which the Council of the American Institute of Mining Engineers has entrusted me is one of much interest. It has been so admirably treated in America by Prof. Carl Barus* that I should have hesitated to deal with it had not the adoption of pyrometric methods in England recently occupied much attention, especially in relation to metallurgical industries and research. I shall endeavor to show what is the present state of our knowledge of practical pyrometry by briefly tracing the history of the efforts which have been made to measure high temperatures. This paper will, therefore, be limited to the consideration of those forms of appliance which have either marked distinct stages of advance, or have remained in use with more or less modification through a considerable range of time. The earliest pyrometers were essentially thermoscopes, and although their graduation presented great difficulties, their importance as affording a means for the measurement of high temperatures has been recognized for centuries. It would be difficult to illustrate this better than by a brief record of the testimony which has from time to time been offered by those who have had to apply the heat of furnaces in research or in industry, and it is mainly for the sake of the light incidentally thrown on the progress of both that the following historical notes are offered. In the eighth century, Geber, the chemist, wrote a treatise on furnaces, and showed that he was familiar with many and varied means of applying heat; but he points to the difficulties that are met with in conducting operations at high temperatures, which he attributed to inability to measure heat, his actual words being: " sed quoniam non est res ignis, quae mensuari possit." t

Jan 1, 1894

THE metal iron has physical and chemical properties which are somewhat different from those of steels, but a knowledge of the pure metal is a useful starting point in studying the behavior of steels. Solid iron exists in two different crystalline forms, called alpha (a) and gamma (?) iron, the former being the ordinary form at room temperature. When heated above the "A2 point," 1400°F. (760°C.), the metal becomes non-magnetic, and at the "As point," 1670°F. (910°C.), it undergoes a change in crystalline form to become gamma iron. In the range 1400 to 1670°F., it is sometimes called beta (0) iron to distinguish it from the magnetic alpha, but the two are identical in crystal structure. When gamma iron is further heated to 2550°F. (1400°C.), it changes into delta (d) iron, which is identical with beta or non-magnetic alpha iron. Pure iron melts (in a hydrogen atmosphere) at 2795°F. (1535°C.); the melting point is generally lowered by alloys or impurities. PROPERTIES OF IRON AT HIGH TEMPERATURES Many of the properties of iron undergo abrupt changes at the transition temperatures. (1) For example, in heating through the As point a sudden shrinkage in volume occurs. Similarly, melting is attended by sharp physical changes such as an increase in volume. Table 27 contains a summary of the measured physical properties of pure iron at several temperatures. Usually the properties change smoothly within the range of stability of a given form, but this is not always the case. For example, the specific heat reaches a sharp maximum at the A2 point although no transformation occurs. Solvent Powers of Liquid Iron. Liquid iron is capable of dissolving most of the other metals and many nonmetallic elements as well. Of the metals which are liquid at the melting point of iron only lead, silver, and bismuth refuse to dissolve to an appreciable extent. The non-metals presumably dissolve by virtue of the formation of an iron compound; for example, sulphur is thought to dissolve as the compound FeS. However, there is no satisfactory method of proving that this

Jan 1, 1944

By Thomas Fraser

There are large coal reserves in Argentina, Brazil, Chile, Colombia, Peru and Venezuela, and growing productive industries in Brazil, Chile, Peru and Colombia. The paper describes current activities in these coal fields, and improvement programs that are in progress, or are planned. Special emphasis is placed on improvements in mining and preparation practice, and expansion of production that have been accomplished by American equipment and technical assistance.

Jan 4, 1951

By R. L. Stegman, M. R. Achter

Nickel, fatigued in vacuum, shows intragranular crack initiation and growth at low temperatures. An increase in temperature initially prolongs fatigue life due to a more homogeneous distribution of slip. With a further temperature increase, the mode of failure undergoes a transitiotz to intergranular crack initiation with concurrent recrystallization which results in a shorter life. The transition temperature varies with bending strain and specimen purity. UNTIL recently, very little work has been done on the effect of temperature on the mechanism of fatigue and the resultant variation in fatigue life. Except for mild steel, where strain aging raises the strength at moderate temperature, fatigue lives had been shown to decrease with an increase in temperature. In their review article, Allen and Forrest' summarized the work of McCammon and Rosenberg and of Forrest and Mann on the fatigue of copper from -269" to 325°C. The fatigue life vs stress curves remained roughly parallel over this temperature range, the fatigue strength decreasing progressively with increasing temperature. When testing was done in vacuum, the present authors' found the results for nickel were different from those quoted above. Initially, the fatigue lives increased with temperature and then decreased as a grain boundary mode of failure was observed. The initial increase was attributed to a more homogeneous distribution of slip, a condition which was not as conducive to crack initiation as the bunching of slip lines observed at 20°C. Ronay, Reimann, and wood3 observed a similar change of slip line distribution in brass, tested in air, with rising temperature. Our previous observations were based on preliminary work with relatively few specimens, fatigued at comparatively low strains. To learn more about the mechanisms, the present investigation was undertaken for the purpose of studying systematically this effect over a wider range of strains and as a function of purity of the nickel. EXPERIMENTAL PROCEDURES The testing equipment, procedures, and specimen geometry have been described elsewhere.' An optical technique to measure bending strains was used as de-

Jan 1, 1968

By Eric Jette

IN order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be .added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a 'reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time' efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned.

Jan 1, 1931

By C. S. Matthews, G. L. Stegemeier

In one field in South Texas, approximately 72 per cent of the pressure build-up results show a characteris-i.rtic "hump" (i.e., the pressure builds up and then falls off) which makes interpretation by. standard methods impossible Correlation of size and time of hump with formation permeability. well productivitv index, and method of completion led to the tentativc, conclusion that the humps were caused by segregation of gas and oil in the wellbore after closing-in"'. This conclusion was confirmed by performance of simple laboratory bubble-rise experiments, by theoretical bubble-rise time calculations, and by a detailed calculation of PVT behavior in the well of a particular well Oil which accurate Surface and bottom-hole pressure measure-ments were untile. The hump behavior has since been found to occur in many other fields. The cause, however, is not the mine in all cases. In some of these the hump is trace-ahie to leaks in the tnbing which allow influx from the annulus after closing-in. In other cases the hump is traceable to leaks in the device separating pay horizons in dually completed wells. It is concluded that the recording of both surface and bottom-hole pressures is desirable in wells which show an anomalous build-up behavior. A number of field examples is discussed where use of both sets of measurements enables the cause for anomalous behavior to he found, (and a reasonable interpreation of bottom-hole pressure to be made. INTRODUCTION Theoretically the pressure build-up in an infinite reser-voir should be a linear function of In [(t + at)/nere t is the production time and At a the closed-in time. Some of the variations from this behavior arc well known, such as the curved portion immediately after shut-in which results from after-production and skin effect, and the flattened end portion which results from boundary effects in a limited reservoir. The effect of stratified producing zones and irregular geometrical drainage patterns may also contribute unusual characteristics to build-ups. However, the effect of still another phenomenon—that of movement of fluids within the wellbore—has been neglected in most build-up studies to date. Fluid movements within the wellbore after shut-in occur as a result of after-production, packer failures, leaks in the casing or tubing, or buoyancy of the gas phase when both gas and liquid are present in the well. Each of these movements can influence the pressure build-up, sometimes sufficiently to negate use of the data for computing permeability or stabilized build-up pressure. Examples of each of these phenomena are discussed below. FIELD OBSERVATIONS ON HUMP BUILD-UPS In approximately 75 per cent of the wells in a medium-sized field in South Texas the pressure build-up curves rise to 3 maximum and then decline to what appears to be a stabilized reservoir pressure as shown in Fig. I. Similar behavior has also been observed in wells in other fields in Texas and Louisian:,. Because of the possibility of such behavior being a mechanical failure of the pressure bomb. the bombs were run in tanden into one well which had been known to exhibit this behavior. When both bombs recorded identical curves with the characteristic hump, it was inferred that the unusual build-up is a result of well or forma-

By M. R. Tek, K. H. Coats, D. L. Katz

A large number of boundary value problems encountcred in unsteady-state heat transfer, fluid flow through porous media, neutron diffusion and mass transfer involve the solution of a linear, parabolic partial differential equation commonly refcrred to as the diffusivity equation, where U is the dependent potential variable. K is the diffusivity (hydraulic, thermal, neutron, etc.) and 1 is the time variablc. Solutions to Eq. I are available in the literature for a wide variety of initial and houndary conditions. The great majority of these solutions are ohtained for geometric boundaries corresponding to linear. cylindrical or spherical flow models. A typical engineering application where the solution to Eq. 1 is required is the calculation of underground water encroachment across the boundaries of oil or natural gas reservoirs, In this particular area of application, the reservoir boundary is invariably approximated by circular geometry. However. the areal shape of many reservoirs can be better approximated by elliptic rather than circular boundaries. Thus the need for a general method of solving the diffusivity equation in elliptic coordinates arises in this problem as well as in other engineering applications involving elliptic boundaries. The solution to the diffusivity equation usually in volves the Error Function for the linear flow model, Bessel functions for the radial flow model and trigonometric or Legendre functions for the spherical flow model. It is well known that the general solution to the diffusivity equation in elliptic coordinates involves Mathieu functions. The significance of Mathieu functions in the analytical treatment of the diffusivity equation in elliptic coordinates is discussed in the literature However, these references do not providc analytical solutions useful in practical engineering problems. The objectives of this papcr are the development of the equations describing the unsteady-state liquid flow through a porous medium with an elliptic inner boun- dary, the development of a numerical method of solving these equations and, finally, a comparison of the water encroachment quantities calculated from the elliptic flow equation with those calculated from the radial flow equation. While the specific problem treated in this paper relates to unsteady-state liquid flow through a porous medium, the basic equations and computational techniques devcloped will apply equally well to problems occurring in the other areas of engincering interest mentioned previously. The solution given here is limited to a single case in which thc outer boundary encloses an area 100 times that of the inner boundary. DESCRIPTION OF THE FLOW MODEL Fig. 1 shows the flow model upon which the calcu lations presented in this paper are based. The inncr and outer houndaries of the flow model are represented by two confocal ellipses with major and minor axes, respectively, equal to 2a1, 2b1, and 2a, and 26,. The height of the elliptic cylinder flow model is denoted by 17. The following assumptions are employed in the development 01 the equations governing the unsteady-state liquid flow through the described flow model. 1. Uniform porosity and permeability throughout the flow model