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By C. R. Clark, G. Swift, D. S. Roberts

The purpose of this investigation was to measure PVT behavior of various types and combinations of heavy hydrocarbon components from the paraffinic, naphthenic and aromatic classes where the relative proportions Of the various components were selected to approximate those of natural gas or gas condensate systems. Synthetic mixtures were used so that the compositions Of the various components could be measured accurately. n-Heptane, methylcyclohexane and methylbenzene were used to represent the paraffinic, naphthenic and aromatic components of the heavy fraction. In the mixtures studied, the heavy fraction composition was held constant at O. O5-mole lraction, the balance being methane except for one mixture where 0.10-mo1e fraction of an intermediate component, propane, was added. The PVT data for the mixtures were determined in a variable-volume, constant-mass apparatus at psuedo-reducedtemperatures from 1.84 to 2.00, over a pseudo-reduced pressure range from 2.3 to 12.0. The experimental results showed that, regardless of the type of heavy material (paraffinic, naphthenic, aromatic, or combinations thereof) mixed with methane or methane and propane, the compressibility factors at equal values of pseudo-reduced temperature and pressure varied by less than 2.2 percent. INTRODUCTION PVT data is used for natural gas and gas condensate fluids in determining reserves of reservoirs and performance of wells, in metering produced fluids, and in recombining samples for laboratory studies. While there are vast amounts of PVT data reported for natural gas and gas condensate systems from which useful correlations have been developed, ' the compositional analyses for these systems and the resultant correlations typically were made with components analyzed through some arbitrary carbon number, usually C6, with the residue reported as a lumped "heavy" fraction. The heavy fraction was stoichiometrically recombined on the basis of an apparent molecular weight to give the final compositional analysis. It is virtually impossible to make a systematic analysis of the effect that variation of the relative amounts of paraffinic, naphthenic and aromatic constituents of the heavy fraction of natural systems might have on PVT behavior. Because there is considerable latitude in the relative amounts of these constituents, one speaks of crudes or condensate liquids as being "paraffin base", etc. It is of interest to determine if changes in the relative amounts of these three types of hydrocarbons in the heavy fraction cause significant changes in PVT behavior. If so, steps should be taken to describe better the nature of the heavy fraction in PVT correlations. If not, more confidence can be placed in the correlations presently employed. DESIGN OF THE EXPERIMENTAL INVESTIGATION We attempted to determine if changes in the base of the heavy fraction would cause significant changes in the PVT behavior of gas or gas condensate fluids. Synthetic mixtures were used to enable us to systematically vary the base of the heavy fraction and to analyze accurately the fluids. We found that the heavy fraction of naturally occurring condensate systems seldom exceeds 0.05-mole fraction. Thus, the mole fraction of the heavy fraction in the synthetic systems studied was set arbitrarily at 0.05, to maximize whatever deviations in PVT behavior that might occur. Further, we judged that since the C7 hydrocarbons normally are present in greater quantities than higher carbon number hydrocarbons in naturally occurring systems, the use of n-heptane, methyl cyclohexane, and methylbenzene to represent the paraffinic, naphthenic, and aromatic species in the heavy fraction would be most appropriate. Finally, to enable us to compare our

Jan 1, 1970

Jan 1, 1970

By N. Arbiter, C. C. Harris

In 1961, a research program started at Columbia into the mechanical aspects of flotation,* and certain ends are now in view. The purpose of this note is to explain these tentative conclusions in the hope of stimulating discussion and eliciting new data, especially industrial data, with which to test the views expressed. The variables presently under consideration are impeller rotational speed, N, volumetric air rate, Q, and impeller diameter, D, the latter being the parameter chosen to designate cell size. The most favorable *The latest work 1 references all previous publications. chemical environment is not under discussion since the procedures for establishing it are better understood than those for optimizing N and Q by virtue of a longer history of more intensive investigation. THE GRADE AND RECOVERY SURFACES With a given ore, chemical treatment, and flotation machine, both grade, G, and recovery, R, are functions of N and Q. The GNQ and RNQ relationships are best viewed in terms of three-dimensional surfaces (Fig. 1) which are experimentally determinate.2 TO maintain grade at an acceptably high level, it is necessary for N and Q to lie within certain limits, and similarly with recovery. However, the ranges of N and Q for grade on the one hand and recovery on the other are rarely the same. Selecting the single N

Jan 1, 1970

By J. B. Cheatham, M. D. Biggs

This paper presents a systematic method for determining the forces on a simplified roller bit. The kinematics of an actual roller bit drilling in rock is complex; nevertheless, it is desirable to obtain an accurate analytical model.. As a preliminary study, the roller bit is represented here by a simple two-dimensional bit and the rock by a Coulomb plastic material. Results from previous work, plus additional assumptions, are incorporated into a computer program to determine the forces required to move the bit in a specified manner. Example problems are worked by use of this program. By studying similar drilling problems and by supporting laboratory work, one could eventually obtain an accurate analytical model for drilling by an actual roller bit. This could lead to the compilation of a catalog of results that, in turn, would allow selection of the optimum drill bit for any given situation. INTRODUCTION

Jan 1, 1970

By Daniel T. Brian, O&apos

Exploration targets and results in the mining industry are commonly summarized in terms of tonnage and grade. Business appraisals require, as additional information, the expected profit or loss implied by the physical summay. The early incorporation of knowledge gained through financial analysis computations can provide a means for economically resolving many common exploration and development problems. Examples of such applications from the activities of exploration planning, reconnaissance, land acquisition, and development planning are presented. While prospecting for mineral deposits, geologists are frequently asked what they hope to find or have found. The response is usually descriptive, such as "50 million tons of 1% copper," and the economic implications are deferred until a capital investment decision is required. At that time, a financial analysis integrating the four analysis components is completed. These components are: 1) Tonnage and Average grade above cutoff grade 2) Capital and operating costs 3) Product value 4) Appropriate profit or loss accounting Close examination of these components reveals that there is no intrinsic reason for avoiding financial analyses at earlier stages in exploration, as long as the uncertainty of the estimate is realized. Tonnage and average grades are commonly estimated at early stages in exploration. For this component, the appropriate cutoff is the major uncertainty. Capital and operating costs are difficult to estimate before detailed quantitative information is available, but estimates useful for the types of applications pertinent to earlier exploration stages are possible. Product value estimates may or may not be difficult, depending on the pricing structure of the particular commodity. A simplified accounting procedure usually may be adopted without introducing any significant loss of validity. This paper describe some of the financial analysis applications which are pertinent during mineral exploration and deposit development. These applications lend additional insight during exploration planning, land acquisition, physical exploration, and development. The examples are oriented toward a hypothetical management investment policy which is based on a single criterion, a minimum 15% discounted cash flow rate of return. In reality, managements use multiple criteria. This simplification is convenient for purposes of presentation and does not invalidate the examples. Computers are useful, but not a requirement, for the applications described. The use of computers provides the results on a more timely basis at costs lower than equivalent manual computations. UNDERLYING PRINCIPLES AND ANALYSIS METHODS Data estimates are subject to uncertainty. The analyst may choose to assess this uncertainty by using one of two principles. Each principle has some advantages. The principle most commonly employed is "assumed certainty." Each financial analysis is based on one set of selected data, which may represent the average estimates, minimum expected conditions, etc. The critical data is identified by making successive calculations, varying the values used. Such studies, called sensitivity analyses, isolate the economic effect of various uncertainties, and guide the allocation of future efforts toward improving the overall accuracy of the analysis. A second principle, "assumed risk," examines the interactive effect of the current uncertainties by qualitatively assigning probability distributions to each data element. These probability distributions indicate the currently appraised chance that a given numerical value will prove to be true. The corresponding procedure, risk analysis, consists of processing many individual financial analyses, each analysis being based on randomly selected numerical values from the probabilistic distributions. The result is a numerical presentation of the uncertainty, but care must be exercised in the interpretation of results. The advantage of this procedure is the direct measurement of economic uncertainty caused by the interaction of uncertain estimates. Kennecott Copper Corp. has developed computer systems for accomplishing sensitivity and risk analyses.

Jan 1, 1970

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By F. Weinberg, L. MacAulay

DAVIS,&apos; in an investigation of solute redistribution along molten rods of dilute silver in tin, concluded that at horizontal temperature gradients below approximately 5°C per cm very little convective mixing takes place. Cole and winegard2 observed temperature oscillations in horizontal melts of tin, with temperature gradients of several deg per cm. They associated the temperature oscillations with the presence of convective flow in the melt. At temperature gradients less than 1°C per cm they did not detect convective flow. In the present work, direct measurements of con-vective flow in liquid tin have been made using a radioactive tracer technique. The results indicate that extensive convective flow occurs at temperature gradients below those previously reported. The apparatus used to determine the extent of con-vective flow is shown in Fig. 1. The graphite boat Fig. l(a), has two rectangular channels both of which contain molten tin. Radioactive Ag110 in the form of Sn-0.2 pct Ag alloy was introduced at the end of one channel, by rotating the cylinder shown. A series of fixed thermocouples were positioned along the center of the second channel to determine the temperature gradient. It was assumed that the two channels had identical temperature distributions. The graphite boat was inserted into a vycor tube which was surrounded by a multiple winding tube furnace as shown in Fig. l(b). The tin was melted in an argon atmosphere. The distribution of Ag110, as a function of position along the boat at a given time after introduction of the ~g"&apos;, was determined with the

Jan 1, 1970

By B. C. Wonsiewicz, W. W. Wilkening

Following a procedure proposed by Wheeler and Ireland, Plane stress yield loci were constructed from Knoob hardness numbers. Basically, six differently oriented hardness measurements were made on three orthogml surfaces through pure poly crystalline magnesium sheet, a magnesium single crystal, and sheet of the magnesium alloys: Mg + 0.5 pct Th, Mg + 4 pct Li, AZ31B, and EKOO. Hardness loci were found to be in poor agreement at small strains (E < 0.05) with loci established by a more rigorous technique. At larger strains (E - 0.10) the agreement is fair, but at this stage in deformation the conventional locus has lost much of the asymmetry that characterizes these anisotropic materials. Two effects which will lead to distortions in the Khn locus are discussed with reference to the geometry of plastic flow during a hardness test. DETERMINING a material&apos;s resistance to multiaxial loading is of interest not only from a structural design viewpoint but also from that of deformation processing. Unfortunately, the determination of the yield locus, although simple in principle, involves tedious procedures if the results are to be at all rigorous.&apos; The idea, first proposed by Wheeler and 1reland2 of determining the yield locus by means of six Knoop hardness impressions along the principal directions in a material has obvious appeal. It is simple, quick, and should be applicable to very thin sheets. If such a technique could be demonstrated to produce consistently reliable results, it would be of interest to both researcher and designer. Lee, Jabara, and ackofen have compared the yield locus determined by Knoop hardness measurements (the Khn locus) to a locus determined by more rigorous techniques. They found good agreement for two titanium alloys at a plastic strain of about 1 pct. The purpose of this paper is to investigate if the Khn locus construction is a reasonable approximation to the locus of a highly anisotropic material. Examples of such materials are magnesium and magnesium alloys which have severely distorted yield loci which in turn reflect markedly dfferent yield strength in different directions.&apos; In pure magnesium, for example, the yield stress in tension along the transverse direction may be four times the yield stress in compression in the same direction and twice the tensile yield stress in the rolling direction. Predicting such large differences ought to serve as a severe test of the Khn locus construction. EXPERIMENTAL PROCEDURES Samples of rolled sheet, 0.250 in. (6.35 mm) thick, of pure magnesium and four magnesium alloys (Mg experimental materials. The pure magnesium together with the lithium and thorium alloys were those used in the study of Kelley and Hosford. The grain size was ASTM number 4 for the pure magnesium and number 6 for the alloys. HARDNESS TESTING The materials were sectioned along the rolling and transverse planes, mounted in a quick setting resin, and mechanically polished. Most of the hardness tests were performed on a surface prepared by electro-polishing (30 pct nitric acid in methanol at 0°C and 20 v) with the exception of the AZ31B and EK00 alloys which were made directly on a metallographically polished surface. However, subsequent hardness tests on the same sample after heavily electropolishing, revealed essentially the same hardness as before. At least twenty Knoop hardness impressions under a 100-g load were made in each of the six orientations shown in Fig. 1. The average hardness number and standard deviation were then calculated for each orientation. CONVENTIONAL LOCUS CONSTRUCTION Yield loci were constructed using a technique described in detail by Lee and ackofen,&apos; in which the flow stress (stress at a given plastic strain) fixes the coordinates of a point on the locus and measurements of the strain ratio serve to establish the slope of the locus at that point. The loading paths which correspond to uniaxial tension or compression tests establish the four intercepts of the locus with the coordinate axes plus one point on the balanced biaxial tension line Tensile testing was performed along the rolling and transverse (r, t) directions. Samples had a uniform rectangular gage length 1 by 4 by 4 in. (25.4 by 6.35 by 6.35 mm) and were deformed at a strain rate of 3.33 x 104 sec-&apos;. The tests were interrupted periodically to unload the sample and measure the plastic strains by means of X-Y post yield strain gages. Compression tests in the rolling, transverse, and through-thickness (r, f, z) directions were performed on 1/4 in. (6.35 mm) cubes at an initial strain rate of 8.33 x sec-&apos;. Lubrication was provided by 0.002 in. (51 pm) Teflon sheet which was renewed after unloading for micrometer measurements used to calculate the strains.

Jan 1, 1970

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,&apos; metal purification,2&apos;3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10&apos;1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge&apos; or where melting is achieved, "dripping" from the charge is encountered.&apos;&apos; At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By E. Mcl. Tittmann

Deep-seated human instincts urge us to positively mark the passage of time. We celebrate the passage of each year. Years give way to decades, and decades to half centuries and centuries. At all these mileposts we are inclined to pause, take a look around and catch our breaths before embarking on the next leg. We are at such a point now and this meeting I am sure will give direction to the road ahead into the decade of the seventies. In looking around at this point, 1973, it is obvious to all of us that the environment in which we must mine, mill, smelt and refine lead and zinc has radically changed. These changes have, of course, occurred over a long period of time. They have, however, all been in the same general direction. They have all had the same motivation. The period of greatest contrast is probably the fifteen years just before World War II and the fifteen years following the end of that war. I thought that I might review briefly with you what seems to me to be four of the more important changes that have developed since World War II that profoundly affect our activities in the lead and zinc industry. I mentioned before that all these changes have been in the same direction; that is, they have all tended to restrict our freedom of action in pursuing our objective of producing lead and zinc on a competitive basis at a profit. Consequently, in discus- sing them you may think that I am merely viewing with alarm. This is not the intent. This is merely supposed to be an objective analysis. I think it appropriate before discussing these trends in de- tail to examine the position of lead and zinc today.

Jan 1, 1970

By Harold H. Haman

In view of Twentieth Century advances in mineral dressing technology, most modern metallurgists would be inclined to class jigging as an early, somewhat primitive, representation of their art. The practice of metallic sulfide concentration by jigging is becoming rare. This is so, in part, because the type of ore amenable to the process is becoming rare. It is appropriate, however, that this symposium recognize that a significant contribution of domestic zinc remains dependent upon coarse preconcentration by jigging, and that the state of the art be described even though the theory and applications are already well delineated in technical literature. One of the few areas still using jigging as a major concentrating process is The Upper Mississippi Valley. AREA HISTORY AND JIGGING The Upper Mississippi Valley (UMV) has produced one billion dollars worth of zinc and lead at current prices. The district includes the southwest part of Wisconsin, the northwest corner of Illinois and an adjoining narrow strip of Iowa. Within a total area of 4,000 square miles, important sub-districts cover about 400 square miles. As is widely known, early mining in this district involved shallow lead---crevice deposits of galena that were very selectively mined, hand sorted and cleaned, and then smelted at or near the site. The district has produced almost a million short tons of metallic lead, a very large part of this during the fifty- year period following 1830. Zinc mining began at the end of the civil war, but at a very low rate until about 1905.

Jan 1, 1970

By T. D. Guldem, J. L. Kaae

ALLOYS with nominal composition of 45-Fe 35-Ni 20-Cr, ASTM-B-163, known under the commercial names of Incoloy 800 and Sanicro 31 (Alloy 800), are often employed at elevated temperatures for extended periods. Therefore, knowledge of the aging behavior of these alloys is of considerable importance. Significant decreases in ductility and increases in yield strength have been observed in the 45-Fe 35-Ni 20-Cr alloys containing about 0.4 pct Ti and 0.4 pct A1 after long-term aging at 540" to 700"~."~ However, no direct evidence has been presented for precipitation phenomena that might result in such changes. Strengthening effects have been attributed to the effects of local or-dering.3 Since y&apos; precipitation (Ni3A1, Ti) is known to occur in similar alloys which contain more titanium and aluminum,4-7 it was decided to explore the possibility that y&apos; might precipitate in these alloys and might be responsible for the changes in mechanical properties on aging. This note reports some observations of two distict types of matrix precipitates made by means of transmission electron microscopy, in a 45-Fe 35-Ni 20-Cr alloy containing 0.31 pct Ti and 0.4 pct Al. The steel used in this investigation was obtained from the Sand-vik Steel Works; it is designated Sanicro-31 (Alloy 800). The chemical composition of the alloy is given in Table I. Aging of solution-treated material at 700" and 800°C for 130 and 100 hr, respectively, produced the matrix precipitates shown in Figs. l(a) and l(b). It is apparent from these micrographs that the precipitate particles occurred in the form of thin square plates parallel to the matrix cube planes. Extraction replication and selected-area electron diffraction showed that the precipitates were M23C6. Coherency strains, consistent with the semicoherent nature of small M23C6 precipitates,&apos; were evident for certain imaging conditions. In addition to matrix precipitation, preferential precipitation of M23C6 on dislocations was common, as has been reported previously for austenitic stainless steels.&apos;" Specimens aged for longer times (-300 hr) at 700°C exhibited a different type of coherent matrix precipitate in addition to the M23C6. An example is shown in Figs. 2(a) and 2(b). In addition to the few large M23C6 precipitates, small precipitates exhibiting strain contrastl0,ll are present. The "line of no contrast" of the strain field of a given precipitate lies along differ-

Jan 1, 1970

By Akira Yokoyama

Japan is composed of four main islands: Honshu, Hokkaido, Kyushu, and Shikoku (Fig. 1). Between Honshu and Kyushu, a railway tunnel and a road tunnel have been open since 1942 and 1958, respectively. Hokkaido, [ ]

Jan 1, 1970

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura&apos; have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By Hans W. Brodbeck

The main problem in tunneling without the use of explosives lies in the development of tools capable of continuous mechanical destruction of rock, resulting in a fragmentation which lends itself to a smooth, uninterrupted transportation of the broken rock away from the tunnel face. While all moles of U.S. design mainly achieve this by crushing the rock by means of "disk cutters" or "roller bits," a boring system based on the principle of cutting the rock came into being in Europe, whereby the rock is worked in a manner very similar to the milling of metals. For tunneling purposes, this principle was first developed by the late Austrian engineer Wohlmeyer. Between late 1962 and the spring of 1965, the first experimental machine was tested in a German coal mine, working in coal and shale over a distance of some 3000 ft, divided over two runs separated by a period of time to allow for equipment modifications. In 1964, a collaboration was started between Wohlmeyer and the Habegger engineering firm of Thun in Switzerland. The normal Habegger range of equipment consists of aerial ropeways, ski lifts, and certain tool machines, to which in later years have been added monorail passenger-transport systems. One of these was installed as the main mode of transport at the 1967 World Fair in Montreal. After taking over the Wohlmeyer patents, Habegger further developed the original cutting principle, aiming at more robust machines in order to be able to tackle harder rock. A first machine was built and tested at a site near Thun in sandstone averaging 17,000 psi compressive strength and limestone of 25,000 psi. In May 1966 this machine was delivered to Japan for the boring of a pilot tunnel for the Honshu-Hokkaido railway connection under the sea. A second machine, incorporating many improvements based on experience gained with this first mole, was built during 1966 and tested in the same limestone as mentioned previously (25,000 psi), before being installed to bore the head race tunnel of the Julia hydroelectric power scheme near St. Moritz, Switzerland, in the early summer of 1967 (Fig. 1 ) .

Jan 1, 1970

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks&apos; and to the precipitation of second phase particles,2&apos;3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these &apos;(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By Billy L. Crowder, John M. Fairfield

The implantation of B+ , P+, and As&apos; into silicon has been studied with the purpose of making shallow p-n junctions. The influence of such parameters as 1) ion energy, 2) target orientation and temperature, 3) total dose, and 4) annealing schedule was investigated. An energy range of 70 to 300 kev was used for boron and phosphorus implants and up to 500 kev for arsenic. It is found that the experimental projected range agrees well with theory and that shallow junction depths can be made reproducibly. ION implantation has received much attention recently as a technique for doping semiconductors. Specifically, it has the potential of supplementing or replacing the diffusion process as a method for making p-n junctions. In a few specific cases it has been used successfully to make semiconductor junction devices. Potential advantages of ion implantation doping over diffusion techniques are: 1) It affords greater control of shallow junction depths (< 0.2 µ) while maintaining high peak concentrations. This is particularly important for high-speed switching devices, since lower junction capacitances and resistances can be achieved. 2) More precise registration of small planar structures can be realized if proper masking procedures are employed. This advantage is especially useful in the design of high-density integrated circuits. It has been used to advantage in FET fabrication since the edge of the source or drain can be aligned precisely at the edge of the gate electrode.&apos; 3) Ion implanatation permits lower temperatures than diffusion techniques. This factor alleviates the problem of compatibility of diffusivities often encountered when designing multiple-junction structures. Also, the lower temperatures create fewer thermal defects and dislocations, which may account for the high efficiency of some ion-implanted solar cells.2 4) Impurity profiles can be more easily tailored to resemble ideal distributions. Successful exploitation of the potential advantages of ion implantation techniques will depend on increased knowledge and understanding of the subject. The factors likely to be influential in determining impurity distribution profiles in ion-implanted single-crystal targets have been reviewed by J. F. Gibbons.3 In addition to the mass and energy of the implanted ion, the total dose, target orientation, and target temperature are important parameters. The annealing temperature required for removing lattice damage and incorporating the implanted species on an electrically active site is very important. This paper describes an investigation of some of these factors. Implants of boron, phosphorus, and arsenic into silicon have been studied. Energy ranges of 50 to 300 kev were used for boron and phosphorus and up to 500 kev for arsenic. In addition to the implantation energy, the effects of total dose, target temperature, and post implant anneal have been investigated. EXPERIMENTAL PROCEDURE The implantation targets were silicon wafers cut from Czochralski-grown crystals, lapped, and chemically polished. The orientations were (111), (110). and (100) with misorientations of up to 7 deg from the principal axis. For this study, accurate target alignment (i.e., within 0.1 deg) was not available and quoted misorientation values should be regarded as approximate . The implantation equipment consisted of an ion source, a 300-kev linear accelerator tube, an electromagnetic separator, and the associated target supporting and beam focusing assemblies. The ion source was a simple oscillating electron type source,4 which has been described elsewhere.5 The gaseous compounds BF3, PF5, and AsH3 were used as ion sources for B+, P+, As+, and AS+&apos;. Analyzed current levels of up to 20 pamp could be obtained; however, for this investigation target current levels of 1-3 µ amp were usually employed. The analyzed ion beam was collimated through a double slit (1.4 x 0.4 cm) and swept perpendicularly to the long axis of the slit such that an area of about 2 sq cm on each target was covered. Dosages of around 1015 cm-2 were normally employed, but smaller amounts were also used for comparison. A uniform flux density over the bombarded area was assured by the continuous use of profile monitors similar to those described by Wegner and Feigenbaum.6 Post-implant annealing was accomplished in an argon atmosphere in a temperature range of 600" to 950°C. It was not part of the purpose of this investigation to study the annealing kinetics; however, some isochronal and isothermal anneal experiments were conducted to determine the time and temperature necessary to render a reasonably high portion of the implanted ions electrically active (i.e., higher than 50 pct). Post-implant anneal temperatures of around 900° and 600°C were required for boron, and arsenic and phosphorus implants, respectively. Arsenic and phosphorus implants increased in conductivity rather abruptly at the proper anneal temperature of the isochronal curve, but boron increased more gradually over a wider range. Isothermal anneal curves were reasonably flat after 10 min, so an anneal time of 1/2 hr was used for the experimental results described below. The profiling techniques were: 1) neutron activation analysis, 2) differential sheet resistance,7 and 3) junction staining.8 The differential sheet resistance technique is commonly employed in this type of study. Its principal disadvantage is the uncertainty of the ef-

Jan 1, 1970

By J. C. Jaeger

It frequently happens in engineering and mining situations that "bad" rock is encountered which consists of rock broken up into blocks a few inches or less in diameter by a network of intersecting joints. These joints may be open, or filled by veins of solid material, or covered with weathering products. Essentially, the material consists of an aggregate of small interlocking blocks. In such circumstances, major joint systems usually can be recognised and studied, but there are probably many minor planes of weakness which may cause the blocks to be of almost random shape. It is extremely difficult to determine the properties of such materials. Measurements on small specimens give the properties of the constituent rock and not the jointed material. At the other extreme, the material has occasionally been tested as loose aggregate in large triaxial pots, but this gives no information about the strengthening effect of the interlocking of the small blocks of rock. One simple approach, which has been much used, is to regard the rock as randomly jointed on a small scale and to apply soil mechanics theory to it. In this case, the normal and shear stress at failure are related by [ ] where the coefficient of friction p and the cohesion c will be those of the individual joints. Even in very bad rock, it is usually possible to drill core in small diameters of 1 to 2 in. which will contain a number of joints, both open and filled. The testing of such joints provides one simple method of determining some of the properties of closely jointed rock and will be discussed in detail in the next section. Calculations based on Eg. 1 with values of c and µ obtained in this way may be expected to give a lower limit for the strength of structures in rock.

Jan 1, 1970

By Douglas Baker

Zinc concentrates assaying approximately 54% zinc and 30% sulfur are roasted in a suspension type roaster to yield a zinc oxide calcine assaying about 65% zinc and 0.40% sulfur. This calcine is the feed material to the sulfuric acid leaching section of an Electrolytic Zinc Plant. The SO2 gases resulting from the elimination of sulfur from the concentrates are passed through a waste heat boiler for the generation of high pressure steam, cleaned by a baghouse, and delivered to the humidifying tower of a sulfuric acid plant system. The gases are then treated in a mist precipitator for final fume removal and then converted to sulfur trioxide in a three pass contact system using vanadium pentoxide catalyst for the manufacture of sulfuric acid. Waste heat steam is used to power the steam turbine which drives the acid plant blower.

Jan 1, 1970

By J. D. Defilippi, E. M. Gilbert, K. G. Brickner

FCC chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Transformation to martensite is considered to be responsible for this behavior in some metastable Cr-Mn-N steels. However, very stable Cr-Mn-N steels also exhibit a ductile-to-brittle transition. The results of this study indicate that deformation faulting is the probable cause of the brittle behavior of stable Cr-Mn-N steels. Deformation faulting accounts for the ductile behavior of these steels in a tension test at -320°F and brittle behavior in an impact test at -320°F. Deformation faulting also accounts for the toPological features observed on the fracture surfaces of impact specimens of these steels. FACE- centered- cubic chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Many Cr-Mn-N steels transform to martensite during deformation,l-5 and several investigatorsl-3 have suggested that the brittle behavior of these steels is caused by martensite formation. However, very stable Cr-Mn-N steels also exhibit brittle behavior. Schaller and Zackeyl reported that a very stable Cr-Mn-N steel (less than 3 pct martensite formed at -320°F) exhibited a transition temperature higher than that for steels in which large volume fractions of martensite formed during testing. The explanation given by Schaller and Zackey for this observation was that in the very stable steel the martensite, because of its higher interstitial content, was more brittle than that formed in their other steels. This explanation was questioned by Tisinai and samans4 and Baldwin.6 Moreover, because the toughness of stainless martensite at cryogenic temperatures is generally very low, this explanation does not account for Thompson&apos;s7 observation that small additions of nickel (1 to 3 pct) greatly improve the toughness of high nitrogen (0.35 pct) Cr-Mn-N steels. The present paper summarizes the results of an investigation of the low-temperature brittleness in very stable Cr-Mn-N steels. The importance of the mode of deformation on the toughness of these steels is discussed. Table I. Compositions of the Steels Invertigated, Pet Steel C Mn P S Si Ni Cr N - A 0.09 14.70 0.018 0.011 0.47 0.22 18.40 0.54 B 0.12 14.90 0.001 0.008 0.48 0.14 17.80 0.38 C 0.12 14.95 0.004 0.005 0.62 3.95 18.43 0.38 MATERIALS AND EXPERIMENTAL WORK The compositions of the steels investigated are shown in Table I. Steels A and B had compositions within the limits of a proprietary Cr-Mn-N stainless steel,* whereas Steel C was similar in composition to the proprietary steel except for its 3.95 pct Ni content. All steels were hot-rolled to 1/2-in. thick plate. The plates were subsequently annealed for 1 hr at 2000°F and water-quenched. Standard longitudinal and transverse Charpy V-notch impact specimens were machined from the annealed plates. Duplicate longitudinal and transverse impact specimens were tested at 212", 80°, 32", 0°, -100°,-160°,-200°,-256", and -320°F. Longitudinal tension-test specimens were also machined from the plates and tested at a crosshead speed of 0.05 in. per min at the aforementioned temperatures. The fractured impact and tension-test specimens of all three steels were examined to determine whether martensite had formed during testing. Magnetic, X-ray, electron-diffraction, and electron-microscopy techniques were used to detect the presence of martensite in the highly deformed areas of these specimens. Metallographic examination of highly deformed areas of impact and tension-test specimens revealed the presence of dark-etching bands, such as those shown in Fig. 1. These bands were observed only in deformed samples and were thought to be associated with the low-temperature brittleness of the Cr-Mn-N steels. Accordingly, a sample 1 in. wide by 3 in. long was cut from the 1/2-in.-thick plate of Steel C. This sample was surface-ground to a in. and then cold-rolled 60 pct at -320°F. Thin foils were prepared from the cold-rolled sample and examined in a JEM electron microscope. Brightfield, dark-field, and selected-area diffraction techniques were used to determine the cause of the dark-etching bands. Fractographic experiments were also performed. Impact specimens Of Steels A, B, and C were broken at -320oF, and the fracture surfaces of these specimens were immediately shadowed with carbon. The carbon replicas were examined in a Siemens electron microscope, and attempts were made to correlate the topological features of the fracture surfaces with the deformation mechanisms that could be occurring during an impact test of these steels.

Jan 1, 1970