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By James Watson Baxter

Fluxes are used to promote pyrometallurgical processes that rely on adhesion (soldering or brazing) or fusion (gas and arc welding) to join metallic surfaces. In the adhesive processes, the metal surfaces to be joined are not melted; the join is formed using a filler metal with lower melting point than the base metal. Fusion welding involves use of heat in excess of the melting point of the base metal. The fused joint may be achieved either by simply fusing together metal surfaces brought in contact with each other or by introducing additional molten metal of similar composition to form a fused joint. ADHESIVE PROCESSES--SOLDERING AND BRAZING In order for molten filler metal, solder or braze, to spread in a manner that creates a successful join; the work surfaces on the base metal must be thoroughly cleansed. Fluxes remove stubborn oxide films and other surface contaminants, promote wetting of the work surfaces, add fluidity to the solder or braze, and enhance workability and ease of spreading. Brazing processes involve higher temperatures than those reached in soldering. Brazing fluxes, which must remain active and effective at the higher temperatures, differ from those employed in soldering. Some common fluxes used in adhesive processes are rosin for soldering tin and electrical connections, hydrochloric acid for use in soldering galvanized iron and other zinc surfaces, and borax for brazing. Soldering and brazing are similar processes, the primary difference being the temperature at which the joining operation is carried out. Soldered joints, produced with low-melting-point fillers (solders) that melt and flow at temperature less that 450°C (Althouse et al., 1988) can sustain loads of 1 to 1.7 MPa for extended periods of time (Anon., 1966). Brazing involves the use of filler materials with melting points commonly above 500°C and generally provides stronger joints than those obtained with solder. Both processes require local application of heat to melt and spread the filler so that the molten filler can wet (adhere to) the base metals by alloying and diffusion. Soldering Soldering is a means of joining metals by adhesion using a metallic bonding alloy as the filler, commonly a mixture of lead and tin. However, the adhesion of solder depends more on its ability to be keyed into minute surface irregularities than on alloying. The most familiar application is to provide and secure electrical connections. Soft solders can range from 1 to 70% tin with the remainder mostly lead. However, for general-purpose, soft-solder work, the alloy is commonly 50% lead-50% tin. Higher lead contents provide a wider range in the melting temperature and, for this reason, a 60% lead-40% tin alloy, which yields a mushy mixture, is used for wiped joints in lead sheet and pipe work. Conversely, 40% lead-60% tin alloys are used in soldering tin and other low- melting-point materials for which a narrower range of melting temperature is required. There are numerous other solder compositions such as tin-silver, 95% tin-5% silver and antimony-tin, 95% tin and 5% antimony (Carlin, Jr., 1992). Heat needed to melt and spread the solders is commonly provided by electrically heated, copper-tipped soldering irons or by means of torches; the solder is applied by hand, usually face-fed by means of wire. For wiped joints in plumbing and lead-cable splicing, the solder is manipulated with cloth pads. The molten solder wets the joint surfaces and is drawn, by surface tension, into minute fissures and capillary openings. Other applications involve use of induction heaters and furnaces with pre-shaped solder appropriately placed prior to fluxing and heating. In some processes, the joints are immersed in molten solder. Constituents and Role of Soldering Fluxes: Soldering fluxes generally fall into one of three categories: highly corrosive fluxes, intermediate fluxes, and noncorrosive fluxes. These same categories are sometimes designated inorganic, organic and rosin-based respectively (Althouse et al., 1988). Common constituents of each group are discussed briefly below. Corrosive Fluxes (Inorganic). Work with aluminum, magnesium, stainless steel, high alloy steel, aluminum bronzes, and silicon bronzes is carried out at temperatures in the upper portion of the range for solder operations. Soldering these materials requires use of highly active, corrosive fluxes to remove and prevent the formation of the especially stubborn, hard, oxide films that form on these materials upon exposure to the atmosphere. The corrosive fluxes consist of inorganic acids and salts that are applied either as pastes or dry. They are active at elevated temperatures and, since they remain active after the soldering is completed, must be completely removed. The main constituent of most corrosive fluxes is zinc chloride with a melting temperature well above the solidus temperature of most commercial tin-lead solders. It is made by the action of hydrochloric acid on zinc. When zinc chloride is used alone, un- melted particles of this corrosive salt get caught up in the joint and weaken it. For this reason, other inorganic salts such as ammonium chloride (NH4Cl) or sodium chloride (NaCl) may be added to lower the melting temperature. A mixture of zinc chloride and ammonium chloride is very effective because the excellent oxide reducing properties of ammonium chloride and the protective action of the molten zinc chloride combine to produce a fluxing action superior to that achieved when either is used alone. In addition to zinc chloride, ammonium chloride, and sodium chloride; common con-

Jan 1, 1994

By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By T. N. Moore, E. M. De Souza

J. Dasher Regarding the March 1991 ME technical paper by De Souza and Moore: For more than a decade since my February 1981 article on how to use modern metric, which SME-AIME had decided to do, I have monthly pointed out metric errors to the editors. In part, I do this because there has been no action to allow editors to fix figures and tables or to allow them to require authors to do so. The latest resulting atrocity provokes this discussion of vibrating drill handle units being stated in decibels. Reply by T. Moore We have read the discussion of our paper by Mr. Dasher. Our reaction is one of surprise and incredulity. It would seem that Mr. Dasher takes exception to the use of the decibel scale to present vibration acceleration data, and the use of hertz as the unit for frequency. The basis for his objection to the decibel appears to be that it has no dimensions (which somehow invalidates its use), that it is "non-metric" and, finally, that it is parochial (of limited or narrow scope). His objection to the use of the term hertz is not stated, but we will assume that it stands condemned as "non-metric" and parochial. Obviously we disagree with Mr. Dasher's views and will now outline our reasons. Although the decibel scale originates from transmission line theory and telephone engineering, it is also at present widely used, not only in the fields of electronic engineering and acoustics, but also in the area of vibration. The original definition of the decibel (dB) was based on power ratios: dB = 10 log 10(W/W0) where Wo is a reference power. However, as the power measured across a given impedance is related to the square of the force acting upon this impedance, Z, a more commonly used definition is: [2 dB = 10 logF /Z) = 20 log F/F 10\ F0 2 /Z(0)] where F and F0 are the r.m.s. values of the forces. Now, if the measurements are related to one and the same impedance, the decibel notation in the form of 20log10(X/Xo) may be used as a convenient relative magnitude scale for a variety of quantities. Thus, X may, for instance, be an r.m.s. displacement, velocity or acceleration. It is only required that XD always be a reference quantity of the same type as X. That is, when X represents an acceleration, then X0 represents a reference acceleration. This is the formulation used in our paper. This was not an arbitrary choice on our behalf but reflects standard practice as specified in the International Standard ISO 5349-1986(E) Mechanical Vibration - Guidelines for the Measurement and the Assessment of Human Despite the metric prefix, the decibel is a parochial expression of (l) the logarithmic ratio of the loudness of a sound to what is normally audible or (2) the logarithmic ratio of two power signals in radio or electronics. A decibel is not a unit, much less an SI, unit and has nothing whatsoever to do with the acceleration of drill handles. Stating that m/s2 (acceleration) is decibels is without reason. Whoever reviewed this material should not have allowed publication of figures of dB and H.[ ] Exposure to Hand-Transmitted Vibration. This was clearly stated in the "measurement protocol" section of our paper. This quantity is then referred to as the acceleration level and is expressed in dB. We may have inadvertently caused some confusion when we simply used the term acceleration to refer to acceleration level on our diagrams. At the time, we felt the use of dB or m/s2 would make the context clear to the reader. For any confusion this decision may have engendered, we apologize. Since the decibel expresses the ratio of two like quantities, it certainly has no dimensions. It is, however, common practice to treat "decibel" as a unit as, for example, in the sentence, "The acceleration level measured at the operator's hand was 160 dB." The expression of measured quantities in dimensionless form is not inherently unacceptable. In fact, in many areas of engineering it is standard practice (consider the use of Reynolds Number, Nusselt Number, etc.). The fact that the decibel is a dimensionless quantity makes the question of whether it is a SI unit nonsensical. However, it is valid to insist that the dimensional quantities used to obtain the decibel values be expressed in SI units. A careful reading of our paper will make it clear that the measured acceleration was, in fact, expressed in units of m/s2 as was the reference acceleration (l x 10-6 m/S2). These are the accepted derived SI units for acceleration. See, for example, the standard ASTM E380-89a Standard Practice for Use of the International System of Units (SI) (The Modernized Metric System). Concerning Mr. Dasher's implication that hertz (Hz) is an unacceptable unit of measure for frequency, we would again refer him to the standard ASTM E380-89a. Here, he will find (section 2.4.2) that hertz is an accepted "special name" for the derived SI units-1. This is in keeping with numerous other international standards including ISO 5349-1986(E) to which we referred in our paper. In conclusion, we agree with Mr. Dasher on the desirability of expressing measurements in modern SI units. But we would remind him that the standards that define the use of these units, and the accepted means of presenting measured data, are in a continual state of refinement. It is, therefore, incumbent upon him to keep abreast of these changes if he wishes to constructively critique the work of others.[ ]

Jan 1, 1992

By W. G. Pfann

A simple method of obtaining multistage batch separations by crystallization was described recently. Known as zone-refining, it comprises passing short molten zones through a long solid charge. This technique can now be used on a continuous basis by means of the zone-void method described in this paper. Feed enters, at an intermediate point, a column down which molten zones travel, and waste and product leave at the ends. Materials move in the column through the agency of voids, which are introduced at the ends and travel toward the feed inlet. The voids and molten zones are moved by external heaters in a simple manner, and the principle of reflux is utilized. ANEW method of obtaining multistage separations by crystallization was described recently.' Named zone-refinina.,-, the method comwrises slowly passing a series of molten zones through a long solid charge. Solute becomes concentrated at one or the other end of the charge, depending on whether it raises or lowers the freezing point of the solvent. The separation increases with the number, P, of zone-passes, approaching a limit as P approaches infinity. Zone-refining has been highly effective in purifying germanium and other substances.2,3 and new applications are steadily increasing. Zone-refining is a batch method and as such it has certain limitations inherent in batch operation. If it could be made continuous, its scope and utility would be greatly broadened. This end has been achieved by the zone-void method described in this paper. In the zone-void method feed is introduced continuously at an intermediate point in a column down which molten zones travel, while impure waste and purified product leave at the ends. Both the flows of feed, waste and product, and also the travels of the zones, are actuated by external moving heaters in a simple manner; and the system utilizes the principle of reflux. The method provides, in the field of crystallization, the counterpart of the continuous fractiona-tion column in the field of distillation. The following will be discussed: apparatus and mode of operation, fundamental nature of the separation, design theory, and practical considerations. The method will be described in terms of a binary solute-solvent system in which the solute is an impurity to be removed and the solvent is the desired product. The distribution coefficient, k, defined as the ratio of solute concentration in the solid freezing out of a molten zone to that in the liquid in the zone, is assumed to be constant and less than one. The process is equally effective for k's greater than one and for ternary or higher order systems. Method and Apparatus The essential features of a continuous zone-refining process are represented in highly generalized form in Fig. 1. A series of molten zones, produced by moving heaters, travels slowly down the column or charge (to the left in Fig. 1). If there were no flows of feed, waste, or product, the process would simply be batch zone-refining, the action of the molten zones being to sweep solute down the column, solvent up the column. For the process to be con- tinuous, with stripping and enriching sections in the column, feed must enter, and waste and product must leave, as indicated. The zone-void process accomplishes both objectives, namely, the indicated movements of zones and the indicated flows of material. Zones are moved by moving heaters, just as in batch zone-refining. Materials are made to flow by creating voids at the waste and product exits and causing these voids to move to the feed inlet. Since there must be a net flow of material from the feed inlet to each of the outlets, the indicated movements of voids are in the desired directions, because movement of a void in a given direction corresponds to flow of material in an opposite direction. In order to produce the desired movements of voids, the column is folded into two vertical sections having the feed inlet in common at their upper ends. Voids are displaced upward by the liquids in the molten zones and their travel is actuated by the motions of the zones. Voids travel with the zones in the enriching section and move continuously. Voids travel opposite to the zones in the stripping section and move intermittently. Creation and travel of voids will now be examined in detail. The enriching section of a column in operation, with its void generator, is shown in Fig. 2. The column section is a vertical tube around which a series of closely fitting, regularly spaced heaters travel slowly upward. Each heater produces a molten region, the temperatures of the heaters and the cooling between heaters being controlled so as to maintain the molten zones approximately constant in size. A void is normally present atop the molten zone in each heater. As the heater rises, it continuously melts solid above it, which drips through the void into the molten zone and continuously freezes out solid below it, of concentration k times that of the liquid in the zone. When a molten zone and void reach the feed inlet, which is kept molten, the void is displaced by an equal volume of feed liquid. Generation of voids of controlled size in the enriching section is shown in Fig. 3. The void generator is a tube of small cross-section, provided with lateral heat-conducting fins which sense the position of the heater. Liquid can escape only when the entire outlet tube is within the heater. If any part of the outlet tube is outside the heater, liquid cannot escape,

Jan 1, 1956

By William Lyman

GENERAL DESCRIPTION Shrinkage or shrinkage stoping refers to any mining method in which broken ore is temporarily retained in the stope to provide a working platform and/or to offer temporary support to the stope walls during active mining. Since ore "swells" when broken, it is necessary to shrink the muck pile a corresponding amount by draw¬ing some of the broken ore out as the stope is advanced-hence the name. Broken ore retained during stoping is drawn out after the stope has reached its limits. The stope may be left empty or may be filled with waste contemporaneous with, or subsequent to, the final draw. Traditionally the method implies conventional overhand stoping methods with miners working between the muck pile and the stope back, in a space which advances updip with mining and is maintained by balanc¬ing "swell" with "shrink." The shrinkage classification is also applicable to so-called "semishrinkage" methods in open pillar-supported stopes where broken ore is temporarily retained as a working platform but offers no wall support; and to various blasthole shrinkage methods which utilize broken ore temporarily retained in the stope for wall support, but which do not require miners to work from muck pile in the stope. The method is generally applied to steeply dipping veins of strong ore between strong walls. APPLICATION Geometry The geometry of a shrinkable vein is described in terms of dip, width, and regularity along dip. Overall strike and dip dimensions and irregularities along the strike generally impose no restrictions on the method. Dip is ideally 1.2 to 1.5 rad (70 to 90°). As dip falls below 1.2 rad (70°), the shrinkage draw begins to strongly favor the hanging wall side, thus leaving a poor working platform for conventional overhand work. This is particularly true in relatively wide stopes. The sup¬port afforded to the hanging wall also diminishes with decreasing dip, reaching nil as the dip approaches the repose angle of broken ore. Dips below 0.78 to 0.87 rad (45 to 50°) are not generally shrinkable except by open stope "seinishrinkage" methods. Minimum mining width is fixed by working space requirements in the stope-generally about 1 m. Shrink¬age in narrower veins requires that waste rock from one or both walls be broken with the ore and the attendant dilution accepted to achieve the minimum width. Nar¬row stopes are less suitable, encouraging hang-ups and bridging of broken ore, with the attendant problems of erratic draw and incomplete recovery of broken ore. Maximum practical width may be 3 m or less to over 30 m, depending upon the competency of the ore and its ability to stand unsupported across the stope back. This is a vital safety consideration in conventional over¬hand stopes, but is much less of a factor in blasthole shrinkage methods. Very wide veins and massive ore bodies have been mined by transverse vertical shrinkage panels separated by transverse vertical pillars which are either abandoned or recovered later by other methods. Regularity along the dip is a prerequisite of shrink¬age as there must be no serious obstruction to the flow of broken ore downward through the stope to the sill level. Gentle rolls along the dip are acceptable if the local footwall dip everywhere exceeds 0.78 to 0.87 rad (45 to 50°). Off-dip hanging wall and/or footwall splits can generally be mined selectively from a conventional shrink stope as they are encountered without ad¬versely affecting subsequent continuation of shrinkage mining updip on the main vein. Vertical offsets or major rolls along the dip which cannot be "smoothed over" generally require that a sublevel be established with new draw control development. Blasthole shrinkage methods are much less flexible (and thus less selective) in their ability to accommodate any of these irregularities. Ground Conditions The wall rock must be strong enough to stand with the minimal support afforded by the dynamic mass of broken ore in the stope. During active mining, local sloughing from the walls is restrained, but the broken ore affords little, if any, useful resistance to closure of the stope walls. Such squeezing, if present, may bind up the stope and cause the loss of much ore. Pillars left between and/or within stopes are effective in preventing closure but reduce overall recovery. Walls may be re¬inforced by bolting after each stope cut in conventional shrinkage but not in blasthole shrinkage. Ore in place must be strong enough to stand with no natural support across the stope width, although tem¬porary artificial support or reinforcement may be used locally in conventional stopes. Some spalling or sloughing is permissible in blasthole shrinkage as men are never present in the stope. Physical and/or mineralogical characteristics of the broken ore may impose restrictions on stope design and/or operational plan¬ning, and may even preclude the use of shrinkage al¬together. Examples include: ores which, when broken, are cohesive or which tend to pack or cement together under the influence of ground water, wall pressure, and/ or chemical reaction. Such conditions precipitate er¬ratic draw during mining and often result in difficult and/or incomplete final draw; pyritic ores which oxidize very rapidly in the stopes and may generate heat, imposing a fire hazard by spontaneous combustion; sulfide ores which oxidize sufficiently in the stopes to adversely affect mill recovery by flotation; and ores (es¬pecially those containing uranium minerals) which ex¬ude radon gas and thereby impose ventilation constraints on stope design. In most cases these problems can be minimized by limiting the size of stopes, by minimizing the duration of mining activity in each stope, and by promptly drawing each stope empty following comple¬tion of mining.

Jan 1, 1982

By R. E. Smallman

R. E. Smallman (University of Birmingham, England)—Recently, Tedmon and Ferriss11 have determined the yield stress parameters oi and ky for tantalum by measuring the lower yield stress as a function of grain size 2d and fitting the results to a relationship of the form They report that although ky , which is taken to be a measure of the dislocation locking strength, is small (- 2 to 4 x 106 cgs units) a substantial yield drop is nevertheless observed in a normal tensile test. Niobium gives a similar result,12-14 as pointed out in the original work by Adams et a1.,12 and in order to check this apparent anomaly the yield-stress parameters of electron beam-melted niobium have recently been reanalyzed15 by the Luders strain technique. In this method the strain hardening part of the stress-strain curve is extrapolated to zero plastic strain; the intercept on the preyield portion of the curve is taken to give oi, whilst the difference between oi and the lower yield stress gives kyd-1/2. The results indicate that ky increases with increasing grain size and hence, a plot of vs d-112 yields an apparent ky, which is lower than the true value. A similar effect could account for the small ky found in the relatively pure tantalum used by Tedmon and Ferriss. The variation of ky with grain size shows that dislocations are more strongly locked in coarse-grained specimens than in fine-grained samples. In niobium, this may be attributed to the fact that the dislocation density in the fine-grained material is higher than that found in the coarse-grained samples which are given a sufficiently prolonged anneal to remove any residual substructure and, since the metal contains only a small amount of interstitual impurity, a variation in locking occurs. By contrast, application of both the grain size analysis and the Luders strain method to yield-stress data from commercially pure vanadium containing a large amount of interstitial impurity gives consistent values of oi and ky, with ky independent of grain size and temperature. Electron microscope observations show minor variations in dislocation density from grain size to grain size, but in any case in this material the dislocations are heavily locked with precipitate. On yielding new dislocations are generated and, as a consequence, the importance of any differences in dislocation density between the various specimens of different grain size is considerably reduced. It is perhaps significant that Adams and lannucci,16 working with a grade of tantalum containing a higher interstitial content than that used by Tedmon and Ferriss, prepared the specimens of different grain size by annealing in the temperature range 1500" to 2000° C to minimize any differences in dislocation structure, and found that ky had a value of 1.04 x 107 cgs units, independent of testing temperature. Such behavior is consistent with the dislocations being locked by carbide precipitates so that the generation of free dislocations is an athermal process. The recent work of Gilbert et al.17 also shows that in tantalum there is no significant variation of ky with grain size provided it contains 150 ppm of oxygen. In this case, however, the dislocations are not locked by precipitate and ky is temperature dependent. C. S. Tedmon and D. P. Ferriss (authors' reply)— We would like to thank Dr. Smallman for his interesting comments and discussion to our paper, "The Dependence of Yield Stress on Grain Size for Tantalum and a 10 pct W-90 pct Ta Alloy".18 It was suggested that perhaps the relatively small values obtained by us for ky of tantalum could be attributed to the same cause that accounts for the apparently small values of ky that result when it is determined by the Luders Strain technique. Since our values were obtained by plotting the lower yield stress vs the reciprocal of the square root of the grain size, it is not clear how this could be the case. The values of ky in this experiment have been calculated, using the Luders strain technique. With this method, values for ky on the order of 2 x 105 to 5 x lo6 cgs units were obtained. In spite of this rather large variation, the magnitudes are still small, and there appeared to be no good correlation between ky and the grain size or the yield stress, probably because of the difficulty in accurately extrapolating the work-hardening portion of the curve back to zero plastic strain. As was shown in the original data,18 there was little work hardening in any of the curves, at any temperature. In his discussion, Dr. Smallman also points out how ky has been observed to increase with increasing grain size, when determined by the Luders strain technique. There are at least two possible explanations for this. In the first case, if it is assumed that the bulk of the interstitial impurities are concentrated at the grain boundaries, then, of course, the available grain boundary area would decrease with increasing grain size, thus presenting less area for the interstitials, which would then presumably increase the concentration within the grains, thereby increasing the locking of the dislocations. In the second case, the increase in ky with increasing grain size would be attributed to the nature of the grain boundary itself. One of the several ways of deriving the Hall-Petch equation19 is based on the stress concentration arising from a pile-up of dislocations at the boundary. The ability of the stress concentration to unlock a source in a neighboring grain would depend on the strength of the grain boundary. As is well-known, the nature and struc-

Jan 1, 1963

The September General Meeting of the Institute was held in Kelvin House, Johannesburg, on 16th September, 1970, at 3.00 p.m. Mr V. C. Robinson (President) was in the Chair. There were also present one hundred and eighteen Fellows, including Dr J. M. Bereza, H. P. Carlisle, R. J. C. Goode, Dr J. P. Hugo, P. Lambooy, Prof R. P. Plewman, W. W. Malan, Dr J. T. McIntyre, Dr M. D. G. Salamon, L. W. P. Van den Bosch, P. A. von Wielligh (Council Members), A. Bain, G. P. Bennet, D. L. Carson, G. L. H. Diering, M. E. E. Douglas, F. A. B. Fouche, R. Fourie, A. R. C. Fowler, E. B. Gordon, J. S. Hay, G. H. Henderson, S. D. Hill, A. C. Hofmeyr, J. M. Jacobs, A. F. Lee, D. G. Malan, L. J. Prince, W. G. Pyne-Mercier, A. H. Mokken, Dr W. S. Rapson, R. R. Richardson, H. V. Solomon, C. G. Sowry, G. G. Stanley, G. R. Still, D. L. Starkey, D. L. Taylor, E. W. Thiel, I. E. Van Aswegan, M. van Ryneve1d Steyn, N. B. Vinson, H. Wheeler, Dr A. Whillier, R. A .Wilson, C. F. Ziervogel. Forty-two Members including R. C. Bertram, F. Collier, G. C. Currie, O. Davel, J. M. Gosnell, A. Hazell, Dr N. C. Joughin, F. Kleinschmidt, D. Love, R. B. Macgillivray, D. Mather, R. D. R. Munro, R. S. Pearson, J. J. Peisl, T. J. Pole, A. J. Rossouw, R. G. B. Skirving, G. S. Schwartz, K. Stee1e, H. A. G. Slater, A. Taylor, B. A. Thomas, P. L. Vaughan, D. T. Watt, W. Wilson. Nineteen Associates including R. K. Briggs, S. I. Du Preez, P. G. Gaylard, P. H. Hartslief, W. M. Mackay, A. D. Ross. Three Students: V. S. Care, R. J. Drummond, P. J. Pretorius. Thirty-one Visitors including C. P. S. Barnard, D. W. Bosch, M. Bain G. L. Brown, G. D. Behrens, C. Coetzer, D. M. Gilbart-Smith, R. L. Man, Dr G. J. Stander, M. W. L. Steinobel, R. H. E. Thorpe, T. D. van Wyk, P. H. van Zyl, E. Vereecken, J. J. H. Viljoen. Secretary, D. C. Visser. Total present: 215. OBITUARIES The President: "It is my sad duty to announce the death of the following: Bruce Donaldson Crawford, Fellow, who joined the Institute in 1951 and passed away on 29th April, 1970. Donald Joseph Powrie, Life Fellow, who joined the Institute in 1935 and passed away on 22nd July, 1970. As a mark of respect to the memory of the deceased and in sympathy with the bereaved I would ask you all to rise and observe a few moments' silence." MEMBERSHIP The President: "I have much pleasure in announcing that the names of the under-mentioned candidates, having been published in accordance with By-Law 5.2.2, Council has elected them to membership of the Institute in the following grades: Associate: WiIliam Norman Carter. Students: Roman Michael Dabrowski, Sean George Dean Eaton, Alan Philip Stonham Howard, Anton du Preez Roos, Richard Harold Tourle. MEMBERS TRANSFERRED TO A HIGHER GRADE From Graduate to Member: Terrance Alexander Ward. From Associate to Member: Bernard Andre Thomas. "I welcome the newly elected members to the Institute and congratulate the members who had been transferred to a higher grade." CO-OPTION The President: "I wish to advise members that, in terms of clause 3.9 of the Constitution, Mc. H. P. Carlisle had been co-opted to serve on Council." PAPERS FOR PRESENTATION The President: "We have two papers today, and I am first going to call on Dr Stander the Head of the Water Division of the C.S.I.R., who IS well known to many of you for his work and talks on pollution, who has had more than a little to do with this industry, and who has been I would say, of the greatest possible assistance to the mining industry in overcoming the problems of pollution which are so prevalent in industry of this nature. He, Mr Henzen and Mr Funke have written this paper, 'The disposal of polluted effluents from mining, metallurgical and metal-finishing industries, their effects on receiving water and remedial measures.' This is the Water Year, as you know, and it is most appropriate that we should have such an authority to talk to us on this very important topic. I now have much pleasure in asking Dr Stander to introduce his paper." After the presentation of the paper the President said, "Gentlemen, I am sure that you would like me on your behalf, to thank Dr Stander very sincerely for a paper which I think has enabled us to get a completely new slant on the Water Year. There are many people who have put their finger on this campaign and said, it is all a gimmick. There are others-I suppose notably some of the bridge clubs which operate on week-day afternoons in Parkview-who seem to think that this is a quick way of getting early rain. Of course, it is not. This is a most important paper which we have had given to us this afternoon. You probably found it here when you arrived and have not read it-I was very lucky to be able to read it last night, and there is an awful lot of meat in it. For as long as I have been associated with mining in any way, there has been a problem of polluted effluent-of effluents carrying a mineral load from mining, and I think Dr Stander is absolutely right-and, of course, the Commission is right when they say that this is not merely the problem of mine management or mine owners-this is a problem which affects every single human being in this country.

By F. W. Bryan, D. H. Lynch

Introduction This paper is a general description of current central Florida phosphate mining, beneficiation, and product transportation. It is directed and believed to be of interest to engineers not familiar with this industry. Deposit: The phosphate deposits of central Florida are generally located in a five county area which includes Polk, Hillsborough, Hardee, Manatee, and DeSota counties. Geologically, the deposit is of marine origin and is identified as the Bone Valley formation. This formation is Pliocene to Recent in geological age and overlies a Miocene limestone formation known as the Hawthorn. The Bone Valley formation sediments are regionally characterized by equal proportions of apatite, quartz, and clay. The clay is predominantly of the mont-morillonite family. On a local scale, however, the proportions of these three major constituents vary considerably. The phosphate occurs as the apatite mineral (Ca 10F2(PO4)(6) and with the clay and sand, the minable ore is commonly referred to as matrix. This matrix is overlain by unconsolidated overburden of sand and sandy clays, ranging in depth from 10 to 45 ft. The matrix usually occurs in fairly horizontal continuous beds from 3 to 25 ft in thickness. The bedded limestone formation lies directly below the matrix and is generally well defined. The phosphate particles range from 3/4 in. to 200 mesh (Tyler) in size. The phosphate particles coarser than 14 mesh are called pebble phosphate and those less than 14 mesh are termed flotation feed which, when beneficiated, subsequently become concentrates. Through mining and beneficiation, phosphate quality is measured in BPL percent which stands for bone phosphate of lime units. In subsequent chemical manufacturing, the quality is indicated by P205 content. The deposit is economically characterized by various ratios such as tons of product per acre and cubic yards handled per ton of product. Magnesium, iron, and aluminum content are also considered in evaluating ore reserves. These elements are often critical to the chemical fertilizer processes. Presently, an ore body is considered economically minable if it meets the criteria shown in [Table 1]. These, of course, are general guidelines and specific costs and returns on investment must be considered in each case for acquiring reserves. On a new grass-root venture, a 20-30 year life is generally expected with a mineral recovery of 80%. History and Uses Phosphate mining in central Florida began around the turn of the century. However, in the early days, only pebble phosphate was produced until about 1930 when technology was available to beneficiate the -14 + 150 mesh particles. The -150 or -200 mesh material was discarded as it is today. The basic processes for beneficiation are washing, scrubbing, desliming, sizing, and flotation. These basic unit processes are essentially the same today although many improvements have been developed since the early days. Phosphate is used primarily in the production of high analysis fertilizer chemicals, typical of which are triple superphosphate, monoammonium phosphate (MAP), and diammonium phosphate (DAP). Phosphate is also used in the production of food preservatives, dyes for cloths, vitamin and mineral capsules, steel hardeners, gasoline and oil additives, toothpaste, shaving creams and soaps, bone china dishes, plastics, optical glass, photographic films, light filaments, water softeners, insecticides, soft drinks, road fill, and livestock feed supplements. Florida produces over 80% of the nation's marketable phosphate rock and one-third of the world production, according to the US Bureau of Mines. This amounted to approximately 35 million tons in 1975. Exports of Florida phosphate rock were to such countries as Canada, Japan, West Germany, Italy, and India, with Canada and Japan being the major users. Almost 95 o of all outbound cargo shipped through the port of Tampa is phosphate rock or related products. Beneficiation Following is a description of Agrico's new Fort Green beneficiation plant which is typical of the newer large capacity plants being built in the field. Agrico's Fort Green mine was completed in 1975 and is located in the southwest corner of Polk County and is directly adjacent to Manatee, Hillsborough, and Hardee Counties. With some minor differences, Fort Green is typical of a modern central Florida plant. The rated capacity is 3,000,000 plus tons of product per year and this varies according to the richness of the ore being handled. A simplified flowsheet is presented in [Figs.1 and 2]. This plant is served by three draglines of the 40-cu-yd class. The phosphate beneficiation is usually divided into three major functional steps: (1) washing and screening to produce a pebble product and flotation feed, (2) feed preparation and (3) flotation to produce concentrates. The typical plant is similarly divided into these three functional areas. Washer: Briefly, the slurried matrix is pumped from two draglines simultaneously at a combined rate of about 20,000 gpm at 2000 tph (solids) to rotary trommel screens sized to make a 7/8-in. separation. ([See Fig. 1]-) The trommel oversize is sent to hammermills where it is crushed and returned to the trommel screens, or pumped to tailings if minor impurities (Fe203, A1203, MgO) are too high. The trommel undersize is pumped to 14 mesh stationary (static) flat screens. The flat screen over¬size is subjected to three stages of 14 mesh vibrating screening and two stages of log washing in order to produce a final pebble product. The pebble product (+ 14 mesh material) is conveyed by belt conveyor to a large on-ground storage pile. Pebble product is reclaimed through a tunnel and loading system below

Jan 1, 1980

By C. W. Merrill

The price records of seven representative mineral commodities for the 68-year period 1890 through 1957 have been compiled and analyzed for significant trends. When these records are reduced to real prices in terms of dollars of constant purchasing power or to the purchasing power of industrial wages at average rates, a substantial overall fall in prices is revealed. This downtrend contradicts the widely held concept that heavy drafts on a mineral resource must lead to scarcity, reflected in rising prices. Three metals (aluminum, copper, and pig iron), two fuels (bituminous coal and petroleum), and two nonmetals (sulfur and cement) have been chosen because of their pre-eminence in their respective categories, their significance in an industrial economy, and the ready availability of their price records. It might be added that these seven commodities were selected before any price figures were compiled; none was selected or rejected to substantiate any preconceived notions as to price trends. The overall importance of the seven is demonstrated by the fact that, taken together, they composed over three-fourths of the value of all minerals produced in the U. S. in 1957. The first step in the analysis was to reduce the price records to a basis for significant comparisons. Two such comparisons have been made: 1) The quantities of each of the commodities that could have been purchased for an average hour's wage in each year, and 2) the unit price of each commodity through the years in terms of deflated dollars. These data are set forth in the accompanying table and two charts. The quantities of the mineral commodity purchasable with the average wage for one hour's work in all manufacturing industries through 1926 were based on annual average prices and on average annual wage rates determined by Paul H. Douglas and published in his "Real Wages in the United States, 1890-1926." The series was extended through 1957 by the Bureau of Labor Statistics, U. S. Department of Labor. Calculations based on these data show that the average worker could have purchased 1.28 lb of copper with his hourly wage in 1890, whereas his hourly wage would have purchased 8.11 lb in 1957, an increase of 633 pct in the 68-year period. An average hour's wage would have bought 10.85 gal of petroleum in 1890, compared with 33.04 gal in 1957. Even more spectacular is the increase in sulfur, of which 25.25 lb could have been purchased with the 1904 average hourly wage; 223.08 lb were purchasable with the wage in 1957—an increase of 883 pct. Comparable price data for sulfur are not available for years earlier than 1904. For every commodity, the calculations show an improvement in the wage earner's purchasing power in 1957 compared with the early years. Measuring purchasing power in terms of wages does not give an entirely fair picture of the availability of a commodity in an economy. When the efficiency of an economy changes and the balance shifts among such elements as raw-material production, manufacturing, and service trade, the economic significance of an hour's work changes. Partly to meet such criticism, but mostly to present another interesting measure of the response of minerals to changing market conditions, a second set of calculations has been made to deflate unit prices for the seven commodities into terms of 1954 dollars. To accomplish this adjustment to a common 1954 parity, the Gross National Product Price Deflator, developed by the Office of Business Economics, U. S. Department of Commerce, was used. Although the results of these calculations are not as striking as those based on labor's increasing purchasing power, nevertheless the declines outweigh the rises in the prices of the mineral commodities. In terms of these deflated prices, aluminum and sulfur are much cheaper today than in the early years; copper was substantially cheaper in 1957 than in 1890; pig iron and petroleum are little changed; and only bituminous coal and cement have increased substantially. Strangely, the two mineral commodities with the strongest reserve positions are the two to exhibit rising real prices. Now this apparent overall downtrend in prices has taken place during a period of almost fantastic increase in the demand for mineral products. The value of minerals consumed in the world during the period greatly exceeds all mineral consumption up to 1890. A stage has been reached in the U.S. in which 95 pct of the energy used is of mineral origin and in which machines, structures, roadways, communication facilities, and most other elements in the industrial economy are primarily of mineral origin. Even agricultural fertility is maintained, in large measure, by mineral fertilizers. A series published in Minerals Yearbook shows that the value of U. S. mineral products has risen from $615 million in 1890 to $18,000 million in 1957, a 29-fold increase. Even in deflated dollars, the increase has been eightfold, while population has expanded less than threefold. Not only are demands of the industrial nations— the U. S., countries of Western Europe, and Japan— increasing at rapid rates, but those countries with agrarian economies are calling themselves underdeveloped and clamoring to industrialize. The ever-expanding mineral requirements in the U. S. and throughout the world show no abatement. Mineral reserves frequently have been described as wasting assets. Much concern has been shown for future users, who have been pictured as finding themselves on a plundered planet. Conservationists have viewed the future with alarm and have demanded legislation and regulations to reduce the drain on mineral reserves.

Jan 1, 1960

What is the preferred electrolytic cell design and why? Hall: Considerable research remains to be done on electrolytic cell design. Studies are presently being conducted to determine optimum voltage and amperage. Zadra cells, which were used in some of the first carbon plants, are efficient when properly installed. Gold and silver are deposited on large-capacity, cylindrical steel wool cathodes. At times high value sludge falls from the cathode to the bottom of the cell. Rectangular cells, which were developed at some smaller operations in Nevada, require less floor space and have some desirable features in that cathodes can be moved and sludge can be removed from cell bottoms without actually shutting down the circuit. In South Africa two types of cells using graphite and diaphragm configurations are being tested. Duncan: The rectangular cell has one problem it's easy for shortcircuiting to occur. If you don't have a good seal on the side of the tank and on the bottom, the solution is going to want to flow around the bottom and sides of the cathodes and you're going to get poor performance in the cell. That is the advantage the Zadra cell has over the rectangular cell. With good sealing, which is a must, you should be able to get a ratio of the value of the solution going in to the value of the solution coming out of 10 to 1. Ken, can you tell me what you're attaining on the Zadra? Hall: At the Homestake gold operation in Lead, the cathode in the No. 1 electrowinning cell is loaded to about 600 ounces when it is moved to the refinery. At this time the No. 2 cathode is moved to the No. 1 cell. The No. 3 cathode is moved to the No. 2 cell and a cathode with new steel wool is placed in the No. 3 cell. In rectangular cells this sometimes is not possible because the loading on the cathode in the last cell may be as high as that in the No. 1 cell. As Don has pointed out this can probably be prevented by good seal design between cathodes. Potter: At the risk of sounding as though I'm straddling the fence, I really believe that either the round cell, as developed by Jack Zadra, or the rectangular cell will do an acceptable job. The Zadra is a fine unit. Leaks are not unknown but there are not very many. However, the rectangular cell is very saving of floor space. Plastics have been greatly improved during the past year or two and there is a very efficient design for the rectangular cell. It would have six cathodes in it and contain about 25 ft of steel wool. The body of this rectangular cell would be reinforced fiberglass plastic but with an integral lining of a high temperature plastic. I think either cell is so efficient and reliable that I would almost be tempted to flip a coin depending on floor space requirements. Either cell can be used to pull a loaded cathode and to advance the lesser loaded cathodes. Don, what is the configuration of your cell? Duncan: The Pinson rectangular cell has dimensions 2 ft wide, 30 in deep, and 10 ft long-long enough to take a dozen cathodes and anodes. We are currently using six of each but are not up to full capacity as yet. It's a steel tank coated with rubber. We have copper bus bars, which brings to mind that the last cathode in the tank, in one instance, was loaded heavier than the first one. That was probably a function of poor contact between cathodes and the bus bar. You can have erosion of the bus bar and if you don't get current flowing into the anode and out of the cathode, the cells will not function properly. Kappes: Just a few comments on cell design. In an alcohol stripping circuit we are running in Beatty„ NV, we are using PVC pipes for all circuitry piping and a commercial polypropylene electrolytic cell. They seem to be working quite nicely. The cell itself has eight cathodes measuring 18 in2. At six gallons per minute flow into the cell, at an average gold content of about 500 ppm, we seem to get good loading on the first three to four cathodes and not much on the end cathodes. At 12 gallons a minute flow we seem to be seeing gold uniformly along all eight cathodes. We are running at quite a high amperage level, about 400 amps into that cell. Gene McClelland, US Bureau of Mines, Reno Research Center (from the floor): I was associated with a company where the packing density of their steel wool cathodes was much too high and created some short-circuiting problems in their electrowinning circuit. I would like to ask the panel if they can recommend a packing density for cathodes in pounds of steel wool per cubic foot. Hall: The weight of steel wool put on one of our cathodes is 10 lb and the dimensions of the cathode are such that density would be about 0.75 lb/ft3. Duncan: I made a rough calculation and I'm estimating about 2 lb/ft3. Potter: In checking over a number of electrowinning operations, I found apparently very satisfactory operation within the limits that have been mentioned. I have come to a figure of about 0.5-1.0 lb of medium grade steel wool per cubic foot packed as uniformly as possible, of course. One consideration in packing is the fact that there should be good contact between the steel wool and the conductor. Operators tend to compact the steel wool more than would be desirable just to try to maintain good contact.

Jan 10, 1981

By Unkown

The Province-wide road ban on movement of heavy loads has had the effect of curtailing or stopping development in several areas. In the Leduc area, the discovery well has been restricted in flow to only a fraction of normal due to limited storage space, but drilling at Imperial Leduc Nos. 2, 3, and 4 has been continued for the past few weeks. The No. 2 well is within 100 feet of the producing horizon and should be completed within the next few days. According to reports, it has been logging slightly lower, structurally, than the discovery well, but, regardless of the outcome, it has been an important test to determine westerly cross-section of the Leduc structure. No official reports have been made available of any tests made during the drilling of the well, but it is understood that promising oil and gas shows have been indicated in higher formations. Actual drilling operations have not been commenced by any of the other companies holding leases in the immediate area but it is expected that, when road bans are removed and equipment is assured, several wells will be commenced. Announcement has been made that Imperial Oil, Limited, will drill a well near Battle lake, about thirty-five miles southwest of the Leduc field. Location of the well has been made following an extensive seismograph survey of the area, with total depth of the test well expected to be in the 8,000- to 8,500-foot range. Drilling will be done with the heavy-duty rig last used at the De Winton test. Imperial Oil have abandoned hope of oil production in the Provost area after drilling nine wells, but will retain their interest in the gas field that has been developed. Of the wells drilled, four indicated gas flows ranging from 1,060 to 13,200 M.c.f. per day.

Jan 1, 1947

Edward Keller, Baltimore, Md. (communication to the Secretary): When, at the New Pork meeting, February, 1899, Mr. Douglas gave an abstract of his highly interesting paper on the Copper Queen mine, he invited the members of the Institute, in his usual progressive spirit, to make a full scientific investigation of the region of that mine during the prospective excursion to Bisbee, Arizona. I volunteered to examine some of the metallurgical processes and products of the works, and obtained from Mr. Douglas a valuable series of samples. Upon the issue of his paper, however, I found that he had already a considerable volume of analyses of those products, and that little was left for me to do in that respect, except to duplicate his results, the importance of which work would not have been commensurate to the time and labor involved. I selected, therefore, only some points which he had not made entirely clear, or concerning which I was skeptical. The details of most of my work will appear in a future paper. From Mr. Douglas's figures I have calculated the values for the elimination of impurities in the so-called Leghorn converter, introduced by him at the Copper Queen works, and have found them to be as follows: Percentage of Elimination of Impurities in Pour Blows of a Converter. No of ' Selenium Sulph'r Iron. Zinc. I Nickel. Lead. Antimony Arsenic. and Blow- ! Tellurium .. 1.......... 99.4 99.6 88.0 92.6 94.4 81.6 83.8 40.3 2.......... 99.0 99.6 98.1 92.5 96.8 71.9 76.6 38.1 3.......... 98.8 99.5 93.5 91.4 96.3 63.8 80.6 25.3 4.......... 99.8 99.5 95.8 95.8 97.5 65.3 76.9 36.3 Average 99.2 99.6 93.8 93.1 . 96.2 70.6 ! 79.5 35.0

Jan 1, 1900

By C. G. Dunn

According to a recently suggested effect of silicon on the re recrystallization textures of high-purity Fe-Si alloys with (111)[112] type rolling textures, the recrystallization texture for a rolled (110)[001] oriented iron crystal probably should be entirely different from that of a (110)[001] oriented 3 pct Si-Fe crystal. Comparative studies of iron and 3 pct Si-Fe crystals, however, show that both have (110)[Ool] recrystallization textures when the rolling textures are the (111)[112] type after reductions in thickness of about 70 pct. Qualitatively the results from the iron crystal are like those of polycrystalline high-purity 3 pct Si-Fe and not like polycrys-talline high-purity iron. The large effect previously noted probably involves unknown impurities or processing variables rather than silicon itself. Some problems on experimental and analytical procedure for a spherical X-ray specimen, which was machined from a laminated composite of sheet specimens, are treated in the Appendix. A possible strong effect of silicon on the textures produced in cold-rolled high-purity Fe-Si (HPFe-Si) alloys during primary recrystallization and normal grain growth was suggested in a recent paper.' All the textures were far from the random-orientation type, but that of iron, or of Fe-Si alloys of low silicon composition, was entirely different from the texture of 3 pct Si-Fe. The same effect was noted for the textures obtained prior to normal grain growth, i.e., for primary recrystallization.2 It is the main purpose of the present paper to provide some clarification of this silicon effect. All the HPFe-Si alloys from zero to 3 pct Si, which were rolled by two or more stages separated by anneals, developed (111)[112] type rolling textures.2 Thus, there was no effect of silicon on the rolling textures. Earlier, Gensamer and Mehl3 also found no effect of silicon on the rolling textures of Fe-Si alloys; they obtained the Kurdjum.ow and Sachs (K-S) rolling texture for iron,4 which is characterized as the three ideal components: (100)[011], (112)[li0], and (111)[112]. There is a difference between the HPFe-Si multiple-stage rolling texture and the K-S single-stage rolling texture, but this is a variable processing effect. Of interest here is the fact that the recrystallization textures from (111) [llZ] type rolling textures were different depending on the amount of silicon in the alloy. There was a relatively strong (110) [001] component in the recrystallization texture of HP 3 pct Si-Fe5,8,2 but no such component in HP 0.6 pct Si-Fe, for example; the recrystallization texture for the latter was two (111) [110] type components and a (111) fiber component 1,2 Several publications have shown that a strong (110) [001] recrystallization texture is derivable from a (111) [112] type rolling texture for 3 pct Si-Fe crystals reduced in thickness by about 70 pct.7-10 Furthermore it appears that the strongest of these (110) [001] recrystallization textures occurred when the orientation of the crystal prior to rolling was (110) [001].7 Barrett and evensoon11 found that the rolling texture of a (110)[001] oriented iron crystal was (111) [llj]. Accordingly, it seemed desirable to determine whether a (110) [001] oriented iron crystal, upon rolling and annealing, would behave like the 3 pct Si-Fe crystal (or the polycrystalline HP 3 pct Si-Fe) and thus produce a (110) [001] recrystallization texture contrary to the suggested silicon effect, or would behave like the polycry stalline HP iron or HP 0.6 pct Si-Fe and thus produce (lll) [110] type components in agreement with a silicon effect. Briefly, the idea here involves the use of more precisely defined textures to obtain if possible better control of important variables that affect the recrystallization process. PROCEDURE A (110) oriented crystal of Ferrovac "E" iron (99.9 pct pure) was prepared in sheet form 0.080 in. thick with the [001] direction parallel to the long dimension of the specimen.'' This crystal was etched to 0.073 in. thickness (to remove some small included grains) and then was cold rolled in a 6-in.-diam mill to a final thickness of 0.022 in. The rolling was unidirectional except for an inadvertent reversal at 0.061 in. thickness. At this thickness, and also at 0.040 in., the rolling was interrupted for transmission Laue photographs. Molybdenum Ka-radiation filtered with zirconium was used in a transmission method1' to obtain the cold-rolled (110) pole figure. The sample was a 0.002-in.-thick section taken from the central region of the 0.022-in.-thick cold-rolled crystal. For the primary recrystallization study, cold-rolled samples were etched from 0.022 to 0.021 in. thick and annealed in hydrogen at 850°C. Primary recrystallization to a fine-grained structure, Fig. 1, was obtained in a 5-min anneal. Eleven sheets after

Jan 1, 1963

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By W. C. Leslie

The textures of cold-rolled and of annealed iron are compared with those of an iron-0.8 pct copper alloy in which the amount of precipitation after cold rolling was controlled. Previously published pole figures -for cold-rolled and for annealed iron are confirmed. The effects of precipztatiotz after cold rolling are to retain the cold-rolled texture after annealing, to inhibit the formation of the usual allnealing texture, and to produce elongated recrys-tallized ferrite grains. It is suggested that the inhibition of new textures by precipitation after cold rolling is a general phenomenon. A great deal of attention has been paid to the development of texture during the secondary or tertiary recrystallization of ferritic alloys, but very little work seems to have been done on the control of texture during primary recrystallization. If such control were attained, it might be possible to simplify the processing of oriented materials or to change the characteristics of current cold-rolled and an-nealed products. From previous experience, it seemed likely that texture could be controlled by recrystallizing a supersaturated solid solution. Green, Liebmann, and Yoshidal found that the formation of preferred orientation in aluminum (40 deg rotation about <111> relative to the deformed matrix) was inhibited when iron was retained in supersaturated solid solution in the strained aluminum. The authors attributed this inhibition to iron atoms in solid solution. There is, however, an alternative explanation. Green et al, took a highly supersaturated solution of iron in strained aluminum and heated it to an unspecified temperature for recrystallization. It is probable that precipitation occurred prior to and during recrystallization, and it is proposed that the inhibiting agent is this precipitate, rather than the iron atoms in solid solution. It is important to note that precipitation before cold work is ineffective; the effective precipitate is that formed after cold working and either before or during recrystallization. The location and distribution of the precipitate are critical. Precipitation in such a manner has been found to have profound effects upon kinetics of recrystallization and the microstruc-ture of the recrystallized alloys.2-4 It would be surprising, indeed, if this were accomplished with no change in texture. Because of the relative simplicity of the system, and because of previous experience,4-7 it was decided to determine the effect of precipitation on texture in an alloy of iron and copper. Bush and Lindsay5 found an unspecified change in texture in cold-rolled and annealed low-carbon rimmed steel sheets when the copper content exceeded 0.1 pct. MATERIALS In earlier work, the rate of recrystallization of a low-carbon steel was greatly decreased by 0.80 pct copper, and, after the proper treatment, the recrystallized ferrite grains were greatly elongated.4 Accordingly, it was decided to investigate the effect of precipitation on texture at this level of copper content. The iron and the iron-copper alloy were made from high-quality electrolytic iron and OFHC copper, vacuum-melted in MgO crucibles, cast, hot-rolled to 0.2 in., then machined to 0.150 in. The compositions are given in Table I. The plates were heated to 925°C and brine quenched, twice. This produced a ferrite grain size of ASTM 0 in the iron and ASTM 1 in the Fe-Cu alloy. Disk specimens were cut from the heat-treated plates, repeatedly polished and etched, then used to determine (110) and (200) pole figures by reflection. Despite the complication of large grain size, these pole figures strongly indicated a random texture. PROCEDURES The copper content in solid solution in ferrite before cold rolling and recrystallization, and hence, the amount that could precipitate during the recrys-tallization anneal, was controlled at three levels by heat treatment. The specimens as quenched from 925° C were presumed to have all the copper, 0.80 pct, in solid solution. Other samples of the quenched alloy were aged 5 hr at 700°C to retain about 0.5 pct Cu in solid solution.6 A third set of quenched specimens was reheated to 700°C, then slowly cooled in steps, to reduce the amount of copper in solid solution to a very low level. All specimens were cold-rolled 90 pct, from 0.150 to 0.015 in. thick. The rolling was done in one direction only, i.e., the strip was not reversed between passes, with a jig on the table of the mill to keep the short specimens at 90 deg to the rolls. The rolls were 5 in. in diameter and speed was 35 ft. per min. Machine oil was used as a lubricant. In a supersaturated alloy, the maximum effect of the copper precipitate on microstructure and on recrystallization can be developed by a treatment at 500°C, after cold rolling and before recrystallization.&apos;

Jan 1, 1962

By G. Y. Chin, W. L. Mammel

The problem of selection of the active slip systems for a crystal undergoing an arbitrary strain has been analyzed by Taylor and by Bishop and Hill. The Taylor analysis is based on a principle of&apos; virtual work, and involves finding, among numerous cotnbinalions of slip systems that satisfy the imposed strain, the combination in which the sum of the glide shears is a minimum. Previously, Taylor has treated the case of axisymmetric flow when slip occurs on (111)(110) (or {110)(111)) systems only. His analysis has now been extended by computer methods to the cases of slip on {112}(111) and {123)(111) systerns and of mixed slip on {110), {1 12), and (123) planes with a common (111) slip direction, all of which are important in the deformation of bcc crystals. The results are computer-plotted as contours of the ratio of the floe strength to the critical resolved slzea-r stress for slip, for axial orientations distributed throughout the standard stereographic triangle. Implications of the computer results to texture develop,merit, texture hardening, and dislocation theories oj work hardening are discussed. WhEN a single crystal is extended in the usual tension test, the lateral dimensions can change relatively freely. In this case, the glide shear produced by slip on a single slip system is sufficient to accommodate the (tensile) deformation. Since slip is governed by a critical resolved shear stress law (the Schmid law&apos;), the single active slip system is one for which the stress, resolved on the slip plane and in the slip direction, is the highest among the several equivalent slip systems. This amounts to saying that a value M = U/t = y/~ is a minimum among the equivalent systems, where M is the inverse of the familiar Schmid factor (a and E refer to tensile stress and strain, and T and y refer to resolved shear stress and shear strain). A grain embedded in a polycrystalline aggregate, on the other hand, cannot freely change its shape due to constraint from its neighbors. In this case, slip from five independent slip systems (to accommodate five independent strains) is generally required.&apos; Based on the principle of virtual work and assuming that the critical resolved shear stress for slip is the same for all systems, Taylor hypothesized that, among all combinations of (five) slip systems which are capable of accommodating the imposed strain, the active combination is that one for which the sum of the absolute values of the glide shears is a minimum. Again, this is equivalent to saying that the value of M = CjlyjI/ is a minimum, in analogy to the single slip case. Taylor aminimum,analyzed the case of {111)(110) slip for fcc metals, and applied the analysis to crystals undergoing axisymmetric flow, that is, the same macroscopic shape change as the poly crystalline aggregate under uniaxial tension (or compression). For the twelve equivalent {111}( 110) slip systems, there are 384 independent combinations of selecting five systems to satisfy the five independent linear equations of imposed strain.4 Taylor calculated the value of M for each combination* and obtained the active com- *A number of the independent combinations were omitted from consideration in Taylor&apos;s original work (see Ref. 5). bination (minimum M) for a number of axial orientations distributed throughout the standard stereographic triangle. Later work by Bishop and Hill*&apos;8 showed that Taylor&apos;s least-shear hypothesis was equivalent to a maximum work principle which they advanced. Using the simplified Bishop and Hill method for {111)(110) slip, Hosford and Backofen&apos; obtained detailed contours of constant minimum M for the same axisymmetric flow case. In contrast to {111}(110) slip in fcc metals, slip in bcc metals is generally described as occurring on {ll~)(lll), {112)(111), {123) (111) systems as well as mixed slip composed of all three. Since the direction cosines of the slip plane normal and the slip direction enter as a product in the Taylor analysis, the Taylor solutions of ,M for {110)(111) slip are identical to those for { 111} 110) slip. The other three cases of slip, however, have not been solved. In view of the numerous combinations of slip systems involved in the calculations, the Taylor analysis is clearly oriented toward computerized solutions. THE TAYLOR ANALYSIS In order to obtain the active combination of (five) slip systems by solving for the minimum value of M = we first express the (small) strain components E,, with respect to the cubic axes 1, 2, 3 ([loo], [010], [001], respectively) of the crystal, in terms of the sum of the glide shears yj from slip systems j: where n, and n,j refer to direction cosines of the slip plane normal, and dri and dsi to direction cosines of the slip direction, of slip system j, all referred to the cubic axes. In practice, the strain components are given with respect to the specimen axes X, y, 2. These components are readily converted to ers through the tensor transformation where irk and 1,~ are the direction cosines between the two sets of coordinate axes.

Jan 1, 1968

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.&apos; Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967