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By D. C. Hilty, W. Crafts

The solubility of oxygen in iron containing aluminum has been determined at 1550°, 1600°, and 1650°C and found to be much higher than predicted from theoretical considerations, possibly due to equilibria with an iron-aluminum spinel phase rather than pure AI,O.. The presence of manganese greatly increased the deoxidizing power of aluminum. DEOXIDATION and inclusion formation in steel have proved to be elusive phenomena that are difficult to control in spite of much effort to understand and evaluate the reactions. Study of the problem indicated that more accurate data on the solubility of oxygen in iron containing deoxidizers were essential to further progress, and an empirical determination of oxygen solubilities has been initiated at the Union Carbide and Carbon Research Laboratories, Inc. The investigation has included the effects of aluminum, silicon, manganese, and combinations of these elements at 1550°, 1600°, and 1650°C. The equipment and experimental procedure as well as the results of a study of the effects of aluminum are described below. In general, it was found that the solubility of oxygen in iron containing aluminum is much higher than predicted, possibly because of the formation of complex nonmetallic phases, and that manganese greatly increases the deoxidizing power of aluminum. The generally accepted deoxidation curves for 1600°C are summarized in fig. 1, from "Basic Open Hearth Steelmaking"'. These curves are assumed to represent the solubility of oxygen in the presence of deoxidizers and should indicate the limits of mis-cibility gaps in the phase diagrams of the systems that control the formation and character of non-metallic inclusions as described by Benedicks and Lofquist'. They were derived mainly by application of the methods of thermodynamics to the available experimental observations, and by calculations based on the thermal constants of the pure substances when experimental data were lacking. Among the more notable researches contributing to the development of knowledge of oxygen solubilities are those of Korber and Oelsen8, 4, C. H. Herty, Jr. and associates5,6, Krings and Schackmann7, Went-rup and Hieber8 Schenck and Briiggeman9, Vacher and Hamilton'" and Chipman and co-authors 1,11,12,13 Practically, the deoxidation curves are of limited value in predicting oxygen content and rationalizing deoxidation practices. The reasons for this inadequacy appear to be error from inaccurate data, oversimplifying assumptions, interacting effects of combined deoxidizers, and possibly unknown extra-equilibrium and side reactions. Although inclusion formation is a very complex reaction it must be re-

Jan 1, 1951

Discussion of the paper of Frederick W. Apgar, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 7S, June, 1913, pp. 1011 to 1022. L. C. GRATON, Cambridge, Mass.:-I presume I am one of the few who are exceedingly interested in microscopic work, and I am sure we have all enjoyed this paper very much. I will not attempt to express my own feelings in regard to it beyond saying that it seems to me that this sort of investigation and study has been overlooked and slighted, and its possibilities are very great. There are one or two, details which impressed me, because they were novel to me, and one was the development of secondary galena with dull luster. I have never seen any galena which seemed to be secondary, and have never seen any that was secondary or primary that did not have a bright luster. KIRBY THOMAS, New York, N. Y. (communication to the Secretary *) :-The present-day mining engineer is expected to " see into the ground farther than the point of the pick " and he is justified in making free claim to his ability to do so. Mr. Apgar has recorded the development of the application to the work of the engineer of a very useful but tardily recognized instrument-the petrographic microscope, an instrument which is helping to shatter the proverbial "point of' the pick" limitation-and he has shown its use and its possibilities very clearly. Some further field examples of the use of the microscope in engineering problems may add to the appreciation of Mr. Apgar's scholarly paper. In exploration by diamond drills in the Sudbury, Ontario, nickel district it is often of great importance to determine when the drill has passed out of the norite and into the foot-wall formation. Structural calculations may give a clue to the expected point of contact, but the variations are considerable, and, since to stop the drill before reaching the contact is futile, and too continue beyond it is needless, it becomes of theoretic and economic importance to determine positively the lithological nature of the corer at critical stages in the work. In some places the foot-wall is an earlier norite, only distinguishable from the nickel norite (Sudbury-: ite), by means of an examination of the rock slides with a petrographic; microscope. Again, certain diabase dikes which cut the norite and. the foot-wall formations cannot be easily or with certainty distin-

Jan 11, 1913

By S. A. Wookey

More than 90 per cent of the ore produced by stoping at McIntyre is mined by horizontal cut-and-fill methods. The remainder is mined by square set and fill. In the stopes on the upper levels, mill holes are spaced 80 ft. apart and usually it is feasible to mine the breast for the full distance between the mill holes in one operation and to break, clean out and fill without any support for the roof or walls, other than the odd crown bar or sprag. The ore is scraped to the mill holes by small (10 to 15 hp.) air-operated slusher hoists. No grizzlies are used over the chutes and care is taken to break up the big pieces beforehand. Fill usually is spread by tramming sand or waste in a one-ton car from the fill raise. Fill raises are driven parallel to the strike of the vein and are inclined at approximately 48°. In long stopes, where more than one fill raise is necessary, they are spaced about 300 ft. apart. It is sometimes necessary to stand square sets for a short distance each way under the brow of the fill raise. support needed increases and on the lower levels and in some wide stopes where closer support of the back is necessary, it has become standard practice to timber the stope with 12 by 12-in. timber. Rough timber sets consisting. of caps, tightly blocked to the back and supported on posts 7 ft. high, are placed at about 5 ft. intervals. These sets are generally salvaged from the lower breast before blasting and are used again on the upper slice after the fill has been placed. In general, two or three breasts may be broken down before mucking out and filling and the ground stands long enough to enable this to be done safely. On the lower levels and in certain wide stopes and in heavy ground, a more intermittent method must be used. Only one breast or even part of a breast can be blasted and the back must be timbered before the ore can be removed. In these cases, sill timbers 16 ft. long, supported at one end on posts from the fill and at the other end on pins inserted in holes drilled in the face, are used. Timber cribs 5 by 9 ft. built from the fill to the roof and tightly blocked to the back are used throughout the mine to reinforce both the timber sets and the square sets.

Jan 1, 1946

By Will Mitchell, T. G. Kirkland, C. L. Sollenberger

BENEFICIATION of a Korean scheelite ore has been studied during the past year in the Basic Industries Laboratory at Allis-Chalmers Manufacturing Co. A flowsheet has been recommended including flotation, gravity separation, and a final cleaning by a magnetic separator. The investigation was continued in the field of flotation in order to establish the effect of certain variables on recovery and grade of rougher concentrates. The results of this investigation are recorded here. Mineralogy The scheelite ore was obtained from Korea and was mined from the Sang Dong deposit. This deposit is described as lying in gently dipping metamorphosed sedimentary beds of Cambrian age.' The metamorphism was probably either metasomatic replacement or recrystallization, or both, with subsequent hydrothermal deposition. Igneous bodies in the form of granite porphyry have been found within 7 km of the main shaft and are considered to be a possible source of the mineralizing solutions. The Myobong formation, the host for the Sang Dong deposit, was laid down in middle Cambrian times and consists of series of mudstone, siltstone, shale, and marl, with local stratification of mica schists, hornfels, and tactites. The scheelite is found in quartz bands in the tactites. Although there are six of these bands, only one, the "main bed" averaging 1.75 pct WOs, has been mined to any extent. The ore sample as received in the laboratory was the product of a cone crusher and was all —2 in. The rock appeared to be even textured, medium to fine grained, and gray green in color. No scheelite could be recognized by the unaided eye. However, under ultraviolet light of 2537 A, the scheelite fluoresced and could be distinguished from the gangue. Under the black light, the scheelite showed no definite vein structure but was disseminated throughout the specimen. The raw ore had a specific gravity of 2.96 and weighed about 125 lb per cu ft at —20-mesh Tyler. The —2-in. material was stage crushed through 20-mesh, and samples were cut for mineralogical, chemical, and spectrochemical analyses. Several polished sections were cut from hand specimens. Figs. 1 and 2 show quartz to be the matrix for scheelite. It was reported by Kim2 that the greatest scheelite concentration in the mine is found with a high concentration of quartz and a decrease in the abundance of garnet. Diameters of scheelite particles ranged from 1.2 mm down to less than 50 microns. Spectrochemical analysis showed the ore to be high in aluminum, bismuth, calcium, iron, magnesium, manganese, silicon, tungsten, and with lesser amounts of beryllium, chromium, lithium, sodium, and titanium. Chemical assays showed the —20-

Jan 1, 1952

By C. M. Young

Wherever salt is extracted from the ground as an artificial brine produced by pumping down fresh water to dissolve the salt, subsidence of the overburden is a possibility, though apparently few cases of such subsidence have been noted and detailed records are wanting. This description is intended as a record of subsidence that may permit the forcasting of similar occurrences in other cases; the data were supplied largely by R. B. Lee, city engineer of Hutchinson, Kans. About eleven years ago, ground movement occurred at a neighboring salt plant, when the surface assumed the form of a shallow funnel. Movement was probably due to a flow of sand into a well through a poor seal or a broken casing. The salt deposit increases in thickness from the east until at Hutchinson, where the subsidence occurred, it is about 310 ft. thick. The interbedded layers of shale vary in thickness from mere traces to about 7 ft. While knowledge of the shale content of the beds is not exact, the log of a shaft 3 miles east of Hutchinson indicates that shale forms about 25 per cent. of the total thickness. This shaft does not reach the bottom of the salt by about 60 ft., but there is no reason to think that the lower part of the bed is different from the upper. Logs of wells sunk to the bottom are not sufficiently detailed to be of much value. Above the salt is the shale of the well-known Red Beds. The thickness of this is variable, principally because of its eroded surface, but at the mine it is 340 ft. This shale is variable in character and strength, but contains no strong members of limestone or sandstone. If the support is removed, very probably it will subside. The Arkansas River flows across the salt district and Hutchinson is situated on the flood plain. Between the top soil, which is about 8 ft. thick, and the shale is 60 to 100 ft. of water-bearing sand and gravel. The process of removing salt, at least in the case of the earlier wells with which we are concerned, is as follows: An 8-in. hole is put down through the sand and gravel by means of a drive pipe, which is bedded in the shale. Prom the top of the shale, a 6411. hole is drilled through the shale, to, or nearly to, the bottom of the salt. Casing is put in to a depth of about 140 ft. to shut off a water-bearing layer in the shale.

Jan 1, 1927

By R. E. Reed-Hill, W. H. Hartt

The "(3034) " twin lamellae in magnesium have been reexamined using electron microscope replicas. The double twinning sequence (1011)- (1012) for these lamellae has been reconfirmed. Evidence is presented showing that the irrational habit of these twins is probably the direct result of a need to accommodate the second-order twinning shear. This accommodation vesults in both an external shear in the matrix and an internal shear in the lamella. A model is presented which accounts for the experimental obseruations. HCP metals are generally characterized by strong textures in which the basal planes of the grains tend to be aligned parallel to the rolling direction in sheet or plate and to the axis of wires and rods. Since these directions are normally those in which finished products may be subjected to uniaxial tensile stress, these textures effectively place the crystals of magnesium objects in orientations unfavorable to both basal slip and {1012) twinning, the easily activated deformation systems of this metal. However, when magnesium crystals are deformed near room temperature by a tensile stress nearly parallel to the basal plane, another mode of deformation can occur.',2 This is _a double twin which forms first by twinning on {loll), followed by retwinning on (1012). The resulting twin lamellae are of considerable interest. First, they can be responsible for "brittle fracture''; when a tensile stress axis lies in the basal plane, because the reoriented crystal structure of a lamella is well-aligned for slip while the parent crystal is not. Extensive internal deformation may thus occur while the matrix is still almost undeformed. This deformation can produce a ductile rupture running the length of the twin.3 Complete failure of the specimen may then oc-cure by the spreading of cracks from one twin lamella to another, or by the movement of a crack into a grain boundary and then along grain boundaries. Since the the volume fraction of these doubly twinned elements is normally very small, the fracture may be classed as brittle, although the fracture mechanism is, of itself, essentially ductile. It is quite probable that the ductility transition, normally observed4 in magnesium at or slightly Obove room temperature, is closely associated with these second-order twins. The detailed relationship of these twins to fracture in single crystals will be the topic of another paper. The present paper is concerned with a second important aspect: the irrational habit of these double twins that falls close to {3034), or approximately 7 deg away from the primary (10il) twin habit. There is good reason to believe that this habit results directly

Jan 1, 1968

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at '5 to 40 tons per sq' in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at '5 to 40 tons per sq' in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By L. L. Foley, C. V. Millikan

The discovery of Bromide production in the Fitts field, shallow production in Jackson County of Southwestern Oklahoma, abundant production in the Edmond field, and discovery of many small pools in all parts of the state, were the events that made petroleum history in Oklahoma in 1934. Wildcatting was much more active, as evidenced by a number of new discoveries. There was no important development in the older fields. The rapid decline of the potential of the Oklahoma City field was an important feature of the history of the year. The accompanying tabulation of oil fields (Table 1) is not complete. Many of the early records of operators and pipe line companies are lost and it will be impossible to work up complete statistics for a number of the older fields. The table includes most of the important fields of the state and includes fields of a number of different types. It is hoped that a great many additional fields may be worked up for next year's report. Fitts Pool.—The Fitts pool, in Pontotoc County, was discovered in 1933. Before the middle of 1934, the Pennsylvanian sands yielded -some oil at depths ranging from 1400 to 2800 ft. The Hunton series (Siluro-Devonian) produced most of the oil with considerable gas. In July, 1934, a well in sec. 25, T.2N., R.6E. was completed in the Bromide (Ordovician " Wilcox ") with an initial production of about 300 bbl. a day. Less than a month later a second Bromide sand well was completed in sec. 30, T.2N., R.7E., which made over 200 bbl. an hour. This started an active drilling campaign, which was accelerated when some of the major companies paid good prices for adjacent acreage. At the end of the year, 23 wells had been completed and the rate of development was increasing rapidly. It is a major oil field. The Fitts pool opened a new geological province for oil production. The structure is a faulted anticline in a graben. The producing formation (Bromide) and the Arbuckle lime below it crop out about 2 miles south of present production. The Hunton lime crops out about 2½ miles north. The field is in a sharply folded and faulted area on the northeast side of the Arbuckle uplift. Heretofore, it was generally considered not favorable for oil production, although some gas had been found in various places. The play has extended east into the McAlester coal basin, and southeast toward the

Jan 1, 1935

By R. S. Christie

Reservoir pressure is the pressure at which a fluid is held in a state of equilibrium in a porous stratum. This pressure may be a result of the genesis of oil or gas and its subsequent migration into and through an adjacent porous stratum, or of hydraulic head. Reservoir pressure is an indication of the potential energy contained in the reservoir, and when it is known the engineer is in a position to use it to advantage in recovering and lifting the oil. It is important to know the pressures in any type of reservoir, but this knowledge is probably of greater value in a limestone reservoir, as at Hobbs, where producing rates or conditions may be more sensitive to changes in pressures. The Hobbs field is in east central Lea County, New Mexico. The discovery well was completed by the Midwest Refining C I. in 1928, but intensive development did not begin until after the completion by the Humble Oil and Refining Co. of No. 1-A Bowers in February, 1930. There are 143 producing wells on approximately 5500 acres. The field has not been defined to the northwest, but a projection of structural contours indicates that the productive area ultimately may cover 7500 acres. The producing horizon is the White or Crystalline lime of Permian age. The top of the lime is found at an average depth of 4000 ft. and the wells penetrate it an average distance of 200 ft. The main pay zone is an oolitic stratum about 25 ft. below the top, and varies from 2 to 15 ft. in thickness. Other porous or cavernous strata are found lower in the lime but have little saturation. The initial production varied from 100 to 25,000 bbl. per day, depending perhaps to some extent on the structural location but chiefly on the porosity of the pay. The initial gas-oil ratio varied from 325 to 16,000 cu. ft. per barrel. In wells where the top of the White lime was found below 350 ft. below sea level (Fig. 1)) the gas-oil ratio was usually less than 1500 cu. ft. per barrel, while in wells higher than 350 ft. below sea level, the ratio was usually above 2000 cu. ft. per barrel. The water table has been determined at about 620 ft. below sea level, by three wells on the west side of the field. With few exceptions, the wells have been completed with 7-in. casing cemented

Jan 1, 1932

By William Marsh Baldwin

[Two of the most useful and important equations available to the metallurgist for the study of plastic deformation of metals are the Huber-von Mises-Hencky1-3 and the St. Venant7-10 equations. HUBER-VON MISES-HENCKY EQUATION The Huber-von Mises-Hencky equation answers the question: When does plastic flow occur in metal that is subjected to a multi-axial stress? It occurs, according to this equation, when the three principal stresses,? al, a2, and a3 satisfy the equation: (s1 - s2)2 + (s 2 - s 3)2 + (s 1 ? s3)2 = 2K2 [I] Here K is the yield strength of the material as determined in an ordinary tensile test. If the quantities a1, a2, and a3 are assigned to the coordinates of a Cartesian three-dimensional system, this expression describes a cylinder whose axis of symmetry is inclined at equal angles to the three coordinate axes4,5 (Fig. I). The radius of this cylinder is v2/3K. For the purpose of simplicity, it is sometimes advantageous to ascribe the values s 1/K = si, s 2/K = s2, s 2/K = s3 to the three coordinate axes instead of the principal stress alone. In this case, Eq. I becomes (s1 - S2)2 + (S2 - S3)2 + (Sl - S3)2 = 2 [2] and the radius of the cylinder becomes 2/3v. In the latter method of representation, a point lying inside the cylinder indicates that the metal will react elastically, whereas a point lying on the cylindrical surface indicates that the metal will behave plastically. Some of the geometric features of this cylinder are worthy of study. Let us inquire first as to what interpretation may be placed upon what we will choose to call the "circles of latitude" of the cylinder (L in Fig. I) and the "meridians" of the cylinder (M in Fig. I). Circles of Latitude Circles of latitude are formed by allowing a plane, passing perpendicular to the cylinder axis, to intersect with the cylinder. Any point, P, on this circle is presumed to have the coordinates s1, s2, and s3. The coordinates of the point resulting from the intersection of the plane and the cylinder axis will be a, a, and a (since the cylinder axis is equally inclined to the three coordi¬nate axes). Let us now pass a line through the point on the circle and the point on the axis.]

Jan 1, 1946

By J. R. Long, T. R. Graham, R. S. Dean

ALTHOUGH considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to 11 pct aluminum, with some incidental information on the single-phase alpha solid solution alloys. Strauss1 gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper5 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50° temperature levels from 400° to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solubility of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 1300°F and higher,

Jan 1, 1947

By N. J. Grant, D. S. Bloom

THE development of high temperature, high stress alloys had proceeded with such rapidity during the war, and for a short time afterward, that our knowledge of the constitution of the alloys had become seriously inadequate. To interpret correctly alloy behavior it is not only necessary to recognize the phases present, but also to know the properties of the phases under all varieties of conditions and treatments. Chromium in these high temperature alloys holds the unique distinction of being the only one element which must be present when an oxidizing or generally corrosive atmosphere is present and when a long life is desired in service. Carbon and nitrogen must also be considered where chromium is present. Carbon is always present, either as an impurity in the raw alloying elements, or as a deliberate addition agent to increase the strength. Nitrogen is generally picked up from the atmosphere during melting or may be added as an alloying element. The effect of nitrogen additions is not too dissimilar to that of carbon additions. As such, chromium carbides and nitrides become of great interest since they are present in a very large number of alloys, including alloy steels, stainless steels, super alloys, and the like. In the chromium-carbon system there are three accepted, carbides: Cr,C, Cr7C8, and Cr3C2. The existence of one more carbide, a still higher carbon form CrC, has been advanced. The phase diagrams of chromium and carbon as published by Friemann and Sauerwald² and by Tofaute, Kuttner and But- tinghaus³ -do not extend beyond the carbide Cr3C2, which contains 13.3 pct carbon; but Hatsuta has extended the diagram up to 20 pct carbon, and in doing so hypothesized, with the use of some questionable experimental results, the compound CrC. This carbide would contain 18.75 pct carbon, 81.25 pct chromium, by weight. It is further known that as the chromium carbides increase in carbon the acid resistance increases but the oxidation resistance decreases4,5 This is of great importance in high temperature alloys where time-temperature stability, as well as oxidation resistance, is of prime importance. The possible existence of a carbide of the formula CrC thus becomes of prime importance and it was considered important to recheck the chromium-carbon binary constitutional diagram for such a compound. In view of the wide spread of values listed for the melting point of chromium (1500° to 1850°C) and 1930°C8, it was considered .that the liquidus temperatures might well be redetermined more ac-

Jan 1, 1951

By Carl F. Floe, Michael B. Bever

TRE solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to 1300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. REVIEW OF PREVIOUS WORK The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available. According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar6 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwas3é reported large hydrogen solubility values for several compositions of copper- tin alloys, which appear to be in error.

Jan 1, 1944

By E. M. Cox, T. Rosenqvist

IN a recent investigation, carried out at the Institute for the Study of Metals, the affinity of sul-phur for iron, copper, and manganese was studied over the temperature range 700" to 1300°C.' It was found that copper exhibits a rather high affinity for sulphur, especially at higher temperatures; and attention was called to the possibility that copper when present together with sulphur in liquid steel would tend to lower the chemical activity of sulphur and thus interfere with the desulphurization process. It was clear, however, that the data for the equilibrium between pure copper and pure copper sulphide (Cu2S) could not give any quantitative information about the effect of copper when dissolved in liquid steel. The present work is concerned with the activity of sulphur in the diluted range of the binary iron-sulphur system, and with the influence of small amounts of copper on this sulphur activity. This investigation is in principle based on the same method previously described for the binary metal-sulphur studies;1,2 namely, reaction with hydrogen to form hydrogen sulphide. The equilibrium ratio PH2s/Ph2 in the equilibrium gas mixture is, for a given temperature, directly proportional to the sulphur activity. The activity of sulphur in liquid iron has previously been studied by Chipman and Ta Li,3 White and Skelly,4 and recently by Sherman, Elvander, and Chipman.5 Morris and Williams6 have studied the effect of added silicon, and Kitchener, Bockris and Liberman,7 and recently Morris and Buehl,8 the effect of added carbon on the sulphur activity. In present day steelmaking processes the steel bath contains between 0.01 and 0.1 pct sulphur, and the copper content may be as high as 0.5 pct. The equi-librium gas ratio (H2S/H2) would, for such a low-sulphur content, be too low to be measured with the experimental technique we use. It has been shown by previous investigators that the H2S/H2 ratio is closely proportional to the sulphur content up to about 1 pct sulphur. The sulphur activity at very low-sulphur content can therefore be calculated by linear interpolation between 0 and 1 pct sulphur. In order to show the general trend with increasing sulphur content, the present work has been carried out to about 3.5 pct sulphur. As the effect of copper was assumed to be more a function of the Cu/S ratio than of the absolute copper content, the runs with copper were made for certain constant values for this ratio.

Jan 1, 1951

By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8,9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation. was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, ½ in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6,9 The measure of internal friction adopted here, 1/Q, is (1/p) X the logarithmic decrement, a measure used by some writers, and is also (1/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the funda¬mental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. 1, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of l00 during the next 100° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e~H/RT [I]

Jan 1, 1942

By F. M. Lewis, J. F. Meyers

This second progress report of grinding presents comments regarding ball consumption and data pertaining to the hydroscillator, which is closed circuited with the tricone mill. A study and postulate of how balls function is presented. The paper summarizes cost reduction obtained by the method of "grinding for the tail race" rather than for "mesh tons." AT the Regional meeting in Columbus, Ohio, in September 1949, the authors presented a progress report of the first year's operation with a Hardinge tricone mill in closed circuit with a Dorr hydroscillator. The present report covers our findings on this grinding circuit to January, 1950. In order to clarify our position, the authors wish to state that no invention or discovery is claimed. The Tennessee grinding circuit is simply an engineered arrangement of known equipment arranged to incorporate all of the recognized efficiency factors of comminution as they are known today. As we concluded our first report, it was not clear how effective the Tennessee mode of operation would be on harder ores. The only information we had at that time was that the Bond grindability test at 48-mesh gave 6.04 g of undersize per revolution. A later test on the same sample at 100-mesh reduced this to 2.04 g, which is definitely in the harder ore class, and which makes the reported 8.80 kw-hr per ton of —200-mesh produced a very creditable figure. Hydroscillator Operation The machine as now developed has proved dependable and easy to operate. It starts easily under full load and responds quickly to operating adjustments. The hydraulic holes in the oscillating plate do not plug when shut down under full load. Absolutely clean hydraulic water is essential. An Elliott water screen or similar device should be an essential part of the machine to keep all scale and trash of all kinds from the hydraulic compartment. The shift operators have expressed approval of the machine. In table I we show a typical screen analysis of the hydroscillator rake sand as compared to conventional classifier rake sand on our ore. We have previously reported that of the 28.7 pct reduction in power, the hydroscillator contributed 6 pct, on a —200-mesh basis. This is a conservative figure. Some of our test runs indicated that the saving was as high as 10 pct. Laboratory studies by the Dorr Co. engineers indicate that still greater efficiency is possible. Nevertheless, the 10-ft plate is overflowing 2100 tons per day at 3 to 4 pct + 65-mesh, which is a very creditable performance by

Jan 1, 1951

By O. F. Thornton, D. L. Marshall

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By D. L. Marshall, O. F. Thornton

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By K. L. Clark, Nicholas Kowall

MAXIMUM furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. WORK OF OTHER INVESTIGATORS In 1938, Burns, Moore and Archer published a curve7 that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the range found in constructional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only 0.20 per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E. 43xx steels. His procedure consisted of chill-casting a test bar that was large enough to give a surface that could be prepared for Brinell indentations. The test piece was quenched immediately after solidification was complete and hardness readings were taken, so that the carbon content could be read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. EXPERIMENTAL WORK Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944