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By P. E. Baker

The commercial neutron-gamma log measures the intensity of gamma-rays produced by the interaction of neutrons with nuclei in the formation and in the bore hole. This measurement gives information concerning the distribution of neutrons around the neutron source, and in particular gives information on porosity or fluid content. Another type of information is contained in the frequency or energy spectrum of the neutron capture gamma-rays. The capture gamma-rays of each element, in fact of each isotope, have only those energies characteristic of that isotope.'" The neutron capture gamma-ray spectrum, if obtainable, would permit the identification of the elements producing the spectrum. Such information would have considerable value in oilfield exploration work if it could be applied practically in well logging. Experiments have been carried out at the La Habra Laboratory of California Research Cop. to determine the feasibility of a method of well logging in which neutron capture gamma-ray spectra are measured down hole. In these experiments, spectra were obtained for artificial formations under simulated borehole conditions, using actual borehole geometry. This paper will describe the experimental apparatus and methods and will present the spectrum curves for several formations. THEORY Basic Formulas The neutron capture cross section of an element is a measure of its tendency to capture neutrons. The macroscopic cross section, or cross section per cubic centimeter, of a material composed of several elements is the sum of the cross sections of the nuclei making up 1 cc of the material. This is expressed in the equation SB = Sn1s2, ..........(1) where SB is the macroscopic cross section, s, is the cross section of a nucleus of type i, and ni is the number of nuclei of type i/cu cm. If N is the number of neutrons absorbed per second by the composite material, then the number captured by element j is Ni = N nisi/SB = N nisi/Si ni si ......(2) When the nucleus captures a neutron, a new nucleus is formed, which is usually in an excited state and falls to its ground or unexcited state by emitting one or more gamma-ray quanta.* The emission spectrum has been measured for many elements (see Table 1). The intensity of gamma-rays produced by an element is proportional to the number of neutrons captured per unit time by the element, which in turn depends on the capture cross section of that element and the capture cross sections of the other elements present which are competing with the first element for thermal neutrons. In a small sample of material the number of neutrons, N, captured per second is N = ?SB, ..........(3) where $ is the thermal neutron flux and SB is the macro-scopic cross section defined above. The number of neutrons captured by element j is N1 = ?ni si = N ni si/SB . ......(4) The number of gamma-ray quanta of energy, E, pro-duced per unit time by element, j, is I(E)=Nni si/SB P(E) .......(5) where P(E) is the emission probability of element, j, for this gamma-ray energy. Borehole Effects The capture gamma-ray spectra of many elements have been measured accurately in academic and government laboratories. These measurements are made on small samples, and from these measurements the emission spectra of the elements are obtained.

Jan 1, 1958

This study of the tin-tungsten ore of the Shepherd and Murphy Mine, in central northern Tasmania, was originally undertaken at the request of the Moina Tungsten-Tin Mining Co., N.L., as part of the research programme of the Mineragraphic Investigations Section of the C.S.I.R.O. It is based on the examination of a suite of specimens supplied by the management, supplemented by a more extensive collection and observations made by the author during a short visit to the mine in October, 1956.The Shepherd and Murphy Mine is at Moina, 36 miles S.W. of Devonport and 22 miles from Sheffield, the nearest railway station. It was worked almost· continuously from 1893 to 1919, when a fire destroyed the mill; to that date it had produced concentrates to the value of £141,000. After a long period of idleness, the mine was re-opened by the present company, but it has been announced recently that unfavourable market conditions have again forced closure.GENERAL GEOLOGYThe mine is on a deeply dissected plateau, about 2,500 ft. above sea level; it lies between the Iris and the Forth Rivers, whose valleys are deep gorges cut to about 400 to 600 ft. above sea level. From Moina westwards to the Iris River, a limestone regarded as part of the Gordon River Group, of Ordovician age, conformably overlies a sandstone containing tubicolar casts which are circular in cross section, half an inch in diameter and up to two feet long, and which resemble marine worm burrows (Elliston, 1953).

Jan 1, 1958

By Jack L. Taylor

WITH the exception of the work of Vogel,&apos; and Rolla and Iandelli, very little information has appeared in the literature on titanium binary systems with the rare earth elements. Rare-earth additions to titanium alloys may possibly parallel the beneficial effects on the physical properties of certain steels. Having this in mind, some knowledge of solubility limits and intermediate phases, if any, would be useful. An investigation of the titanium-rich Ti-Ce system was started. Alloy Preparation The iodide titanium from the New Jersey Zinc Co. and the cerium metal from the Institute for Atomic Research Ames Laboratory used in this work were supplied with the typical analysis shown —iodide titanium: 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb; cerium metal: <0.01 pct Fe, <0.03 pct Si, <0.05 pct Ta, <0.02 pct Pr, <0.03 pct Ca, <0.02 pct Mg, with no trace of Nd, La, or Th. The cerium metal, stored in oil, was washed and scraped just before weighing into capped cups machined from iodide titanium. The cold hearth helium-arc furnace described by Schramm et al3 was used for melting. The alloy buttons from the arc-melted cup were cut in two, mounted, and examined. Homogeneous alloys were demounted and rolled to approximately 1/4-in.sq bars. Sections l/8 in. thick were cut from the bar to provide samples. The Ti-Ce alloy buttons analyzed for cerium were of the following composition: 0.19, 0.36, 0.48, 0.61, 1.15, 2.52, 3.06, 3.70, 4.30, 9.20, 14.26, and 18.50 wt pct. Nominal

Jan 1, 1958

By H. A. Koch, R. L. Slobod

This paper discusses a new oil recovery process called the "miscible slug process." This process involves the injection of propane or LPG into the reservoir prior to gas injection. The operating conditions are maintained so that the slug is miscible with both the reservoir oil and the injected gas phase. Thus, a miscible phase displacement is achieved, and high recoveries are obtained from the area of the reservoir contacted. The most striking discovery of the laboratory study which included displacements from cores up to 123 ft in length was that relatively small slugs of LPG are effective over reservoir distances in the miscible displacement of oil. This makes possible the commercial application of the process. The important factors controlling the size of the slug are: (I) reservoir length, (2) reservoir fluid composition, and (3) reservoir pressure at the displacement front. Of lesser importance are the effects of injection rate and porous medium type. Questions which have not been completely answered deal with the effects of gravity and reservoir inhomogeneities on the process. INTRODUCTION One of the major problems facing the oil industry today is recovery of the large fraction of the discovered oil which will remain unrecovered unless some new processes are found. Water flooding has been one successful method used to increase recovery over natural depletion. But even successful water floods may leave 25 to 40 per cent of the pore space filled with residual oil. Recently a process which involves the use of thermal energy has been reported1,&apos;*&apos; which may prove useful in increasing recovery from shallow reservoirs containing highly viscous crudes. This paper deals with a new oil recovery process involving use of miscible phases to displace the oil from the reservoir. Miscible phase displacement oil has been an intriguing idea because the elimination of capillary effects in the reservoir leads to 100 per cent recovery in the areas contacted by the miscible displacing phase. The big deterrent in the past to the practice of miscible phase displacement has been the high cost involved in using large volumes of solvent in the process. The use of high pressure gas to achieve a miscible phase displacement of reservoir oil has been reported4,5 as one economically feasible method. However, this process calls for the maintenance of pressures above 3,000 psi at the dis-placement front. The process described in this paper is not restricted to high reservoir pressures; the only qualification being that the slug of material which is injected into the reservoir must be miscible with both the displaced oil 2nd the displacing phase. Two such cases are the use of an alcohol slug followed by water to achieve a mis-cable water flood, and the use of a low boiling hydrocarbon slug such as propane followed by gas to achieve a miscible gas drive. This paper will deal specifically with the propane dug process. This process will obtain a miscible phase displacement at pressures as low as about 1,200 psi at a reservoir temperature 01 150°F. The process is very simple. The propane displaces oil completely at one front because it is miscible with the oil, and gas displaces the propane completely at a second or trailing front because it is miscible with the propane. A small band of propane should thus remain wedged between the gas and oil phases. This idea has been called the "miscible slug process."6 Unfortunately, the propane slug will become diluted as it flows through the reservoir. This results from a mixing action since the fluids flow through a complex reservoir porous medium rather than simple capillaries. Fig. 1 diagrams a miscible slug displacement. The effects of some of

Jan 1, 1958

By A. J. Rambosek

An evaluation of diamond-bit performance data accumulated from core drilling in quartzite shows that core recovery and physical characteristics of drill bits and diamonds have economic significance. Relatively inexpensive, low-quality, small Congo diamonds will perform as well as, or better than, other diamonds used as drill bart. M-type bits set with oriented Congo diamonds provide those engaged in core drilling with near optimum combination. Various factors that affect bit performance, including size of diamonds, size and type of bits, grade or quality of diamonds, and percentage of core recovered, are evaluated by means of tables, charts, and discussion.

Jan 1, 1958

By P. J. Colbassani

Samples of mine atmospheres collected by Federal coal-mine inspectors during their inspections and investigations of coal mines, in accordance with provisions of the Federal Coal Mine Safety Act (66 Stat. 692; 30 U. S. C., sees. 451-483) are analyzed routinely by chemical methods at Bureau of Mines laboratories. When samples collected in open workings of nongassy coal mines at points not less than 12 inches from the roof, face, or rib contain 0.25 percent or more methane, the act requires the operator, during operation of such mine, to comply with the provisions of sec. 209, Title II, of the act, which pertain to gassy mines. The methane con-tents of such samples are determined by a physical method based on infrared absorption spectrometry to provide an independent check on analytical results obtained by chemical methods. This information circular describes the equipment and procedures used by the Bureau for determining low concentrations of methane in coal mine atmospheres by infrared absorption spectrometry. ACKNOWLEDGMENTS The authors are indebted to Dr. R. A. Friedel, Chief of Spectrometric Section, Branch of Coal-to-Oil Research, Bureau of Mines, for suggesting the analytical method and for furnishing valuable advice and assistance, and to J. A. Queiser of his staff for making exploratory measurements by this method; to Dr. M. G. Zabetakis of the Division of Explosives Technology for his assistance during the conduct of preliminary experimentation; and to L. B. Berger, Chief, Branch of Health Research, under whose guidance the equipment was procured and the work conducted.

Jan 1, 1958

By T. E. Leontis, D. H. Feisel

MAGNESIUM alloys containing rare earth metals have received considerable attention during the past several years because of the need for light alloys having high strength and creep resistance at elevated temperatures. Although much of the work reported earlier has dealt with alloys containing Mischmetal, it has been shown in two previous papersl, V hat distinctly different effects are produced by various rare earth metals and rare earth metal mixtures on the properties of magnesium. For example, much higher strengths are obtained in magnesium alloys containing didym-ium (essentially neodymium plus praseodymium) than in alloys made with Mischmetal, which contains all the rare earth metals in the proportions in which they occur naturally in the monazite ore. Mg-rare earth metal alloys are characterized by a relatively coarse grain size, which greatly impairs castability. The addition of zirconium as a second alloying ingredient has been shown8,7 to refine the grain size, which also produces a distinct improvement in the strength properties. Certain Mg-Mischmetal-Zr and Mg-Mischmetal-Zn-Zr alloy compositions which are currently being produced commercially have been discussed in dytail by Nelson and Strieter,8,4 who also present some in- formation on a Mg-low Ce-Mischmetal-Zr alloy, and by Nelson.8 A patent issued to Jessup, Emley, and Fisher9 emphasizes the superiority of Mg-didymium-Zn-Zr alloys over the corresponding alloys made with Mischmetal. The purpose of this paper is to present the results of an extensive investigation concerned with the effect of increasing amounts of zirconium on magnesium sand casting alloys containing several different rare earth metal mixtures in varying amounts. The effect of the addition of zinc to some of these alloys is also being reported. Preparation and Testing of Alloys The alloys studied in this investigation were prepared in small laboratory melts according to the melting procedures described by Nelson1" as the Crucible Method. Electrolytic magnesium having the composition shown in Table I was used as the starting material. The rare earth metal alloying ingredients used in preparing these alloys were essentially of the compositions listed in Table 11. Some of the didymium-containing alloys were prepared using a Mg-didymium hardener. The rare earth metal content of this hardener analyzed 1.2 pct Ce, 10.4 pct Pr, 80.8 pct Nd, and 7.6 pct La. The zirconium was added in one of three forms: 1) as sponge zirconium obtained from the Bureau of Mines; 2) as a fused salt consisting of 50 pct ZrCl, and 50 pct alkali chlorides from which the zirconium is reduced by the magnesium; or 3) as a Mg-Zr hardener. The alloying procedures and melt hand-

Jan 1, 1958

By E. S. Machlin, S. Weing

GRAIN boundary stress relaxation has been the subject of several investigations in recent years, but as yet the phenomenon is not well understood. One of the major difficulties has been the lack of a sufficient amount of data with which to evaluate any proposed mechanism. Little information is available on the effect of small amounts of substitutional solutes on grain boundary stress relaxation. It is with this important phase of the problem that this investigation is concerned. The influence of substitutional solutes on grain boundary stress relaxation has been recently investigated in copper by Pearson: and in aluminum by Dorn et al.&apos; Pearson studied the effect of zinc, gallium, germanium, and arsenic on the relaxation peak of OFHC copper.* The pure OFHC copper decreased the peak intensity and a second peak appeared at a higher temperature. This latter peak was termed the alloy grain boundary peak. At the lowest binary concentration studied, approximately 1 atomic pct, the primary peak was almost completely obliterated. Pearson found that the activation energy calculated from the alloy grain boundary peak for all solutes, irrespective of the concentration, was 44,000 cal per mol. Pearson concluded that the increase in activation energy from 33 to 44 kcal per mol is not continuous but abruptly changes from the lower to the higher value. As no attempt was made to investigate the intermediate range of concentration and hence calculate the possible variation of the activation energy for the initial grain boundary peak, this conclusion is hardly valid. In contrast to these results, Dorn et al. studied the effect of zinc, silver, copper, germanium, and magnesium on the grain boundary stress relaxation of aluminum. No change in the energy of activation was observed for binary alloys of the flrst four solutes, but a linear increase was found for increasing concentration of magnesium. Saturation was not found up to the maximum of 1.6 atomic pct. The energies of activation were obtained by plotting the horizontal displacement of the dynamic modulus curve vs temperature for two vibrational frequencies. As the modulus is proportional to the square of the frequency, this requires the measurement of the torsional frequency over a range of temperature. However, the technique does not lead to an unambiguous interpretation of the grain boundary

Jan 1, 1958

By L. Segle, R. Resnick

NUMEROUS experiments in the past few years have proven that void formation occurs quite generally in the diffusion zone of bimetal specimens1-4 The phenomenon has been explained in terms of the accumulation of lattice vacancies resulting from unequal diffusion of the constituents and their eventual precipitation as holes.= Attention has recently been directed to the fact that voids also form within homogeneous metals during high-temperature creep.&apos; The idea has been put forward that these voids form by the condensation of excess lattice vacancies generated by intersecting dislocations.".&apos; If the precipitation of lattice vacancies from solution is treated as a nucleation and growth process, the predicted vacancy concentration for homogeneous nucleation of voids at an observable rate is 100 to 1000 times the normal thermal equilibrium concentration. It appears that voids actually form during diffusion at vacancy supersaturations which are much lower than this8 According to the calculations of Machlin,&apos; the same must be true for voids formed in homogeneous metals during creep, if these are considered to arise from the precipitation of lattice vacancies. Therefore, if the vacancy mechanism is valid, it seems that the holes which form in diffusion and creep specimens are heterogeneously nucleated by imperfections or impurities in the metal. Irregularities in the frequency and distribution of voids in diffusion couples bear out this explanation.&apos; , It is not known at the present time what the nuclei are on which vacancies condense. Various investigators have speculated that they could be certain dislocation configurations, already existing voids produced during solidification or working, gas pockets, or inclusions in the metal. Relatedly, the precise value of the degree of vacancy supersatura-tion for void nucleation is still uncertain. An initial attempt to estimate this value from diffusion data, made by Balluffi, indicated that voids form in diffusion couples at vacancy concentrations which may

Jan 1, 1958

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By A. B. Dyes, P. H. Braun, B. E. Cole

This paper presents a reservoir engineering analysis of the performance data for a waterflooding project in the Johnson Lease, South Ward field. This type of engineering analysis adds to the knowledge of the mechanics of water flooding. This study reveals that in general (a) high ultimate areal sweep-out efficiencies (95 to 100 per cent) can be expected, and (b) cross-flow among strata of different permeabilities during the fill-up phase can have an important influence on the behavior and should be dealt with in studying reservoirs for water flooding. The analysis further showed that the recovery predictions based on what was considered a consistent interpretation of core data and logs were low because little contribution was assumed from the low permeability, oil-bearing sand sections which have apparently yielded considerable waterflood oil. This project has yielded in excess of 2 1/2 times as much oil by water flooding as by primary depletion. These very favorable results were achieved without the use of any special injection well completion techniques. However, all of the low permeability material war included in the section open to injection despite its poor estimated primary yield. LEASE PERFORMANCE HISTORY The South Ward field lies in the southeast corner of Ward County near the southern tip of the tremendous Yates trend. Deposition of sand bodies along the seashore reefs during the latter part of the Permian period established what have turned out to be ideal conditions to form a great number of independent productive sands. Probably, these reservoirs in Ward and Winkler counties are providing operators with some of the nation&apos;s richest sources of secondary oil reserves through the use of waterflooding techniques. In South Ward field water has been very successfully used to flood oil from the Bennett sand occurring at a depth of about 2,300 to 2,400 ft. About 150 ft above the Bennett sand reservoir, the Grand Falls sand produced gas from a large cap extending over most of the field. The Atlantic Refining Co.&apos;s 320-acre W. D. Johnson lease (Fig. 1) is on the northwest edge of the structure with only gas cap apparently present in the Grand Falls sand. The Bennett sand under this lease is oil productive, however, having a gross sand thickness averaging about 80 ft with a net of 18 ft of fairly clean, highly permeable sand, and about 36 ft of oil-bearing sand with low permeability and high water saturation. The lower permeability sand is interbedded with numerous layers of lime, shale, and anhydrite. Radioactivity logs from 12 wells and cores from two, examples of which are shown in Fig. 2, reveal that the total Bennett sand pore volume is about 71,000 bbl/acre. The estimated initial water saturation averages 41 per cent in the 54 ft of sand considered to contain oil; thus, also considering an estimated 18 per cent oil shrinkage, the lease originally contained about 34,000 bbl of oil per acre. Original pressure was probably about 1,400 psig. PVT correlations indicate that the reservoir fluid was originally saturated with gas. After discovery of the field in 1930, Atlantic completed the first well on the Johnson lease in March,

Jan 1, 1958

By Charles Zahn

Gas chromatography is a method of separating mixtures of gases and volatile materials by entraining their vapors in a gas stream, which passes over an appropriate stationary phase. Two techniques are in common use: Gas-Liquid Chromatography, in which the stationary phase is a liquid supported on an inert solid, and Gas-Solid Chromatography, where the stationary phase is a solid adsorbent, such as charcoal or alumina. In both techniques components emerge from the column after a characteristic residence time. Gas chromatography is applicable as a qualitative or quantitative tool in a wide variety of problems in chemical research and processing. It may also be employed for purification and separation. A running bibliography on gas chromatography has been maintained at the Bureau of Mines synthetic liquid fuels laboratories, Bruceton, Pa., for several years for the benefit of research workers, who use chromatography as an analytical tool. Since the number of references grew and interest in the technique became more wide-spread, the Bureau is publishing this list rather than maintain it as a purely internal source.

Jan 1, 1958

By C. R. Garr, A. R. Troiano

FLAKING or hair-line crack formation has been a major problem confronting the producer of large alloy steel forgings.&apos; Today it is generally conceded that hydrogen in one or more forms in alloy steel sections is a requisite for flaking. Hence an obvious remedy is a thermal cycle that reduces the hydrogen content to some low level. In practice, this generally means holding the material at some subcritical temperature for a period of time depending on the size of the ingot or forging. Another method that will suffice in some cases is to cool large forgings slowly, i.e., bury in ashes. In practice, this hydrogen bake is sometimes accemplished inadvertently by a series

Jan 1, 1958

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier&apos;s specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.&apos; The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

OFFICERS AND DIRECTORS President and Director AUGUSTUS B KINZEL, &apos;60, New York City Past President and Director GROVER J HOLT, &apos;59, Ishpeming, Michigan President-elect and Director HOWARD C PYLE, &apos;61, Los Angeles, Calif

Jan 1, 1958

By Oren C. Baptist, Eliot J. White

Samples of four reservoir sands having different degrees of water sensitivity were subjected to several laboratory tests to determine differences in capillary behavior attributable to clay-mineral effects. The degree of water sensitivity was estimated by the difference between gas and water permeability. Unsaturated pore volumes determined with mercury injection were comparable to irreducible water saturations determined with the semipermeable bar-rier method only for the non-sensitive sands that contained small amounts of non-swelling clay minerals. Irreducible saturations were independent of salinity of the water, which suggests that most residual water is adsorbed 0.7 a film over solid surfaces and that internal retention by clay minerals is relatively insignificant. The water-sensitive sands imbibed water to higher saturations than did non-sensitive sands, and this result is believed to be a combination of the effects of clay minerals and preferential wettability; however, the relative importance of each of these effects is riot determinable. Thus it is concluded that the semipermeable barrier method is the best of the laborafory methods used for estimating formntion water .saturations in the sands studied. INTRODUCTION This investigation is a continuation of studies of the role of clay minerals in petroleum production in the Rocky Mountain area. Previous work has shown large differences in gas and water permeability in numerous reservoir sands; these water-sensitivity effects observed in the laboratory have been correlated with well behavior in the field, and the degree of water sensitivity imparted to reservoirs by the various clay minerals has been determined.&apos;.&apos; The effect of interstitial clay minerals on formation water3 saturations is not so well known. It has been reported that formation water saturations probably are higher in clayey than clean sands,&apos; but this effect has not been evaluated in the laboratory, and the relative effect of the various types of clay minerals on formation water saturation has not been determined. The clay-mineral groups of most importance to this study and to petroleum production in general are kaolinite, illite, and montmorillonite. The minute layers of montmorillonite are loosely bound to one another so that water enters between them, causing great expansion of the particles. Kaolinite and illite do not exhibit interlayer hydration, but they do immobilize considerable amounts of water owing to their large surface areas, which are of the order of 15 to 97 m2/gm of clay.5 The four Wyoming sands used in this study were selected to represent a wide range of water sensitivities. These sands, with the number of wells and fields from which the samples were obtained, are: Second Frontier, five wells in two fields; Newcastle, six wells in one field; Tensleep, two wells in two fields; and Lower Muddy, five wells in one field. EXPERIMENTAL METHODS AND PROCEDURES Water-displacement data were obtained by the semipermeable barrier method," using both fresh water and brines having either 16,500 ppm sodium chloride or calcium chloride. A displacement pressure of 35 psi was found to be sufficient to obtain the practical irreducible water or brine saturation (IWS, IBS) in most samples. Mercury-injection data were ob-tained with equipment and pro-cedures similar to those described by Purcell.7 Exceedingly high pressures are required to attain complete mercury saturation by this method; however, since saturations in most samples change very little with large pressure increases above 1,000 psia, the maximum pressure used was 1,400 psia. To facilitate comparison of mercury-injection and water-displacement results, it is convenient to express mercury-injection data in terms of unsaturated pore volume. The abbreviation, (100 - SHg)min, is used to denote the pore volume unsaturated by mercury at 1,400 psia injection pressure. Gas permeabilities, ki, were deter-mined by the method proposed by Klinkenberg.8 Methods of determining types and amounts of clay minerals by X-ray diffraction analyses, as well as methods of determining water permeability, have been described previously.&apos; The imbibition characteristics of

Jan 1, 1958

By John C. Shyne, Eric R. Morgan

BORON as a hardenability agent of commercial importance has been the subject of extensive study in recent years. It has been suggested in the past that boron increases hardenability by combining with nitrogen, thus rendering it innocuous.&apos; More recently it has been proposed that boron increases hardenability by reducing the free energy of sites of ferrite and pearlite nucleation.&apos; The segregation of boron to grain boundaries, the primary site of nucleation, would account for the large hardenability effect of minute additions of boron in steel. This grain boundary theory has found general acceptance while the concept of boron as a nitrogen scavenger has been disregarded. However, the interaction of boron and nitrogen in steel is considered to be important to hardenability because boron may be made ineffective by combination with nitrogen.". * The present work was undertaken to examine some of the effects of boron and nitrogen arid their interaction in steel. A base composition of moderate hardenability was chosen. This was a 0.35 pct C steel containing 2.50 pct Ni and 0.30 Mo. This composition was used because it contained no strong carbide, nitride, or Table I. Composition of Steels by Analysis, Wt Pct Steel C Ni Mo 0&apos; B N* Base 0.35 2.50 0.30 0.0012 nil <0.0001 Boron 0.35 2.50 0.32 0.0012 0.0022 <0.0001 Nitrogen 0.33 2.60 0.35 0.0015 nll 0.0052 Boron plus nitrogen 0.35 2.48 0.30 0.0006 0.0020 0.0040 * Obtained by vacuum fusion technique. boride-forming elements. The other alloys examined were modifications of the base composition and contained nitrogen, boron, or nitrogen plus boron. The compositions of the four alloys used are listed in Table I. The alloys were vacuum melted from electrolytic iron, electrolytic nickel, ferromolybdenum, and fer-roboron. When required, nitrogen was added by admitting a partial pressure of nitrogen over the melt after vacuum melting. The alloys were cast into 21h-in. diam ingots and hot rolled to %-in. sq bars. No ingot pattern was discernible on the polished and etched cross sections of the hot-rolled bars. The alloys were normalized at 1650°F, then machined into standard %-in. diam end-quench hardenability test bars. Four different austenitizing treatments were used: 60 rnin at 1550°F, 45 rnin at 1800°F, 30 rnin at 2000°F, and 20 rnin at 2000°F followed immediately by 30 rnin at 1550°F. The 1550" and 2000°F treatments were carried out in duplicate for each of the four steels. In order to prevent surface oxidation the bars were austenitized while buried under charcoal in an atmosphere of argon. After quenching the bars in a conventional end-quench fixture, the hardness surveys were made in the usual fashion on parallel flats ground along opposite sides of each bar. These were ground 0.050 in. deep rather than the conventional 0.015 in., to avoid decarburized or deboronized regions.5 The austenite grain sizes which resulted from each heat treatment were observed metallographically using Vilella&apos;s etch for martensite. The criterion used as a measure of hardenability was the distance from the quenched ends of the bars at which a hardness of RC 35 was observed. This hardness represented the inflection point on the hardness vs distance plot. Fig. 1 shows the hardenability of each steel after the several heat treatments. The duplicate tests demonstrated excellent reproducibility; the distance to Rc 35 was reproduced within 1/16 in. for duplicate test bars. All four alloys had the same grain-coarsening characteristics. Neither boron nor nitrogen had any observable effect on grain size. The grain sizes resulting from the various austenitizing treatments were ASTM 7 at 1550°F, ASTM 4 at 1800°F, and ASTM 2 at 2000°F. The small amount of boron in the boron steel greatly enhanced hardenability when the samples were austenitized at 1550°F. The low hardenability of the boron plus nitrogen steel showed that nitrogen eliminated the boron contribution to hardenability. Both steels containing nitrogen, with and without boron, exhibited lower hardenability than the base composition when quenched from 1550°F.

Jan 1, 1958

By Goro Shimaoka, Kichizo Niwa

IN the past, the crystalline states of graphite in cast iron have been studied by many investigators. Recently several authors 1-4 have published interesting information on the crystal texture of the individual graphite grain, especially spherulites in nodular cast iron. In regard to the crystal structure of graphite, Lipson and Stokes0 howed by powder X-ray analysis that most of the crystals contain about 14 pct rhombohedra1 structure (ß-form) which differs from the hexagonal structure (a-form) in the sequence of layer stacking. Hoerni6 onfirmed the existence of the ß-form in a single crystal with electron diffraction by Kossel-Moellenstedt&apos;s method. Furthermore, Hoerni and Weigle7 found extra reflections in electron diffraction patterns, which are given by a unit cell twice as large as the usual one in the basal plane. Recently, Lukeshs observed graphite twinning and satellite reflections in his X-ray work and considered them as evidence for the existence of an orthorhombic superstructure. Owen and Street" and Matuyama" studied the structures of graphite crystals in several types of cast iron, using the X-ray powder method, and they showed that the graphite crystal contains a certain amount of the ß-form, an amount which varies with the sources of the cast iron used. The present study was made in order to secure structural information on graphitization in cast iron. Electron diffraction studies on the structure of single graphite flakes segregated from molten carbon or silicon-rich iron at 1200" to 1500°C are reported. Experimental Honkeiko pig iron (4.05 pct C, 1.59 pct Si, and 0.65 pct Mn) was used as the solvent of carbon or silicon. The pig iron was melted in an open furnace and a small quantity of metallic silicon was added to the melt at 1300°C. The melt was heated to 150O°C, and then retort black carbon or metallic silicon was added little by little. The components added to the bath contained approximately 5.0 pct C and 2.0 pct Si in the carbon-rich material, and 3.8 pct C and 5.4 pct Si in the silicon-rich iron. These two types were held at 1500°C and then cooled without graphitizing by cutting the heat sup-

Jan 1, 1958

Jan 1, 1958

By Earl A. Gulbransen, Kenneth F. Andrew

DRY oxidation of zirconium has been studied by several groups.&apos;" The present work extends our early study1 to the high-temperature studies of Cubicciotti2 and Belle and Mallett.8 ulbransen and Andrew1 showed that the parabolic rate law fitted the 2-hr experiments between 200" and 425°C after an initial deviation. An energy of activation of 18,200 cal per mol was calculated. Cubicciotti,&apos; in a study between 593" and 880°C, showed that the parabolic rate law fitted the data and an energy of activation of 32,000 cal per mol was calculated. In contrast to these studies on sheet specimens, Belle and Mallett3 studied the oxidation reaction on rod specimens and found a cubic rate law to fit the data.

Jan 1, 1958