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By A. U. Seybolt, V. A. Phillips

Binary iron alloys containing 1 pct of Al, Cr, Mn, Mo, Si, Ti, or V, and 0.4 pct C, 1 pct Cr steels with and without 1.2 pct A1 or 2.0 pct Ti additions, were ion-nilrided at 550° to 600° in N-H mixtures. Nitriding increased the inicrohardne ss of all the binary alloys except those containing manganese or molybdenutn, and also hardened the heat-treated steels if aluminum or titanium urns present. Transmission electron microscopy revealed particle formation in all casts where hardening occurred. Electron diffraction gare positive identifications for ALN, CrN, and a, Si3N4 in the binary alloys, and AlN and CrN in the aluminum- cold chromium-bearing steels, respectil&apos;uly. Cubic VN with a, = 4.13A was tentatively identified. Particles, apparently of CrN, also formed in the base steel but did not increase the hardness very much. Chromium and vanadium formed nitride platelets on {001}° matrix planes, while titanium gave clusters <15A diam. Aluminum nitride precipitated at grain and subgrain boundaries, and within the grains. Silicon gave profuse precipitates of several Morphologies at grain boundaries and cubical particles within the grains. No effect of the alloy carbides on nitride precipitation was observed in the heat-treated steels. THE nitriding of steel has been a well-established commercial process for about 40 years, but in spite of this comparatively long period of use there have been few studies aimed at understanding the process. Most studies, like the early but very competent work of Jones and organ&apos; and nones.&apos; were concerned with establishing the pertinent engineering variables of steel composition, gas composition, temperature, and time. As far as the present authors are aware, there have been no studies of the composition, size, shape, or distribution of the nitrides formed in the nitriding of steel. Noren and Kindbom3 did, however, examine a few nitrided steels by surface replica electron microscopy, and were able to show the presence of car-bonitrides and AlN and TiN nitrides. pitsch4,5 and Hrivnak6 examined nitrided pure iron by transmission electron microscopy. Baird7 found manganese nitrides in Fe-1.6 pct Mn when nitrided at 650°C, using the same technique. In the present work, emphasis was placed on transmission electron microscopy because of its inherently better resolution, using principally binary alloys of iron containing 1 pct of alloying element. In addition, a few simple 0.4 pct C steel compositions were examined to investigate possible carbonitride formation. It was not anticipated that all of the added elements would form nitrides under the conditions used, but it was considered desirable to obtain direct experimental evidence on this point. It would be considerably easier to ascertain the presence of alloy nitrides by examining appropriate binary alloys in preference to relatively complex steels. The work reported here could have been done using orthodox ammonia-nitriding procedures, but an operating ion-nitriding equipment was available, and was therefore used for specimen preparation. EXPERIMENTAL DETAILS 1) Materials. Binary alloys were made up from vacuum-melted electrolytic iron with 1 wt pct additions of Cr, Ti, V, Al, Mn, Mo, and Si of about 99.9 pct purity. In addition, three steels were similarly made up—a basis steel with 1 wt pct Cr and 0.4 wt pct C and two steels with further additions of 1.2 wt pct A1 or 2.0 wt pct Ti, respectively. The materials were vacuum-melted and cast as 11-lb heats into tapered square molds of about 2 by 2 in. average cross section. The castings were forged and hot-rolled to 11/4 in. rounds. Discs of 4 in. thickness by about 1 in. diam were machined from the rods. Some of these discs were hot-forged and hot-rolled to about 0.020 in. thick, sand-blasted, and then cold-rolled to about 0.003 in. thick. At this point, the surface was cleaned by light etching with HC1, then washed, dried, and vapor-degreased prior to nitriding. 2) Ion-Nitriding Procedure. The type of ion-nitriding equipment used here is similar to that described by Jones and Martin.8 Briefly, a mixture of nitrogen and hydrogen at 5 mm total pressure is placed in a vacuum chamber with a dc potential of 450 to 500 v applied between the work (cathode) and the grounded metal vacuum enclosure (anode). Nitrogen ions are accelerated to the work where a thin layer of Fe4N forms on the surface and thus sets up a nitrogen concentration gradient. This causes nitrogen atoms to diffuse into the surface layers of the alloy forming a finely divided dispersion of alloy nitrides, causing hardening of the surface. In the work to be reported here. the nitriding was carried out at 550° to 600°C to be consistent with commercial nitriding practice. The temperatures cited are those measured by a thermocouple located under a platform on which the work was sitting. Except where otherwise stated, the mixture used in nitriding the binary alloys contained -2.0 pct N, balance hydrogen. The nitrogen concentration in the nitriding gas mixture used for the binary alloys was purposely kept lower than normally used in nitriding steels. 10 to 20 pct, in order to minimize Fe4N formation. In this way only the alloy nitrides would be present as a second phase. However, in the case of steels which would contain a- carbide phase along with as

Jan 1, 1969

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

By Edward J. Felten

Binary Cr-A1 alloys containing from 2.5 to 30 wt pct Al and 0.7 wt pct Y were heated in oxygen, air, and nitrogen between 1000" and 1200°C. The reacLivity of the alloys was found to be dependent both on the alloy composition nnd the nature of t he atmosphere. In oxygen, nllojs containing up to 15 to 20 wt pct A1 reacted to produce an external scale of Crz03 and a subscale consisting Predominently of Al203. Alloys contazning 20 to 30 wt pct A1 react in oxygen to produce an A1203 external scale and little m no subscale. The latter alloys were markedly more oxidation resistant than those of low alurninum content. In air, the alloys on which an external Crz03 scale was formed were found to be permeable to nitrogen ns evidenced by the copious amomts of chromium and aluminum nilrides observed ns part of the subscale. The reactizities in nir (or nitrogen) of these alloys increase <m their aluminurn contents increase. However, alloys on which Al,O, us an external scale is formed were nol culnerable to nccelerated attack in air, and no eltldence of nitvide subscnles were observed. For all alloys, yttrium serwed pYimarily to improve oxide adhrence. THE role of chromium in the oxidation resistance of Fe-Cr alloys &apos;-&apos; and that of aluminum in Fe-Cr-A1 al10s&apos; has received considerable attention in recent years. This is understandable since many of these alloys have excellent oxidation resistance due to the formation of either a Cr203 or a-Ala03 film between the metal and the oxidizing atmosphere. Small additions of yttrium or other rare earth metals are effective in preventing spalling of the protective oxide from the metal substrate."" In contrast, little is known regarding the oxidation resistance of Cr-A1 alloys, although some work has been done by Tumarov et a1.&apos; The poor niechanical properties exhibited by Cr-A1 alloys make them undesirable for use as structural components, but their use as coatings cannot be disregarded. The use of chromium-rich aluminide coatings for refractory metal alloys is an example of the potential use of this type of sytem. The purpose of this work is to examine the oxidation behavior of Cr-A1 alloys containing 2.5 to 30 wt pct A1 and 0.7 wt pct Y. The effects of temperature, atmosphere, and thermal cycling have been determined. EXPERIMENTAL PROCEDURE The alloys used in this investigation can be divided into two groups. Those containing 2.5, 5, 7.5, and 10 wt pct A1 and 0.7 wt pct Y were extensively evaluated in the temperature range from 1000" to 1200°C. Alloys containing 15, 20, 25, and 30 wt pct A1 and 0.7 wt pct Y were tested only at 1200°C. All of the alloys were prepared by standard arc-melting techniques in the form of cylinders approximately 4 in. long and 19 in. in diam. Wafers were cut from the cylinders and subsequently subdivided into rectangular coupons. The alloys were brittle and therefore some cracks were found in almost all specimens. The coupons were prepared for oxidation by mechanically polishing through 600 grit Sic paper, and were thoroughly degreased just prior to testing. Two types of oxidation experiments were conducted, namely; cyclic tests in which the specimens were examined and weighed after each 2 hr exposure, and continuous thermal balance tests run in a controlled atmosphere (oxygen, air, or nitrogen) for 20 hr. In the former test the spalled oxide was not included when the specimens were weighed. The physical condition of a specimen was noted visually after each cycle and testing was continued either to failure or until the performance of the specimen was well characterized. Both Micro and Semi-Micro Thermal Balances (Ains-worth) were used in the continuous tests. The oxidized specimens were sectioned and prepared for metal log raphic examination. The specimens were polished through 600 grit Sic paper. After polishing through 6 and l p diamond, a final mechanical polish with Linde B-Alz03 was used. Specimens containing 2.5 pct A1 were etched electrolytically using a 10 pct oxalic acid solution at 4 v for about 2 sec. Selected specimens were examined in the electron microprobe analyzer. Oxide specimens were examined by standard X-ray diffraction techniques. EXPERIMENTAL RESULTS For convenience, the test results have been broken down according to the exposure temperature, and further subdivided according to the type of test and atmosphere employed. Because of the poor quality of the specimens a larger than normal amount of scatter was observed in the measured rate constants. Also, the evaluation of the weight gain data was done on a somewhat arbitrary basis and may not be truly representative. However, the results obtained do show a significant trend in behavior regarding both alloy composition and the nature of the oxidizing atmosphere. I) Oxidation Behavior at 1000°C. A) Continuous Oxidation estsin Oxygen. This series of experiments was run in the Ainsworth Micro-Thermal Balance using pure oxygen at a pressure of 76 mm Hg. Under these conditions all specimens oxidized in accordance with the parabolic rate law over a major portion of the exposure time; the rate constants appear in Table I. The oxide formed externally on all specimens was predominantly Cr,O,, which was generally adherent. In some cases a slight amount of spalling in the form of a fine powder was noted. a-A1203 was observed as a subscale, along with Yz03 in all alloys. Alloys containing up to 7.5 wt pct A1 oxidize more rapidly than the Cr-0.7Y alloy.

Jan 1, 1970

By M. J. Marcinkowski, Gordon E. Lakso

An extensive investigation has been made of the deformation behavior associated with the Fe3Si super-lattice using transmission electron microscopy techniques. Above 243°K the stress-strain curve exhibits three stages. Stage I occurs at a very low stress level and is related to the generation of perfect superlat-tice dislocations. Stage II is characterized by an extremely rapid rate of work hardening and is associated with the Taylor type locking of these superlattice dislocations. Finally Stage III is related to dynamic recovery processes since the work hardening rate is very small. Below 243ºK, only Stage I is observed, but it occurs at a much higher stress level. This latter observation is related to the generation of imperfect dislocations in Stage I with the consequent production of second nearest neighbor antiphase boundaries. The reason for this is that insufficient thermal energy is available at these low temperatures to generate the complete and perfect superlattice dislocations. It has been shown that the fully ordered FeCo alloys, i.e., those possessing the B2 type structure, exhibit three distinct stages of work hardening whereas the corresponding disordered alloys show only one.&apos;" This difference in behavior between the disordered and ordered alloys has been attributed to the fact that dislocations in the former case travel only as ordinary 1/2ao(111) types whereas in the latter case the move through the lattice as coupled 1/2a0(111) dislocations separated by an antiphase boundary (APB), i.e., the so-called superlattice dislocation. Although some preliminary work has been carried out concerning plastic deformation in ordered alloys possessing the DO3 type superlattice,3 no detailed analysis similar to that described in Refs. 1 and 2 has been attempted. Specifically, it has been suggested that the superlattice dislocation in this particular type structure should consist of four ordinary 1/2ao<111> types bound together by first and second nearest-neighbor APB&apos;s. Fe3A1 and Fe3Si are the two classic alloys possessing the DO3 type lattice; however, because of the somewhat higher ordering energies associated with the FesSi alloy, which in turn assures that dislocations will travel through the lattice as perfect superlattice dislocations under at least some conditions, it was chosen for the present investigation. Because of the extreme brittleness of Fe3Si, all deformation was done in compression. Stress-strain curves were obtained using both polycrystalline samples as well as single crystals. In the latter case the crystals were oriented so that deformation could be controlled either by single or double slip. They were then wafered parallel to and at various angles to the operative slip planes. These wafers were in turn examined by transmission electron microscopy (TEM) techniques in order to determine the extent of the interaction from the dislocation configuration contained therein. EXPERIMENTAL PROCEDURE The alloys used in this investigation were arc melted under helium from electrolytic iron of greater than 99.90 wt pct purity and transistor grade silicon of 99.99 wt pct purity. A typical analysis of interstitial impurities showed 120 ppm 0, 15 ppm N, and 65 ppm C Because of the extremely low ductility of the Fe3Si alloys, it was necessary to spark cut 0.230-in. diam polycrystalline cylinders 0.400 in. long from arc-melted fingers using a thin-walled brass tube as a cutting tool. The polycrystalline alloys could not be recrystallized since very little strain was induced in preparation. However they were annealed at 1273°C for 15 min in evacuated vycor capsules to relieve any cooling stresses that may have developed during solidification and then air cooled. The resulting grain size of the alloy was 0.50 mm. According to warlimont4 1273ºC is just within the single phase field where FesSi possesses the DO3 type lattice. In addition because of this high critical ordering tem-ature, air cooling from this temperature was believed sufficient to fully order all of the Fe3Si samples used in the present investigation. For the same reason, no attempt was made to achieve any degree of disorder by quenching. In fact, rapid quenching from 1123°K caused cracking. Such cracking was first suggested by sato5 with respect to the experimental observations of Glaser and Ivanick.6 Single crystal compression specimens were spark cut from single crystal ingots grown in a Bridgman type furnace. The iron and silicon for the crystals was prealloyed by arc-melting two 130-g buttons which were cut into small pieces before remelting in the furnace. This procedure resulted in a long-range inhomogeneity of 0.5 at. pct Si between the top and bottom of the 2-in.-long single crystal ingot, which was assumed to be negligible in the present investigation. The single crystals, after orienting and spark-cutting, were about 0.37 in. by 0.37 in. in cross section and about 0.5 in. long. True stress-strain curves were obtained using an Instron Tensile Testing machine in conjunction with techniques described previously. 1,7 The strain rate was 0.05 in. per in. per min. Prior to testing, the ends of all the compression cylinders were hand polished using a special jig to insure parallelism after which the sides of the samples were electrochemically polished to eliminate stress risers and to facilitate slip line observations. Test temperatures between 77" and 823°K were obtained using various cooling and heating media as described in Ref. 7 while at the upper end of this temperature range, a mixture of equal

Jan 1, 1970

By H. Rosenthal, A. L. Jamieson

The action of mercury on stressed brass to produce cracks was known before Moore, Beckinsale and Mallinson1 showed that actual season cracking did not occur spontaneously but could be induced by ammonia. These investigators studied other substances, including diphenylamine, without finding that anything other than ammonia could cause season cracking Grimston2 reported season cracking in cartridge cases stored in wooden boxes wetted with dilute sulphuric acid pickling solution. Season cracking associated with sulphur dioxide, water vapor and air has been reported by Johnston,3 although he reported that trimethylamine and pyridine did not cause cracking. Jevons4 has ascribed season cracking of brass in certain instances to trimethylamine, "aldehyde amine," "ketone amine" and pyridine, but no experimental work was done evidently to prove this definitely. Pyridine was investigated by Morris,5 who found it to have considerable cracking power. In the present investigation, the object was a qualitative evaluation of a number of representative amines with respect to their ability to cause season cracking. Thus it was desired only that an appreciable vapor pressure of each amine be obtained in order to make the test as severe as possible, without attempting to test equivalent concentrations for comparative purposes. MEthods Specimens TWO types of specimen were used: 1. Unannealed 70-30 brass CUPs formed from 0.040-in. thick sheet. Height of cup Was 13/8 in. and diameter was 17/8 inches. 2. First draw pieces of caliber .50 cartridge cases in the unannealed condition (70-30 brass)- The cups were representative of a thin wall and thin base specimen, whereas the draw pieces have a thick base (1/4 in.) and a thick wall (approximately 3/32 in.). Both types of specimens contained high residual stress and cracked in less than one minute in a solution of I per cent mercurous nitrate and I per cent nitric acid provided that this was receded by a 30-sec. pickle in 40 per cent nitric acid. Specimens were prepared as follows: (1) degreased in trichlorethylene, (2) rinsed in H2O, (3) pickled 5 min. in 10 per cent by volume H2SO4 (1.84 SP. gr.), (4) rinsed in H2O, and (5) dried. Amirtes Tested In selecting the amines, representatives of the three series of amines, and one series of substituted amines were chosen. The aliphatic series was represented by the methyl and ethyl primary, secondary and tertiary amines. These are the simplest aliphatic amines. For the aromatic series, the phenyl primary, secondary and tertiary amines were selected as being the simplest. The heterocyclic series was represented by pyridine, which is a simple heterocyclic base (tertiary amine).

Jan 1, 1944

By Walter Miller

Petroleum refining, like other industries in the United States in 1940, focused much attention on its duties and opportunities in the field of national defense. In crdiiter-distinction to the situation during the World War, the industry is well constituted as to existing equipment, processes, and capacity, together with planned additions, to handle any demands that may be made upon it by the defense program needs. Evident throughout was the growing sense of ability to manipulate oil molecules for the production of materials not hitherto considered as being available commercially from petroleum. The development and application of catalytically induced reactions on a broad front is one of the distinguishing characteristics of refining progress during the year. In the hands of the refiner, catalysis has developed into a most important means to secure higher antiknock motor fuels and 100-octane fighting grade aviation gasoline in greatly increased quantity. One illustration of the importance being assigned to catalytic refining is the construction by the Houdry group of an experimental laboratory at a cost of $7&apos;307&apos;30&apos;3, to be staffed with over 100 research men7 solely for the purpose of studying catalytic reactions. In the aviation gasoline picture a modification of specifications by the Government widened the field from which acceptable fuel can be secured, and the continued expansion of the alkylation process in itself promises to go far in filling the demands expected from 50,000 fighting planes. It is conservatively estimated that eyen now the industry can turn out 1,300,000 gal. of 100-octane aviation gasoline daily. The upper limits of octane numbers for regular grades of motor gasoline reached in 1939 were not exceeded, but the average octane number approached the upper level more closely. A survey made of the 1940-model cars showed no rise in average octane requirement of the engines. The trend throughout the year was for greater reliance on the A.S.T.M. method for octane determination. The "1939 Research Method" is less widely used, although still considerably in evidence; the older L-3 method seems to have lost considerable ground and to be on the way out. Re-forming Capacities Increased Interest continued to grow apace in re-forming low-octane naphthas into high-octane gasolines. Some additions, although not great, were announced in thermal re-forming capacity. Interest in catalytic re-forming was greatly stimulated by the technical success of the operation of the converted hydrogenation unit at the Bay-way, N. J., rehery of the Standard Oil Company of New Jersey, mentioned in last year&apos;s review, and also by the knowledge that recoverable proportions of toluene are present in the hydroformed (catalytically

Jan 1, 1941

By Donald C. Branford

The place of geophysics in the curriculum of a college or an engineering school has been much discussed. There is uncertainty as to whether the graduate may be called a "geological geophysicist" or a "geophysical geologist." Some have used the term "geophysical engineer." The question of the specialized undergraduate curriculum versus a general undergraduate training in the parent sciences with the addition of cultural electives has been and is still being argued. The literature during the past Io years shows that there are two rather definite schools of thought on this subject. The prospective employer, engaged in active geophysical exploration, visualizes the graduate in terms of the routine work he will do in the field. The school administrator, grounded in many years of tradition in the cultural type of education, visualizes the graduate in terms of his position in a political and cultural society as well as in his work as a professional geophysicist. Both are right and both wrong. A third school of thought, that of the student himself, has been almost totally ignored. It would seem best, for the purpose of this paper, to treat these various points and allied material separately, and then to integrate the conclusions as a set of conditions that should be fulfilled as far as possible in the ideal curriculum. At the end the relationship of our findings to the curriculum that has been tentatively adopted at the University of Pittsburgh will be considered. Divisions in Definition or Field of Geophysics Geophysics is that field of science in which geological and earth problems are solved with the use of physical and chemical techniques. Altogether too much attention has been paid to the artificial separation in this science of the commercial applications from the so-called "pure" or academic geophysics. The only real difference in the two types of work is one of scale of operations. In the commercial field the scale is large in terms of fmancial backing, immediate economic importance, and speed of operations. In the academic field the scale is large in terms of breadth of interests, in eventual economic importance, and length of time allowable for theoretical investigations. In exploration work the scale is small in terms of dimensions, since the methods are applicable only to the outer 20,000 ft. or SO of the earth&apos;s crust. In academic work, the student is not pressed for results of immediate economic importance, and therefore can afford to spend more time on problems that seem unimportant at the time. In the sense of background knowledge of the parent sciences necessary to the geophysicist, no essential difference can be found. Physics, chemistry, geology, and mathematics together, and in their proper proportionate amounts, form the matrix from which geophysical ideas and methods may spring.

Jan 1, 1946

By Walter Miller

Petroleum refining, like other industries in the United States in 1940, focused much attention on its duties and opportunities in the field of national defense. In crdiiter-distinction to the situation during the World War, the industry is well constituted as to existing equipment, processes, and capacity, together with planned additions, to handle any demands that may be made upon it by the defense program needs. Evident throughout was the growing sense of ability to manipulate oil molecules for the production of materials not hitherto considered as being available commercially from petroleum. The development and application of catalytically induced reactions on a broad front is one of the distinguishing characteristics of refining progress during the year. In the hands of the refiner, catalysis has developed into a most important means to secure higher antiknock motor fuels and 100-octane fighting grade aviation gasoline in greatly increased quantity. One illustration of the importance being assigned to catalytic refining is the construction by the Houdry group of an experimental laboratory at a cost of $7&apos;307&apos;30&apos;3, to be staffed with over 100 research men7 solely for the purpose of studying catalytic reactions. In the aviation gasoline picture a modification of specifications by the Government widened the field from which acceptable fuel can be secured, and the continued expansion of the alkylation process in itself promises to go far in filling the demands expected from 50,000 fighting planes. It is conservatively estimated that eyen now the industry can turn out 1,300,000 gal. of 100-octane aviation gasoline daily. The upper limits of octane numbers for regular grades of motor gasoline reached in 1939 were not exceeded, but the average octane number approached the upper level more closely. A survey made of the 1940-model cars showed no rise in average octane requirement of the engines. The trend throughout the year was for greater reliance on the A.S.T.M. method for octane determination. The "1939 Research Method" is less widely used, although still considerably in evidence; the older L-3 method seems to have lost considerable ground and to be on the way out. Re-forming Capacities Increased Interest continued to grow apace in re-forming low-octane naphthas into high-octane gasolines. Some additions, although not great, were announced in thermal re-forming capacity. Interest in catalytic re-forming was greatly stimulated by the technical success of the operation of the converted hydrogenation unit at the Bay-way, N. J., rehery of the Standard Oil Company of New Jersey, mentioned in last year&apos;s review, and also by the knowledge that recoverable proportions of toluene are present in the hydroformed (catalytically

Jan 1, 1941

By W. A. West

ONE who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult&apos;s law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener&apos;s paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion of the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1946

By R. W. Brown, J. L. Loper

The process of sand erosion has been harnessed to perform a useful function—the directed perforating of oilfield tubular goods and formation rock. In this process the sand is carried by a liquid medium and the resrrlting slurry is forced through a nozzle at an extren~ely high velocity. Upon impingement against casing or formation, the fast-moving sand particles erode a perforalion in the casing followed by cavity formation in the medium behind the casing. The many factors influencing the rate and extent of this penetration are inherently difficult to establish experimentally. Equations describing submerged jet behavior have been applied to these conditions. The following paper develops the equations for predicting the performance of the perforating jet. INTRODUCTION The cutting power of high-velocity sand has been well known in the petroleum industry for many years. Sand carried by a high-velocity gas stream causes severe erosion. This effect has been the cause of numerous production problems in certain areas. It was logical to expect that this phenomenon would one day be adapted to useful industrial applications. Development of mobile, high-pressure, high-horsepower pumping equipment in the last decade has made this possible. The sand erosion process involves pumping a fluid containing abrasive solids through a set of nozzles at a high differential pressure (2,000 to 4,000 psi). The pressure conversion into kinetic energy imparts high velocity to the sand particles which, upon impact with the formation face or casing wall, erode the material in an organized pattern. This paper attempts to establish the effects of the various parameters and to predict the performance and limitations of the process. The following factors will be considered: nozzle differential pressure, perforation size, sand concentration, nozzle stand-off distance and backpressure. In general, this discussion is presented along theoretical lines and is substantiated by field results and data where reliable field data exists. POWER EQUATIONS The penetration rate of a high-velocity hydraulic jet is proportional to the power or energy of the jet at the point in quesion. The power of the submerged jet will decrease with distance (or penetration) into the cavity created by the jet. As the cavity is extended into the formation, the power of the jet diminishes to a value equal to the threshold cutting power of the particular formation which is defiined as the lowest power level at which the formation will be abraded by the jet. Obviously, when this point is reached, no further cutting of the formation can occur. It is assumed that this power level for a particular formation is a function of the hardness of that formation. The following equation can be written for the hydraulic process of formation abrasion.

By Donald C. Branford

The place of geophysics in the curriculum of a college or an engineering school has been much discussed. There is uncertainty as to whether the graduate may be called a "geological geophysicist" or a "geophysical geologist." Some have used the term "geophysical engineer." The question of the specialized undergraduate curriculum versus a general undergraduate training in the parent sciences with the addition of cultural electives has been and is still being argued. The literature during the past Io years shows that there are two rather definite schools of thought on this subject. The prospective employer, engaged in active geophysical exploration, visualizes the graduate in terms of the routine work he will do in the field. The school administrator, grounded in many years of tradition in the cultural type of education, visualizes the graduate in terms of his position in a political and cultural society as well as in his work as a professional geophysicist. Both are right and both wrong. A third school of thought, that of the student himself, has been almost totally ignored. It would seem best, for the purpose of this paper, to treat these various points and allied material separately, and then to integrate the conclusions as a set of conditions that should be fulfilled as far as possible in the ideal curriculum. At the end the relationship of our findings to the curriculum that has been tentatively adopted at the University of Pittsburgh will be considered. Divisions in Definition or Field of Geophysics Geophysics is that field of science in which geological and earth problems are solved with the use of physical and chemical techniques. Altogether too much attention has been paid to the artificial separation in this science of the commercial applications from the so-called "pure" or academic geophysics. The only real difference in the two types of work is one of scale of operations. In the commercial field the scale is large in terms of fmancial backing, immediate economic importance, and speed of operations. In the academic field the scale is large in terms of breadth of interests, in eventual economic importance, and length of time allowable for theoretical investigations. In exploration work the scale is small in terms of dimensions, since the methods are applicable only to the outer 20,000 ft. or SO of the earth&apos;s crust. In academic work, the student is not pressed for results of immediate economic importance, and therefore can afford to spend more time on problems that seem unimportant at the time. In the sense of background knowledge of the parent sciences necessary to the geophysicist, no essential difference can be found. Physics, chemistry, geology, and mathematics together, and in their proper proportionate amounts, form the matrix from which geophysical ideas and methods may spring.

Jan 1, 1946

By Warren E. Wilson

PRESENT-DAY design of launders is essentially an art depending to a marked degree upon the experience of the designer, whose problem is that of determining the dimensions of a conduit that will transport the pulp within the physical limitations of the plant and in the most economical manner. This paper has been prepared in an effort to place launder design upon a more scientific basis. A method is developed from elementary principles and presented in a form that may be used directly by the designer in determining launder dimensions.. The equations that are developed are believed to represent an advance over older ones, in that they give due consideration to all the pertinent variables, either including them in the analysis or showing that they may be neglected within the limits of applicability of the equations. Experimental data from several sources are used in evaluating the coefficients that are not determined in the mathematical analysis. On the basis of the material presented, it is concluded that launders may be designed with a much greater degree of accuracy than previously believed possible, when due consideration is given to all the factors involved in the problem. However, a great deal of work still remains to be done in the laboratory before a complete answer to all the questions in launder design can be made available. HISTORY OF LAUNDER DESIGN Among the references1-11 are cited accounts of many experiments that have been conducted in an effort to advance the knowledge of the flow of liquid-solid mixtures in flumes and pipes. With three notable exceptions, this work was carried on in such a manner that the results have limited value in solving the general problem, since not all the pertinent variables were measured and controlled. The exceptions are found in the works of Blue,6 Gilbert,7 and Blatch,11 who exercised great care in controlling and measuring all the significant quantities involved in the experimentation. It is notable that much of the work done by men directly connected with the mineral industries1-4 lacks somewhat in completeness, owing apparently to preconceived notions concerning the factors that determine the flow. For example, many measurements on flow in pipes and flumes carrying liquid-solid mixtures determined only the slope and percentage of solids, with no mention of size of particles, depth of flow, roughness of channel or specific gravity of solids. Material in current handbooks8,9 and textbooks is based largely on the experimental work cited above. Although most discussions of the topic-include statements that the results to be obtained by using the data presented are limited by the fact that all variables have not been considered, it is

Jan 1, 1943

By C. S. Matthews, H. C. Lefkovits

The performance of depletion-type reservoirs at the stage in which the gas is at such low pressure that gravity is essentially the sole driving force has been investigated both theoretically and by use of scaled models. A simple theory is developed which completely explains the scaled model experiments. It also agrees with some field data. When the range of production rates to be considered is less than 25, the theory predicts that the production rate decline curve for homogeneous reservoirs in which there is a free surface will be of the hyperbolic type with n = 2: The theory gives a physical significance to the parameter y. INTRODUCTION This investigation was undertaken to determine a method for prediction of performance of reservoirs where gravity is the sole driving agent. Depletion-type reservoirs fall into this category after the pressure has fallen to some low value. Some examples of this type are found at Healdton (&apos;Oklahoma), Oklahoma City (Oklahoma), Midway-Sunset (California), and East Coalinga (California). Generally the production rate per unit thickness is quite low in such reservoirs, with the conse- quence that this stage is sometimes called the stripper stage. However, per well production rates may be of the order of 50 B/D because of the considerable sand thickness open in some of the reservoirs. In the past, predictions of behavior of such reservoirs have been based on empirical extrapolation of the rate of production to the economic limit. Difficulties arise when new wells are drilled in the field or when production is artificially curtailed, since in such cases the decline rate of individual wells or leases changes and no clear trend can be detected. It was hoped that the present study would lead to improved methods for evaluation of such reservoirs. The study was initiated by building a scaled model for a particular field and by running a number of experiments on this model. Later a simple theory was developed which explained the laboratory results completely. The theory led, as shown below, to a hyperbolic-type decline equation which had been used previously&apos; in a completely empirical manner. THEORY The General Case The problem to be treated here is the following: We are given a homogeneous cylindrical porous reservoir with exterior radius r, wellbore radius r., and height h,, containing, from the bottom up to a height hit oil, some gas, and interstitial water (see Fig. 1 A). The portion of the reservoir between K, and h, is filled with gas at low pressure, with residual oil, and with interstitial water. If at a time t = 0, the level of the oil in the wellbore is lowered to a height h,, what is the production rate from the reservoir at a time to The configuration within the reservoir at some instant

Jan 1, 1957

By J. C. McCarthy, J. B. Stone

At Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. Location The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in. the world. Another famous old silver district, Sombre-rete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo On on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is Surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proano hill are the Fresnillo mines, and it is marked now by a great gash cut by glory-hole mining. According to an account written in 1834 by Francisco Garcia, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between zacatecas and sombreretea Little is known of the earliest mining at Fresnillo, which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notably active in 1751 under an administrator named Murguia, who left detailed notes describing them. In I757, however, the mines became inactive because of dificulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor Garcia had been aroused by the long disregarded notes of Murguia. Under Garcia&apos;s energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difliculties, including abnormal rains and an epidemic of cholera. In 1835 English capital was sought to allow installation of steam-driven is pumps at the two principal shafts and to build the great hacienda de beneficio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1949

By J. C. McCarthy, J. B. Stone

At Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. Location The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in. the world. Another famous old silver district, Sombre-rete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo On on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is Surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proano hill are the Fresnillo mines, and it is marked now by a great gash cut by glory-hole mining. According to an account written in 1834 by Francisco Garcia, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between zacatecas and sombreretea Little is known of the earliest mining at Fresnillo, which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notably active in 1751 under an administrator named Murguia, who left detailed notes describing them. In I757, however, the mines became inactive because of dificulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor Garcia had been aroused by the long disregarded notes of Murguia. Under Garcia&apos;s energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difliculties, including abnormal rains and an epidemic of cholera. In 1835 English capital was sought to allow installation of steam-driven is pumps at the two principal shafts and to build the great hacienda de beneficio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1949

By J. W. Hickman, E. A Gulbransen

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn&apos;s6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By Simon D. Strauss

COPPER In terms of mining activity, copper is the leading nonferrous metal. It is true that in recent years the volume of aluminum consumption in the non-Communist world has exceeded the volume of copper consumption, but virtually the entire primary aluminum supply is derived from bauxite. On the average, only four tons of bauxite need be mined to produce a ton of aluminum. By contrast, the highest-grade, large-scale copper mines now in operation (those in the Congo) must mine at least 20 tons of ore to produce a ton of copper. In the United States an average of 150 tons of ore must be mined to produce a ton of copper. This does not take into account the huge amounts of waste overburden that must be stripped from the open-pit mines to account for their steadily rising share of the world&apos;s copper output. Copper epitomizes the economic problems of the mining industry in many ways. Its price is highly volatile, considering its great economic importance. It has been a tool of mankind longer than any other of the base metals-the dawn of history has been classified as "The Bronze Age." World Copper Production Although copper is mined in many countries, in recent years 70% of the non-Communist world production has come from six countries. Two of these are industrialized countries and are large consumers-United States and Canada. The other four are developing countries with very small domestic requirements-Chile, Zambia, Zaire, and Peru. Heavily dependent on copper exports to sustain their domestic economies, these countries find themselves oscillating between prosperity and depression with the changing levels of copper prices. In an effort to control their own destiny, in 1968 they formed an organization of copper exporting countries (CIPEC) which was designed to study copper markets and possibly to intervene actively in these markets. (When this chapter was being prepared, no actual steps along such lines had been taken.) Many of the leading industrialized nations are wholly dependent on imports for their primary copper supplies. These include West Germany, the United Kingdom, France, Italy, and many others. Japan, now the non-Communist world&apos;s second largest copper consumer, produces only 10 to 15% of its requirements from domestic mines. Although the bulk of the copper output is smelted in the country where it is mined, there is a limited international trade in copper concentrates. Canada, the Philippines, Australia, and Papua-New Guinea are significant exporters of copper concentrates; Japan, Germany, the United States, and Sweden are importers. However, this trade accounted for only about 10% of the non-Communist world production of copper during the decade of the 1960s.

Jan 1, 1976

By E. A. Gulbransen, J. W. Hickman

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn&apos;s6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.&apos;-a In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative and may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole. These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in Pennsylvania, carried out by the Pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author&apos;s knowledge, in the published literature. The potential differences across the contacts of sandstone and shale are called in this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored Well In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored with diamond tools. The potentials were first measured with fresh water in the hole. A null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and crystals surrounding a pure copper elec-

Jan 1, 1944

By Walter Crafts, C. M. Offenhauer

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

Jan 1, 1942