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By C. G. Dunn, P. K. Koh

TWO recent review papers have considered the origin of primary and secondary recrystalliza-tion textures from the point of view of oriented nucleation and oriented growth theories."' Both theories require nuclei for primary recrystallization but provide no unequivocal answer to the question of what nuclei are. The answer to the same question regarding secondary recrystallization, however, often is that nuclei are certain primary recrystallization grains or primaries. The two theories differ, however, in specifying what the certain primaries are. In support of the oriented growth theory Beck and Hua originally stated "It may be assumed that in a re-crystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as nuclei for the coarse grains, provided that conditions are favorable for their growth." In commenting on this statement one would say that there are two restricting conditions: namely, that 1) the certain primaries (nuclei) are large enough to grow, and 2) their boundaries have high mobility. More recently Beck2 has con-

Jan 1, 1958

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies. Theoretical Considerations: Most existing relationships between energy and size reduction of a brittle solid stem from a single, simple, empirical proposition.&apos; Although this proposition can be demonstrated by observation and experiment, no theoretical derivation is yet possible. Mathematically, the proposition may be stated as follows: dE = -Cdx/xn [1] where dE = infinitesimal energy change, C = a constant, dx = infinitesimal size change, x = object size, and n = a constant. Eq. 1 states that the energy required to make a small change in the size of an object is proportional to the size change and inversely proportional to the object size to some power n. No stipulations are placed on the exponent n in either magnitude or sign. In 1867 Rittinger2 postulated that the energy required for size reduction of a solid would be proportional to the new surface area created during the size reduction. As far as can be determined there is as yet no physical basis for Rittinger&apos;s hypothesis. Rittinger&apos;s hypothesis can be stated mathematically as follows: E, = K(oa-a-0 . [2] Er = energy input per unit volume, K = a constant, <ti = initial specific surface, and o2 = final specific surface. In the size reduction of particles of size x, to particles of another smaller size, x2, Eq. 2 becomes the well known relation: ET = K&apos; {l/x2-l/xx) [3] where K&apos; is a constant. Eq. 3 may be arrived at from the proposition given in Eq. 1 by integrating and by assigning a value of 2 to the exponent n. J dE = J - C dx/x2 E = Kt (1x - 1x) where K&apos; = C. In 1885 Kick3 proposed the theory that equivalent amounts of energy should result in equivalent geometrical changes in the sizes of the pieces of a solid. For example, if one unit of energy reduced a number of equal-sized particles to particles of one half the size, then the same amount of energy applied to the particles resulting from the first test should result again in a size reduction of one half or a final size one quarter the original size. The Kick concept may be expressed as follows: Ek = K" log x1/x2 [41 K" = a constant and E, = energy per unit volume. The expression for Kick&apos;s law may be arrived at by again integrating Eq. 1 and in this case assigning a value of 1 to the exponent n. dE= J - C dx/x Eh = - C In {x/x2) = K" log (x,/x,) where K" = 2.3 C. Application of Kick&apos;s and Rittinger&apos;s laws to comminution has met with varied success. Gross and Zimmerley4 and Piret5 have shown that Rittinger&apos;s equation applies under certain conditions of experimentation. Walker and Shaw6 express the belief that in metal turning and shaping and in grinding of both metals and minerals the production of very fine particles (less than lP) follows Kick&apos;s hypothesis, whereas Rittinger&apos;s concept is valid for the size reduction of coarse particles. For the practical case of crushing and grinding, however, neither of the above hypotheses has received general acceptance. Bond&apos; has lately proposed that since neither Kick&apos;s nor Rittinger&apos;s hypotheses seem correct for plant design work, an energy-size reduction relationship somewhere between the two would be more applicable. The fundamental statement of Bond&apos;s work

Jan 1, 1958

By C. D. Cochran, F. H. Deily, M. M. White, Victor Horner

A laboratory study of the effects of physical and easily measured rheological properties upon dynamic filtration was carried out. The purpose was to determine the factors affecting dynamic filtration and thus learn how to control this important property. The recommended procedure for determining the amount of fluid loss prescribed by API Code RP 29 "Field Procedure for Testing Drilling Fluids,"&apos; is very useful for mud conditioning purposes, but inadequate for comparing filtration properties of different muds under dynamic conditions. Where dynamic filtration control becomes important for purposes such as logging and coring, other means of evaluating filtration properties are needed. A special device and testing technique were developed to provide reliable data on filtration characteristics of different fluids under dynamic conditions. Liquid saturated rock samples were drilled with a microbit, and the amount of connate liquid displaced by the fluid being investigated was measured. The empirical testing procedure was considered reliable. A large number of laboratory-prepared and field-mixed dritling fluids with a wide range of physical properties were studied. These properties included: (I) shape of consistency curves, (2) apparent viscosity, (3) plastic viscosity, (4) yield value, (5) density, and (6) API filter loss. Test results indicate that very little, if any, trend could be established between changes in these fluid properties and dynamic filtration. INTRODUCTION During the process of drilling, excessive loss of liquid from the mud to the formation is undesirable for many reasons. Filtration can reduce production-zone permeability, cause sloughing of formations, affect electric log curves, and render the fluid data obtained from cores unreliable. Thus, it is very important that we gain a knowledge of the factors that control filtration. It is generally agreed that in any type of filtration (static, dynamic, or combinations thereof), the mechanics of filtering depend in great part upon the composition of the fluid. Moreover, it is also true that the physical and rheological properties are influenced by the composition of the fluid. Indirectly, then, it was hypothesized that a relationship existed between dynamic filtration and physical-rheological properties, two effects of a common cause—fluid composition. This paper discusses an attempt to relate filtration-while-drilling to physical and easily measured rheological properties. It is believed that the results of this study may prove useful to others in the industry who are working on the problem of understanding filtration. The industry accepted practice for determining fluid loss from drilling mud is described in API Code RP 29. The practice is to measure the amount of filtrate that passes during a given interval of time from a quiescent drilling fluid under applied pressure through a piece of filter paper. This is primarily a test of static filtration properties. Other investigators have studied filtration under dynamic conditions. Williams5 and Pro-kop5 studied radial filtration and filter-cake buildup by circulating fluid through a porous cylinder under conditions similar to actual mud flow. Nowak,4 Krueger,3,4 and Vogel3 studied the effect of filtration upon permeability by flowing mud past the face of rock Samples. In their tests, the bit action was simulated by mechanical scrapers that kept the filter cake from building up. Ferguson and Klotz2 studied three types of filtration: static, dynamic, and beneath-the-bit. They investigated each type separately, using a model well in which bottom-hole hydraulics and mechanics were closely approximated.

Jan 1, 1958

Jan 1, 1958

By M. E. Nicholson

IT has been suggested by a number of investigators, I including Hume-Rothery and Raynor,&apos; that certain intermediate phases in metal systems take on interstitial crystal structures because of an appropriate ratio of radii of the two atoms. If the size factor is an important parameter in determining whether or not an intermediate phase will have an interstitial structure, then it would appear reasonable that the relative sizes of interstitial atoms should have a direct relation to their solubilities in interstitial compounds. It was on such a basis that Petch,&apos; in his discussion of the cementite structure, concluded that nitrogen is the only possible element which could replace carbon. Recent X-ray studies by Jacka indicate that the solid solubility of nitrogen in cementite is negligible. If this is the case, then on the basis of size factor it would not be expected that any element can replace carbon in FeaC, since according to Schwarzkopf and Kieffer4 the covalent atomic radii of nitrogen, carbon, and boron are 0.71, 0.76, and 0.87A, respectively. Nevertheless, Vogel and Tammann in 1922 indicated that a quasi-binary relation exists between the interstitial compounds FeaC and Fe2B and that the solid solubility of boron in FeaC at approximately 1150°C is 1.4 pct B by weight. Because of the apparent disagreement between theory and experiment, the solid solubility of boron in FeaC has been reinvestigated. In addition, the influence of boron on the saturation magnetic moment (per gram) and Curie temperature of cementite was determined. Experimental Procedure A series of Fe-B-C alloys which varied in boron content from 0 to 5.4 wt pct B were prepared by arc melting a 50-g ingot using carbonyl iron, Ache-son AUC graphite, and Cooper grade A boron for starting materials. The composition of these alloys is listed in Table I and shown graphically in Fig. 1. The samples represented by the solid circles were used for X-ray analysis and Curie temperature measurements; by the squares, samples used for quantitative metallography; and by the triangles, samples used for saturation magnetic moment measurements and Curie temperature measurements. After arc melting and subsequent quenching from 1000°C, so that all phases in the resulting microstructure were brittle, one half of the 50-g ingots were pulverized until a powder was obtained which was less than 100 mesh. These powders were then homogenized in evacuated Vycor capsules at 1000°C for 24 hr and water quenched. Although the homogenized powder had sintered somewhat, it was suitable for saturation magnetic moment and Curie temperature determinations, for which the 60 to 100-mesh fraction of the powder was used. For X-ray analysis the homogenized powder was crushed again until a 300-mesh powder was obtained. After crushing, the powder was mixed with Alundum of approximately the same grit size to prevent sinter-

Jan 1, 1958

By G. Sachs, B. B. Muvdi, E. P. Klier

IT is now generally i-ecognized that hydrogen is responsible for delayed failures encountered in high-strength steels,&apos;.&apos; and the hydrogen responsible for the embrittlement is introduced in the cathodic cleaning and plating operations to which these steels are subjected. Numerous test methods have been used in the past for the determination of brittleness in embrittled parts, namely tension? = notch-tension:&apos; impact,&apos; stress-rupture: a and bend tests.% * Several of these tests are not suitable for routine testing.

Jan 1, 1958

By Eric R. Morgan, J. C. Shyne

STRAIN aging is the name given to time-dependent changes which occur in the properties of cold-worked metals and alloys during storage. These changes are best observed through a study of mechanical properties, as illustrated in Fig. I for low-carbon steel. The effects of strain aging are usually regarded as being detrimental, particularly in deep-drawing steels. For example, an increase in yield strength and loss in ductility lead to buckling and tearing during drawing. At the same time the return of the yield point results in the formation of Luders bands or stretcher strains during the pressing operation. As a result of these effects many attempts have been made to eliminate strain aging from low-carbon steel. The problem still remains, however, because all known methods of preventing strain aging result in a more costly steel. The present work is an assessment of the situation in terms of theoretical, practical, and economic factors and suggests a new solution to the problem. Previous Work According to the Cottrell theory,&apos; strain aging in a-iron may be regarded as the migration of interstitial atoms to free dislocations and the anchoring of dislocations by the resulting atmospheres. It may be concluded that the important factors which will govern the degree of strain aging are the diffusivity, the effective amount of interstitial element in solution, and the time of aging. The diffusivities and effective amounts of carbon and nitrogen in solution in low-carbon rimming steel are such that significant aging occurs in a few hours&apos; storage at room temperature. Strain aging in deep-drawing steels cannot be controlled by controlling the time of aging because in commercial practice this is determined by economic factors concerned with inventories and may be several weeks. The diffusivity of nitrogen is twice that of carbon at room temperature but the diffusivities can be controlled by controlling the storage temperature. The retardation produced by only a 25 °C drop in temperature is significant but the cold storage of large steel inventories is an impractical solution to Table I. Analysis of Base Materials Alloy Pet C Yet 0 Pet N Vac 0.0037 0.052 0.0003 H 0.0044 0.013 0.0008 C 0.06 0.0014 0.0001 the problem. By far the most simple and effective ways to control strain aging are through control of the amount of carbon and nitrogen in solution. This may be effected through alloying, controlled precipitation, or by eliminating the carbon and nitrogen. Consider first the control of the amount of carbon in solution. The simplest approach would be alloy -ing in which strong carbide-forming elements are added. Examples of this approach are the additions of titanium&apos; and niobium9 0 steel. These elements also combine with nitrogen and oxygen and when added in sufficient quantity result in a completely killed and non-aging steel. They are, however, impractical additions because they result in a costly steel. Carbon and nitrogen are often removed from iron on a laboratory scale by annealing in wet hydrogen, but because of cost this process has never been adopted on a commercial scale. In practice the amount of carbon in solution is controlled by the rate of cooling from the annealing temperature (710°C or 1310°F). In commercial box

Jan 1, 1958

By C. L. Rabe

The Muddy and Dakota sands, more commonly known as the "D" and "J" sands, respectively, of the Denver-Julesburg Basin are correlative over a large area. It is reasonable to believe, therefore, that depositional environment throughout the Basin was comparable. Local variations in sand development do occur, however, and productivity is often governed by permeability as well as structural position. Experience indicates permeability is commonly a function of cementing material. While cases of siliceous or calcareous cementing have been observed, the bonding material is, for the most part, clay. Under the latter circumstance, clay should bear some relation to permeability. Similarly, gamma radiation should bear some relation to the amount of clay. This study was undertaken to determine if a cross relation exists between gamma radiation and permeability. RESULTS OF INVESTIGATION A qualitative relation does exist between gamma radiation and permeability for clay-bonded Muddy and Dakota sands of the Denver-Julesburg Basin. This is illustrated graphically by Fig. 1, which shows corrected gamma ray deflection vs permeability for five wells over an area approximately 50 miles long and 8 miles wide. The "corrected" gamma ray deflection cannot be read directly from the gamma ray survey in all cases. It became apparent early in the investigation that methods would have to be developed for converting all gamma ray surveys to a common deflection scale and to correct for thin bed effects. COMMON SCALE DEFLECTION Because all logs are not recorded in the same calibration units or at the same sensitivity, it was felt they could be most readily converted to a common scale by measurement of deflection in inches from zero. Initially, four wells in the Jacinto field of Nebraska were carefully correlated, and selected intervals were planimetered to obtain average deflections. Average deflections of planimetered intervals from three of the wells were plotted vs those of the fourth well which was to be used as a common reference. The plots are shown in Fig. 2. While results obtained by this method in the Jacinto field were relatively good, the planimetered intervals were not easily correlated with logs from other fields. Furthermore, the planimetric method is laborious and not readily adapted to routine operations. Deflection of the "Bentonite marker" was found to

Jan 1, 1958

By John P. Dolan, Charles A. Einarsen, GiIman A. Hill

his paper discusses how the following formation characteristics can be determined mathematically from drill-stem test pressure charts: true formation pressures, effective permeability of the entire section tested, well productivities, wellbore damage, and possible detection of barriers (faults, pinchouts, etc.). This paper also presents a practical method for im-mediate determination of eflective permeability and well-bore damage from successful double shut-in pressure tests. A list of recommendations for improving the reliability of drill-stem rest pressures is also presented. INTRODUCTION A drill-stem test is a temporary completion designed to sample the formation fluid and to establish the possibility of commercial production. Early pressure recording devices were used merely to verify proper operation of the testing tool. Until recently the accuracy of the pressure gauges has been insufficient for any reliable quantitative use of the recorded pressures. In view of the need for more reliable formation evaluation and as a result of the recent interest in exploration work employing the concept of hydrodynamic en-trapment,1,2,3,4 better pressure recording gauges are now in use. These devices can record pressure within 1 per cent above 1,000 psig and can detect differential pressures as low as 1/2 psig. In addition to formation pressure, several other reservoir characteristics can be determined from DST charts; namely, well productivity, formation permeability, wellbore damage, and the possible existence of bar- riers (faults, pinchouts, changes in permeability, etc.). This paper presents a practical method to interpret DST pressure charts for formation pressures and many other reservoir properties, a method that has been developed in analyzing approximately 4,000 DST charts during the last five years. The techniques used are a composite of published articles on drill-stem testing5,6, together with well-known pressure build-up analysis methods. THEORY It has been shown7,8 that the following equation may be used for analysis of pressure build-up curves: Po - Pw = 162.6 qu/kh log ( to + ?/?) .....(1) When this equation is applied to the curves obtained in drill-stem testing, the assumptions and boundary con-ditions are more nearly realized than in conventional flow and build-up tests on producing wells. Zak and Griffen9 have recently discussed in detail the use of this equation in analyzing DST charts. One of the problems with DST curves is the lack of reservoir data for precise analysis. Therefore, it is necessary to develop empirical rules and field methods for analyzing DST charts in quantity. For this reason, the empirical methods presented in this paper have been developed, and their derivation is found in Appendices A and B. METHOD USED FOR ACCURATE READING OF DRILL-STEM TEST CHARTS In order to apply the pressure build-up theory to DST charts, it is necessary to obtain a digitized expression for the pressure and time data recorded by the pressure gauge. These data may be either provided by the service company or interpolated by projecting a

Jan 1, 1958

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.&apos; However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams&apos; and Wright4 also have found evidence of this body-centered-cubic constituent. William&apos;s hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher&apos;s body-centered-cubic constituent is the embrittling phase. According to Preston&apos;s data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher&apos;s constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

Jan 1, 1958

By J. H. Frye, J. L. Scott, J. W. Woods

THERE are at least two effects of temperature on the stress required to produce plastic flow. 1) Metals plastically strained for the same amount at different temperatures possess different stress-strain curves and different internal structures (e.g., nature and density of imperfections). 2) There is both experimental and theoretical evidence that the stress necessary to produce plastic flow may vary with temperature even though the internal structure remains constant.1-5 Much of the data in the literature is difficult to interpret because these two effects are simultaneously present. In the work reported here, they are considered separately. Standard 0.505 in. tensile specimens were prepared from high-purity Mond nickel and OFHC copper. Nickel specimens were annealed in hydrogen at 1150°C for 30 min and furnace cooled. This produced an average grain diameter of 1.4 mm. Copper specimens were annealed in vacuum at 525°C for 6 hr and furnace cooled. This produced an average grain diameter of 0.11 mm. Nickel tensile specimens were prestrained in tension at 500°K, whereas copper tensile specimens were prestrained in tension at room temperature. All specimens were cooled to 74°K and heated to room temperature. After these treatments all of the tensile specimens of a given set possessed identical structures. All specimens were returned to the tensile machine and tested at various temperatures and constant cross-head speed. Many of the tensile curves showed well defined yields but, in order to minimize personal judgment, the yield was always chosen as the stress corresponding to 0.2 pct plastic deformation. Results are summarized in the graph of yield vs temperature of test, Fig. 1. All of the specimens corresponding to any one line have had identical treatments and, therefore, have identical internal structures. Thus, each line gives the relation between yield stress and temperature for one constant internal structure. The lowest line, which is for annealed nickel, shows no measurable variation of yield with temperature. This is similar to Blewitt&apos;s6 results on copper single crystals, but a variation in yield with temperature was found by Andrade and Henderson&apos; in single crystals of nickel, and by Car-recker and Hibbard8 in annealed polycrystalline copper. The three other lines, which are for prestrained materials, show that there is a linear relation between yield stress and temperature when the internal structure remains constant. Such a relation might be expected from a rate equation such as that of Kauzmannl on the assump- tion that the activation energy is either independent of or linear with temperature. These results would also be expected if the shear moduli of copper and nickel are linear functions of temperature for, as Cottrell and Stokes have pointed out," in all dislocation theories of strength the flow stress appears proportional to the shear modulus of the material. In copper and nickel, since the modulus of elasticity decreases roughly linearly with increase in temperature," it is probable that the modulus of shear also decreases approximately linearly with increasing temperature. A detailed discussion of the effect of these and other factors on the temperature dependence of flow stress in face-centered-cubic metals has recently been given by Seeger.4

Jan 1, 1958

By F. W. Luersson

High carbon, low phosphorus steel can now be made from pig iron containing 0.7 pct P or more, in a commercial sized open hearth furnace. No external heat is required for refining, and steel produced is identical with basic open hearth steel. THE classical Thomas process, which requires liquid pig iron containing over 11/2 pct P, yields a product relatively high in phosphorzs and nitrogen. Unless large quantities of recarburizers are added to the refined steel, the product is low in carbon content. Thus, the Thomas process is not well suited to American raw materials, and its product is often not acceptable according to the standards set by American industry. The shortcomings of the Thomas process have long been recognized; with the advent of low cost oxygen, studies were initiated to develop pneumatic processes which would conceivably overcome the inherent objections to Thomas steelmaking. Several such modified basic pneumatic processes have been tested experimentally in commercial trials during the past decade. Probably the most widely publicized of these developments has been the oxygen converter process as practiced in Austrial,2 and in Canada.8 n this process, oxygen is substituted for air and introduced above the liquid bath in order to increase the heat available to the metallurgical system. This avoids the need for high phosphorus raw materials and gives a product low in nitrogen. In this process, the phosphorus content in the final product depends, to a considerable extent, on the total amount of that element in the burden. The rotary furnace4 which is now in commercial operation at Domnarvet Steelworks, Sweden, is producing low phosphorus steel from iron containing 1.8 to 2 pct P. One or more early slags are removed and by this means high carbon steels of open hearth quality can be produced. At this stage of development there is some question as to the applicability of the rotary process to large heats. Another development has been the use of oxygen in combination with either steam6 or carbon dioxide yn the basic bessemer, thus avoiding the introduction of nitrogen gas into the refining system and giving a product relatively low in nitrogen content. A double slag process has been used in Europe7 in conjunction with a regular Thomas converter, by means of which it is possible to obtain a phosphorus content in the product approaching that obtained in basic open hearth steels. The Turbo-Hearth process:&apos; which uses the side blowing principle so as to produce low nitrogen steel from normal American pig irons, has been developed experimentally in this country. A process fitted to U. S. raw materials All of the preceding processes, with the exception of the rotary furnace, suffer from the common shortcoming that they cannot be adapted to the production of high-carbon, low-phosphorus steels unless large proportions of recarburizers are added. In 1947, a program was initiated by the Inland Steel Company1&apos; to study an oxygen steelmaking process specifically designed to utilize the full range of phosphorus analyses encountered in American pig irons and to give finai products with phosphorus and nitrogen contents comparable to steel produced by the basic open hearth process. Some of the objectives of the proposed process are: 1) the process should be able to accommodate molten pig iron conta;rl;rrg up to 1 pct P., 2) sne process should be subject to close control of carbon analysis, 3) the process should be capable of producing high carbon

Jan 1, 1958

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,&apos; is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors&apos; sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By Nicholas J. Grant, Gordon D. Gemmell

CREEP rupture characteristics of high purity Al-Mg solid solution alloys were studied by Mul-lendore and Grant&apos; to investigate solid solution strengthening of pure aluminum and the accompany- ing effects on deformation and fracture characteristics. This paper presents the results of an extension of that work to A1-Cu and Al-Zn alloys to permit a comparison of the relative effects of the three solute elements on the high temperature strength and on the deformation and fracture characteristics. Experimental Procedure A total of nine alloys was studied. They were all made of ultra high purity aluminum alloyed with high purity copper, zinc and magnesium. The corn-

Jan 1, 1958

By A. M. Gaudin

Activation of sphalerite with silver ions results from the exchange of two Ag ions for one Zn ion in the sphalerite lattice. The exchange is proportional to the logarithm of time and proceeds until either of the reactants is consumed. Sodium cyanide prevents the activation of sphalerite by controlling the ratio [Zn++]/[Ag+]&apos; in solution. If sphalerite has already been activated with excess silver, cyanide ions can deactivate sphalerite provided oxygen is present. SOLUBLE: silver salts are effective activators for flotation of sphalerite with potassium ethyl xan-thate as collector.* Since sphalerite takes up large quantities of silver ions rapidly,2-4 investigation of this system appeared fruitful for studying the mechanism of sphalerite activation and deactivation. Experimental data presented here comprise studies of the mechanism and rates of activation and deactivation of sphalerite with silver and cyanide ions. A 20-lb sample of sphalerite from Ottawa County, Oklahoma, was handpicked, crushed, screened, hy-drosized to produce a 65/100-mesh fraction, and purified by electrostatic separation. The sphalerite was then leached with benzene and absolute ethyl alcohol to remove possible organic contaminants and with 0.1 M NaCN to remove any copper that might have been picked up during screening. The benzene had been specially purified by grinding with fine sphalerite for 12 hr to remove trace impurities that might have had a specific affinity for sphalerite. Ii&apos;inally, the mineral was washed, dried in flowing nitrogen, and stored in large ground-glass stoppered weighing bottles under a small nitrogen pressure. The specific surface of two samples from the 65/100-mesh sphalerite stock, measured by krypton gas adsorption," was 420 cm2 per g. Compared with spheres of the same size and specific gravity, the prepared mineral had five times as much surface. Results of a wet chemical analysis and of a spectro-graphic study are given in Table I. Manganese, nickel, tin, indium, thallium, cobalt, and magnesium were not detected spectrographically. All solutions were preparid by -adding reagent-grade chemicals to conductivitv water. which had been previously saturated with the desired gases. Nitrogen and oxygen were purified, but no attempt was made to purify the laboratory air. Radioanalysis was carried out with prepurified Ag110 tracer obtained from the Oak Ridge National Laboratory. The complete decay scheme for Ae is complex. Its primary emissions are 0.09 and 0.55 mev ß rays and 1.48 mev y raysB and its half-life is believed to be 270 days. In preparation of solutions of AgNO3, the amount of Ag110 added was negligible compared to that of the inert silver. Abstraction of silver from solution by sphalerite was measured after agitation of 1.5 g sphalerite with 20 ml of solution in 50-ml pyrex flasks. All sample preparations were carried out in a dry box so that the proper atmosphere could be maintained. After the mineral had been agitated in the silver nitrate solution, an aliquot of the solution and a sample of the wet mineral were transferred to separate counting vials and weighed. The solid sample was dried and re-weighed and the activity in both vials measured by means of a scintillation counter. With scintillation counting it is possible to count y radiation from the solid and liquid, a distinct advantage over the older ß-ray counting techdiques.4 All measurements of silver activity were made using a sodium-iodide well-type scintillation counter. The amount of zinc in solution was measured colorimet-rically by the monocolor method of Sandell.7 Activation Studies Exchange Between Zinc Ions and Silver Ions During Activation: The increase of Zn++ in solution during activation with Ag+ is shown in Table 11. These data indicate a replacement of one Zn++ by two Ag+. Analysis of a separate two-month agitation test indicated that the replacement of Zn++ by Ag+ was, as expected, in the molar ratio of 2.0.

Jan 1, 1958

By Nicholas J. Grant, Robert F. Wilde

TAYLOR and Floyd&apos;s"" work in establishing phase diagrams based on the elements Ni-Cr-Ti-A1 has led to an understanding of the precipitation hardening mechanism in alloys based on these elements. Nordheim and Grant4 concluded that in simple alloys, and where the aluminum to titanium atomic ratio was such that less than three out of five aluminum atoms were replaced by titanium, the precipitate on aging is the face-centered-cubic Ni 3A 1 phase, called They further found that increasing amounts of hexagonal ? phase, Ni3Ti, precipitated from these alloys when the titanium content exceeded the solid solubility of both matrix and Ni3A1. For alloys of Ni-Cr-Ti-Al, in which the titanium and aluminum contents each ranged from 0 to 4 wt pct, the titanium-rich was superior for strengthening to either pure ?&apos; or 7. It was also noted that the combined titanium plus aluminum content (atomic pct) was a direct measure of the high temperature strength and overaging temperatures for these alloys.4 The present investigation was undertaken to extend existing data on precipitation hardening in the more complex commercial alloys containing higher titanium plus aluminum, and with significant quantities of cobalt, molybdenum, and carbon. Experimental Procedure Reforging of As-Received Bar Stock—The alloys were received as ground, forged bar stock. Chemical analyses and the as-received bar diameters are shown in Table I along with the ASTM grain size after the various treatments. All stock except the Waspaloy was reforged to % in. diam to gain material and to facilitate machining of stress-rupture specimens. Forging was carried out at 2100°F, and discontinued when the bar temperature fell to 1800°F. Heat Treatments—For experixental simplicity it was desirable to heat treat all of the alloys at, the

Jan 1, 1958

By R. M. Goldhoff, J. W. Spretnak

IN connection with establishing the mechanism by which boron enhances the hardenability of heat treatable steels, this research work has been undertaken. Spretnak and Speiser1,2 indicated the need for studying high temperature effects in boron steels and, chief among these, the possible nonhomogeneous distribution of boron in iron grains. The occurrence of this effect may be of significance in explaining the mechanism of enhancement of hardenability by boron as well as in explaining some of the observed characteristics of boron steel behavior. Primarily, then, this work was undertaken a) to establish whether or not boron is adsorbed in ? solid solutions, b) to determine the nature of any such adsorption effects, i.e., whether it is positive or negative as well as its temperature coefficient, and c) to establish the magnitude of any such effect. While past literature on this specific subject is rather sparse, a number of authors have postulated that the observed temporary loss of hardenability as well as the occurrence of the characteristic boron constituent in these steels is due to the nonuniform distribution of boron in austenite.3-0 Experimental Techniques Attempts to obtain direct evidence of grain boundary effects in boron steels have been unsuccessful, both by using the technique of Chalmers&apos; in which small concentrations of solute made radioactive by irradiation are detected by autoradiographic means, and by means of studying cleavage fractures with the electron microscope.8 The present study attempts the design of experiments to measure the effect of boron on properties which might be subject to variation because of grain boundary effects. A study of the theoretical aspects of grain growth indicates that such studies may be pertinent. Another valid type of experiment involves the measurement in polycrystalline materials of properties whose values depend on the bulk of the grain, being negligibly influenced by grain boundaries. One such property is the lattice parameter measured by X-ray diffraction. The value of the lattice parameter reflects the average conditions which obtain over a relatively large number of atoms in a fixed crystalline lattice, and is therefore mainly dependent on bulk grain material. Measurement of lattice parameter variation over the austenite range of temperature in iron with and without boron should give evidence of concentration variations in the bulk grain material if adsorption effects are significant. Finally, use is made of the Grange and Garvey3 metallographic test for boron in which a characteristic boron constituent can be developed in austenite grain boundaries. The very occurrence of this phenomenon suggests grain boundary enrichment of boron and a study of the occurrence of this constituent and its varation with austenitizing temperature should help to detect grain boundary effects. Materials One lb ingots of pure iron, an Fe-B alloy, an Fe-C alloy, and an Fe-C-B alloy were prepared. The melting technique included an initial melting of electrolytic iron under vacuum followed by remelting under hydrogen and, finally, by melting under argon with the addition of alloying elements. Each ingot was surface machined between meltings. A quantitative spectrographic analysis was obtained on the pure ingot and, in addition, oxygen, nitrogen, and carbon were determined by the vacuum fusion method. The results of these analyses are given in Table I. Semiquantitative spectrographic analyses were performed on the alloy ingots, while quantitative determinations of the alloy additions were obtained. These analyses are shown in Table 11. The cast ingots were subjected to the following sequence of fabrication treatments: forging to 5/8 in. bars, swaging to 0.300 in. rounds, drawing to 0.025 and 0.010 in. wire. Portions of each ingot were retained in the swaged condition for experimental use. For certain portions of the work typical commercial steels were used. These materials were supplied by the Republic Steel Corp., Canton, Ohio, and correspond to AISI 8640 and AISI 86B40 compositions.

Jan 1, 1958

By J. E. Chappelear

We are concerned with the problem of calculating the forces produced by passing waves on a submerged object (in particular a drilling barge) located on the ocean floor. We employ the linearized theory of waves (the Airy1 theory), since solutions are generally more easily obtained in such a theory. It will be indicated how an approximate solution to the problem can be obtained for waves of finite height by use of a linear combination of Airy waves. We shall assume the submerged object has an infinite length, thus neglecting diffraction and making the problem two-dimensional. We find that there is not a considerable difference between our solution and the usual engineering solution. The force, as a function of time, is plotted in Figs. 4 and 5, together with the usual solution for easy comparison. So far, no experiments have been found to compare with the results. As will be shown, the calculations can be extended to waves of finite height (Stokes2-Struik3 waves) in an approximate fashion. This can be done by calculating the force produced by each Fourier component of the wave, separately, and omitting the coupling between the various harmonics produced by Bernoulli&apos;s theorem. The problem and its boundary conditions will be briefly stated. We seek a function, +, the velocity potential, which is harmonic, ?2?=0...........(1) and which satisfies the boundary conditions ??/?n =0 .......(2) (the normal derivative of + is zero) on the ocean floor and the sides of the barge, and s??/?y = ?..........(3) on the ocean surface, where s = g/w2........(4) The physical reasons for these choices and an interpretation of ? are given by Lamb.&apos; As previously stated, we assume also that the problem is two-dimensional. We set up our coordinates such that x = 0 is the center of the barge and y = 0 is the ocean floor. The coordinates are shown in Fig. 1, together with the location of the barge on the bottom. Our solution may be decomposed into a function which is symmetric about x = 0,?e, and one which is antisymmetric, +,, ? = ? + ?o...........(5) Thus directly above the barge we have as boundary conditions that for x = 0, ?o = 0, ...........(6) and ??e/?x = 0........(7) Now, far from the barge, we have that (for x positive and assuming the waves are incident from the left) ?e ? Ae cosh ky cos k (x + a) , . . . (8) and ?e ? Ao cosh ky cos k (x + ß) . . . . (9) where + means ". .. approaches ... for x large." Let us put Ae, Ao, and k equal to one, and remember that, in accordance with the derivation of Eq. 3, a sinusoidal time factor is to be supplied. Then we may rewrite Eq. 8 for ?e, and we find that

Jan 1, 1958

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors&apos; previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958