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By M. C. Makepeace

"It is the objective of designed experiments to obtain more information for less material and process cost than can be obtained by traditional experimentation. In this paper, the fundamental concepts on which the statistical design of experiments is based are briefly re-viewed according to the following outline: The Experiment The Design The Analysis Two simple 2"" factorial experiments are presented as examples."

Jan 1, 1967

By Donald B. Hunter

The Ti-Be system up lo 10 wt pct Be with cortlmercialll' pure titanium has been determined using metal-lographic techniques. Beryllium forms the p eutec-toid type of dinqarz with titanium; the eutectoid occurs at 0.5 xt pct Be azd 1500 F, while an eutectic is foritled at 1887°F containing between 5 and 7.5 rt pct Be. The solubility of beryllium in a titanium does not exceed 0.05 zvt pct and the maximum solubility of Beryllim in 0 titanium is 1 wt pet. PREVIOUS work on the Ti-Be phase diagram indicated that additions of beryllium to titanium resulted in a marked lowering of the melting point,''' and it was also observed that the solubility of beryllium in both a and p titanium was retricted.- With the limited data available, McQuillan and McQuillan constructed a partial hypothetical diagram of the Ti-Be system,= assuming that beryllium formed the 0 eutectoid type of system with titanium. Subsequently Bedford published a tentative diagram of the entire Ti-Be system: although he did not investigate alloys containing less than 10 wt pct Be. This diagram included several compounds described by other authorities.'-l3 The following account describes work directed toward determining the form of the titanium-rich portion of the phase diagram up to 10 wt pct Be. MATERIALS AND METHODS Titanium sponge and a master alloy containing 25 wt pct Be were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 250-g compacts which were melted into buttons by arc melting under purified argon on a water-cooled copper hearth. Results of analyses for beryllium are shown in Table I but no determination of other elements was made at this stage. The alloys were hot-rolled at 1650°F to produce 0.1-in.-thick sheet. Alloys containing up to 1.5 pct Be were fabricated without trouble; samples containing 2 pct cracked initially upon hot rolling, but thereafter rolled satisfactorily to sheet. The 5, 7.5, and 10 pct were hot short and could not be rolled. Surface contamination was removed from samples by sandblasting and pickling in a 5 pct HF-35 pct HNOs solution. For metal log raphic examination, heat-treated specimens were mounted transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and electropolished at 20 v using a solution containing 600 ml of methanol, 60 ml of perchloric acid, 360 ml of butyl cellosolve, and 2 ml of Solvent "X". Difficulty was experienced in obtaining good electropolished surfaces with samples containing more than 1 pct Be, the degree of difficulty in-

Jan 1, 1967

By J. P. Morris

The Bureau of Mines investigated the mechanics of fuming of iron-carbon melts during top-blowing with oxygen. Melts weighing 45 lb were prepared in an induction furnace and blown with oxygen by means of water-cooled lances. The rate of fuming was measured and correlated with the operating variables. The data showed that the primary cause of fuming was a boil at the bath surface in the impingement zone of the oxygen jet. Nucleation of the carbon monoxide bubbles producing the boil was apparently brought about by the precipitation of an oxide phase. The actual fuming mechanism involved partial oxidation and vaporization of bubble films and fine metal spray generated by the bursting of the bubbles. Bubbles that formed outside the impingement zone produced little fume. The distribution of trace elements between the metal and fume strongly indicated that the fume contained fine spray particles as well as particles that had condensed from vapor. The rate of fuming was found to be proportional to the carbon content of the metal) the concentration of oxygen in the jet) and the bath temperature) provided that a continuous boil occurred. In the absence of a boil) very little fume was produced.

Jan 1, 1967

By Bernard Porter

The rate of the heterogeneous reaction between reactor-grade yttrium and lithium fluoride in lithium fluoride-yttrium fluoride mixtures was measured using a quartz spring balance. At 950° C the magnitude of the rate of reaction is 10-5 grams of yttrium/cm2-sec. The heat of activation for the reaction is 38.3 kilocalories per mole of LiF. A surface-controlled mechanism is proposed in which LiF is adsorbed on the yttrium metal surface. An activated complex is formed when additional LiF reacts with the adsorbed LiF-metal site. The activated complex then decomposes to the products) which are lithium metal and YF3. The importance of the reaction in the electrowinning of yttrium metal from fluoride electrolytes is discussed.

Jan 1, 1967

By Maurice Lauzon

"Aerial surveys of the open pits have been conducted regularly at Lake Asbestos of Quebec, Ltd. -a subsidiary of American Smelting and Re-fining Company -since 1958. Ground controls are supplied by Lake Asbestos, and a topographic map of the pits at a scale of 1 in. to 50 ft., with 2-foot contour intervals, is obtained by aerial photography. The information from the topographic map is then transferred by the Lake Asbestos engineering staff to sections from which the volumes removed are calculated. Considering the size and complexity of the operation, this system has proved to be the cheapest, fastest and most accurate way of determining the quantities of rock and overburden removed. More than 11,000,000 tons of ore and waste are mined each year in three different pits. Further-more, the nature, shape and extent of the orebodies make it necessary to mine on many (up to eight) benches of a pit during a single year. In addition, there are sections of the pits where it is impossible or un-safe to survey the crest of some benches by standard ground methods. For these reasons, the tonnages obtained by truck count are checked and adjusted by aerial survey. These surveys are now taking place every six months. With this system, it is possible for a two-man surveying crew to look after all field work in the mine area."

Jan 1, 1967

By C. E. Coleman, D. Hardie, A. E. Wraith

A photoguaplric method of measuring crack velocities has been applied to an examilzation of- the effect of hydrogen on the impact properties of zirconium. Results indicate that the crack in hydrided zirconit travels at about 26 m per sec whereas that in the uacuum -annealed is dependent on the speed of the hammer. RECENT work on the effect of hydrogen on zirconium reveals that when hydrided zirconium is tested in slow bending the crack producing failure can be unstable. The mode of fracture seems to involve the crack linking up broken hydrides by a ductile mechanism in the zirconium matrix.2" In order to compare the fracture of zirconium with that of other metals which show unstable crack propagation, notably steel, the rate of the crack spread must be known. As the methods previously used for measuring crack growth are either unsuitable for the present work5-'' or very costly," a simple technique has been devised in which the maximum crack velocity is derived from a series of crack position-time measurements. EXPERIMENTAL PROCEDURE The experimental arrangement is shown schematically in Fig. 1. The flash unit12 was triggered when the Charpy hammer touched the specimen and the 6-psec flash of the lamp delayed by a preselected time interval in the range 100psec to 10 msec. The camera was left on open shutter during the test. From direct measurement on a calibrated photographic print, Fig. 2, the position of the crack and the specimen was found at a known time after impact and, from a series of such tests using an appropriate range of flash-delay times, the crack velocity was estimated. Preliminary experiments were carried out on mild steel above and below its transition temperature. Vacuum-annealed zirconium, and zirconium hydrided to 100 ppm H were then tested at 20" and 150°C. For comparison, Zr-2.6 pct Nb alloy (in the 0 + transformed /3 condition), vacuum-annealed or hydrided to 100 ppm H, was tested at 20 C. The chemical analyses of these materials are given in Table I. For the high-temperature tests a fine chromel-alumel thermocouple was spot-welded onto each specimen close to the notch. The test piece was heated up to 200°C to allow enough time for preparing the apparatus while the specimen cooled to the testing tem- perature. It was assumed that the specimen cooled uniformly. The accuracy of the flash-delay time was better than i2 pct i 5 psec. The crack length was taken as its maximum distance traveled normal to the length axis of the specimen. Errors in these measurements arise as a result of the uncertainty in the location of the crack tip and the difficulty in defining the exact position of the crack starting point. The latter was due to the bonding and large amounts of deformation at the hammer contact point, especially in the vacuum-annealed specimens tested at 150°C. The maximum error in the measurements was however estimated to be about 5 pct. DISCUSSION OF RESULTS From the trial experiments using mild steel above its transition temperature it can be seen from the plot of crack length against time after impact, Fig. 3. that a reasonable estimate of the maximum crack velocity at the surface of the specimen may be made. Other features of note are the initiation time before the crack is first seen and the slowing down period

Jan 1, 1967

By A. Balint

The Photometric Optical Separation process is introduced and examples of sorting machines are given. Applications of the process are outlined in general terms with reference to specific types of industrial installations. Brief description is given of the capabilities and limitations of available equipment, including cost estimates.

Jan 1, 1967

By W. C. Maurer

Although millions of feet of rock are drilled annually, the basic drilling mechanisms involved are not well understood. The primary reason for this lack of knowledge is because the basic principles of rock failure are not well understood and rock failure is the primary mechanism in drilling. A better understanding of the drilling mechanisms would enable a more scientific approach to the design and use of drills and bits. The paper reviews several models which have been proposed to explain various aspects of the different drilling methods. These models are described and their limitations and areas of application are discussed. Drilling rate relationships are developed and related to the basic rock failure mechanisms. TYPES OF MECHANICAL DRILLS There are three basic methods of mechanically attacking rock: 1) percussive action, 2) rotary action, and 3) combined rotary-percussive action. A percussion drill applies a force perpendicular to the rock surface and the bit moves into the rock perpendicular to the surface, forming a crater beneath it (Fig. 1). A rotary drill applies a constant thrust to the bit while a torsional force moves the bit parallel to the rock surface, breaking the rock ahead of it. A rotary-percussive drill applies both a rotary force and a percussive force to the bit which moves into the rock at an angle to the surface. The commonly used drills can be classified as: rotary-drag, diamond; percussive-hammer, piston, churn; and combination-rotary-percussive, roller.

Jan 1, 1967

By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

By John S. Berber

To improve the economics of low-temperature carbonization of coal, the Bureau of Mines is conducting research on the upgrading of the product tar to marketable chemicals. This report describes experiments on the catalytic hydrodealkylation, followed by catalytic vapor-phase oxidation of the dealkylate to phthalic and maleic anhydrides, of mixed residues from the urea adduction of lignite-neutral oil fraction and on the catalytic thermal dealkylation of high-boiling tar acids. The hydrodealkylation experiments were conducted at pressures from 1,000 to 1,750 psig and at temperatures from 600° to 1,000° F. The oxidation was, in all cases, at atmospheric pressure and 9500 F. Maximum yield of maleic anhydride, based on the liquid feed to the hydrodealky1ation unit, was 12.2 percent at 750° F and 1,500 psig; that of phthalic anhydirde was 6.9 percent at 650° F and 1,500 psig. Maximum yield of combined anhydrides was 18.8 percent at 650° F and 1,500 psig. The non-dealkylated feed material, upon oxidation, yielded 8.9 percent and 3.8 percent maleic anhydride and phthalic anhydride, respectively.

Jan 1, 1967

By David B. Brooks

I gratefully acknowledge the help of a number of American and Canadian geologists, in both federal surveys and in private firms, who took the time to discuss this problem with me. Hans Landsberg and Bruce Netschert also followed the study with interest and encouragement. In their 1961 monograph, THE FUTURE SUPPLY OF THE MAJOR METALS, Bruce Netschert and Hans Landsberg noted that identified potential resources (that is, known but submarginal resources) of lead and zinc were much lower relative to reserves (that is, known and supermarginal resources) than was the same ratio for other metals.1/ Put another way, it seemed that for such metals as iron, manganese, copper, and aluminum, slightly more favorable economic conditions or modest advances in technology would greatly increase reserves by permitting the exploitation of vest quantities of leaner or deeper or otherwise less valuable mineral deposits. But for lead and zinc, Netschert and Landsberg concluded that either: "(1) there is relatively little material below present cutoff grades; [or] (2) such material exists, but for some reason there are no data.? 2/ This situation, which they called "the lead-zinc anomaly" has been subsequently discussed by other authors. The purpose of this paper is to carry the discussion further by examining the evidence in favor of (1) and (2) and by advancing a third alternative.

Jan 1, 1967

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By Joseph M. Singer

Having established that sodium chloride reduces the incendivity of explosives, the Bureau of Mines studied the effect of sodium nitrate in reducing ignition hazards. Gallery experiments showed that sodium nitrate reduced the incendivity of certain explosives to 8 percent natural gas in air but increased their incendivity to coal dust predispersed in air. Laboratory experiments using hot jets from explosions of stoichiometric mixtures of methane-oxygen-nitrogen showed that both sodium chloride and sodium nitrate reduced the incendivity to methane, to mixtures of coal dust and methane) and to coal dust. The difference between the gallery and laboratory results with respect to coal dust is attributed to temperature-time effects.

Jan 1, 1967

By G. H. Charlewood, J. W. McBean

"One hundred years after being developed, the diamond drill is still an essential tool in mineral exploration. The basic principle is unchanged, but the technique has been revolutionized, particularly in the past fifteen years. The cost of core drilling has not kept pace with the rising cost of living. The price of machinery, supplies and labour in drilling has doubled and trebled since 1946. Some of the techniques which have made it possible to hold the price line are described."

Jan 1, 1967

By A. T. Chatas

A description of the geometrical characteristics of spherical reservoir systems, a discussion of unsteady-state flow of such systems and examples of engineering applications are presented as backgmund material. The fundamental differential equation, a description of average spherical permeability and the introduction of the Laplace transformation serve as theoretical foundations. Engineering concepts are investigated to indicate particular solutions of interest, which are analytically obtained with the aid of the Laplace transform. These are numerically evaluated by computer, and presented in tabular form. INTRODUCTION A tractable mathematical analysis of unsteady fluid flow through porous media generally requires incorporation of a geometrical symmetry. The simplest forms include the linear, cylindrical (radial) and spherical. Most analytical endeavors have concentrated on cylindrical symmetry because it occurs more often in petroleum reservoirs. Nevertheless, some reservoir systems do exist that are better approximated by spherical geometry. Review of technical literature revealed but a single reference to unsteady spherical flow in petroleum reservoirs.l The motive and purpose of the present work was to remove this gap in technical information, and to provide the practicing engineer with some useful analytical tools. The mathematical details associated with the particular solutions of interest involved use of the Laplace transformation. Hurst and van Everdingen previously demonstrated the efficacy of this operational technique, and in many respects the present treatment was patterned after their earlier work.2 PRELIMINARY CONSIDERATIONS GEOMETRICAL CHARACTERISTICS Geometrically, a spherical reservoir system is defined at any instant of time by two concentric hemispheres whose physical properties of interest vary only with the radial distance. Every physical property is thus restricted to be a space function of only one variable: the distance along a radius vector emanating from the center. Such a system is composed of an outer region and an inner region, separated by a defined internal boundary. The inner region simply extends inward from this boundary, whereas the outer region extends outward from it to an external boundary. The position of the internal boundary is presumed fixed, so that the size of the inner region remains constant. On the other hand, the position of the external boundary at any given instant of time is determined by the distance into the system that a sensible pressure reaction has occurred, Thus, the external boundary may change position with time. It initially emerges from the inner region and advances outward to its ultimate position. When this ultimate position coincides with a geometric limit, the reservoir system is said to be limited. When it coincides with points subject to pressure gradients furthest removed from the internal boundary, yet short of a geometric limit, the system is said to be unlimited. In this investigation two different boundary conditions are imposed at the ultimate boundaries of limited systems. The first requires that no fluid flow occur across this boundary; the second that the pressure remain fixed at this boundary.3-5 UNSTEADY-STATE FLOW In a strict sense virtually all flow phenomena associated with a reservoir system are unsteady-state. The transient behavior of these phenomena requires accounting, however, only when time must be introduced as an explicit variable. Otherwise, steady-state mechanics may be used. Analytically, steady-state conditions prevail in a reservoir system only over that portion of its history when this relation is satisfied:

Jan 1, 1967

By R. R. Goddard

By use of the frequency response method with a radioactive tracer, it was possible to determine fluid dispersion and distribution in a natural consolidated and an unconsolidated medium. Measurements were made in a linear flow system at oleic saturations of 69 per cent in the consolidated medium, and 100 per cent in both media. Dispersion and distribution were obtained by measuring the amplitude attenuation and the phase velocity of sinusoidal waves with a dual monitor apparatus. The gamma ray emissions permitted in situ measurements at any distance along the porous samples. One result of importance was that the effective diffusivity increased as the wave length increased. As a consequence, a dispersion coefficient appropriate for the injection of large slugs might exceed the value measured by use of small slugs. Since flow models based solely on fluid velocity and an effective diffusivity coefficient imply that the diffusivity should be independent of frequency, such representations were not adequate for the data of this study. A comparison was made with a capacitance model of porous media with deadend PVs, but even this model was not completely adequate. By using attenuation and phase velocity data, fluid dispersion can be predicted without postulating a differential equation satisfied by the tracer concentration, thereby eliminating the need of a complicated model to represent dispersion. INTRODUCTION The flow of similar miscible fluids through a porous medium can be fairly adequately described by two parameters: the average fluid velocity and the effective diffusivity.1-3 It has been pointed out recently, however, that significant discrepancies exist between this representation and the experimental data.4-7 An improved agreement can be obtained by introducing additional parameters based on the concept of dead-end pores. The purpose of the present investigation was to find out whether the frequency response method could be used to measure the relevant parameters. The method was used in the following form. A stream of fluid was flowed at a constant rate through a sample of porous material and the concentration of a radioactive tracer in the fluid was varied sinusoidally at a fixed frequency. The effects of flow through a porous medium are a decrease in the amplitude of the concentration wave and an increase in the velocity of the peaks of the waves above the average velocity. Attenuation and phase veIocity of the waves were measured as a function of frequency and fluid velocity. The simple two-parameter model implies that the diffusivity should be independent of frequency. Data reported in this paper show that the diffusivity decreases as the frequency increases. Hence, as shown also by many others, the two-parameter model is not completely adequate. Coats and Smith 5 used two additional parameters in their model: the volume of the dead-end pores and the rate of mass transfer between dead-end pores and the flowing stream. Their capacitance model of a porous medium containing some stagnant fluid, to which transfer occurs by molecular diffusion, did not explain the dispersion results of either the present study or of theirs. Instead, the capacitance effect can be better described as the result of extreme velocity variations within the pores of the medium, with transfer between the velocity zones by convection. EXPERIMENTAL PREPARATION OF POROUS MEDIA Data reported here were obtained with a natural Berea sandstone, and with two packings of 20/25 mesh sand. Pertinent information about these media is listed in Table 1. The sandstone core was first sealed with a non-

Jan 1, 1967

By R. W. Smith, R. W. M. Lai

Although several recent papers have shown that equilibrium contact angle in dodecylamine solution-quartz systems can often be directly correlated with flotation behavior, it appears that under conditions of relatively high amine strength and pH such a correlation can't be made. Under these conditions, when there are precipitated amine dipoles present, it appears that a dynamic contact angle formed immediately after introduction of fresh gas bubbles into the system is also of importance. The dynamic angle decreases in magnitude as a function of time. Apparently the decrease is the result of changes in interfacial tensions (liquid-gas and solid-gas) as a function of time. Dynamic angles of the type described can't be observed in trimethyldodecylammonium chloride solution-quartz systems. Several recent papers1-3 have shown quite conclusively that contact angle data can often be correlated directly with flotation behavior in cationic surfactant solution-quartz systems. At the same time, Iwasaki, Cooke, and Colombo4 have shown data for a dodecylammonium chloride solution-goethite system where, in the vicinity of pH 12 and a collector concentration of 10" M, 100% flotation occurs when equilibrium contact angle appears to be zero. A clue to this discrepancy can be found in the work by smith2 who reported the occurrence of dynamic, time dependent, contact angles in a quartz-dodecyl-amine solution system at relatively high pH values and at surfactant concentrations greater than or equal to 10-4 M. It was found that under these conditions, if a fresh bubble was brought into contact with a properly conditioned and polished quartz surface, a large angle was obtained. The large angle, however, instantly started to diminish in magnitude, sometimes to a smaller stable angle and sometimes to its complete disappearance. Also, if the bubble was preconditioned for some minutes (or sometimes even seconds) in the same amine solution, the smaller or sometimes zero stable angle was obtained when the bubble was brought in contact with the quartz surface. One is immediately led to the thought that perhaps it is these dynamic angles when they exist, not stable angles, that are of primary importance in flotation. The present investigation attempts to further study the relationship between contact angle and flotation

Jan 1, 1967

By V. Patarini, D. Kuehl, F. Galasso, M. Salkind

In recent years, a great deal of research has been directed toward the production of continuous low-density, high-strength, high-modulus boron fibers for aerospace applications. A technique which has proven to be quite successful for forming these fibers involves the reaction of boron trichloride and hydrogen on a hot tungsten wire. In this process, a boron fiber is produced which consists of a tungsten boride core covered with amorphous or crystalline boron depending on the temperature of the preparation.2,3 The purpose of this paper is to present the properties which have been obtained to date from measurements and observations on these fibers. Selected samples of boron filament produced by reacting boron trichloride and hydrogen on a 0.5 by 10-3 in. diam tungsten wire substrate using different reacting temperatures were cross-sectioned, polished, and photomicrographed with cross-polarized light. The temperature of the wire was measured using a two-color optical pyrometer. Photomicrographs of these samples are shown in Fig. 1. Three general types of boron, in addition to the tungsten borides, have been identified by means of X-ray powder diffraction techniques: a) at low temperatures (below 1400°C) the boron is deposited in the amorphous form; b) at temperatures between 1400° and 1500°C the boron is deposited in the ß tetragonal form; and, c) above 1500°C the boron is deposited in the B rhom-bohedral form. In the depositing range of 1400" to 1500°C the boron initially deposits as amorphous and becomes crystalline as evidenced by the large equi-axed grains which then merge into columnar grains in later stages of boron deposition. This can be seen in Fig. 1 and has been observed in the X-ray patterns of these fibers, which contain both halos from the amorphous boron and lines from the ß tetragonal form. Above 1500°C the only boron reflections observed in the X-ray patterns were those of the ß rhombohedral form and only columnar grains are seen in the photomicrographs. Photomicrographs of the surface in Fig. 2 show the smooth-surface kernal-type deposition which corresponds to the amorphous form and the rougher surfaces which correspond to the crystalline form. Mechanical measurements were made on amorphous boron produced at 1300°C rather than the crystalline boron because the strengths of these filaments were greater and were more consistent. A tensile tester consisting of a fixed crosshead containing a double

Jan 1, 1967

By J. Skrove, C. R. Boardman

In situ permeability of the rock outside the Hardhat chimney was determined by pressurization of long holes with air. Experimental data indicated a remarkable difference between fracture permeability of the rock near the chimney and that at a considerable distance. Although permeable fault zones were known to exist in the granite stock, the measurements of background permeability were quite low, on the order of tenths to several millidarcies. The observed difference is about two or three orders of magnitude above this background in the region 125 to 215 ft radially from the shot point, or 80 to 165 ft radially from the vertical axis of the chimney. The presence of a collapsed drift immediately beyond this region precluded measurements which could have defined the maximum extent of the zone of high permeabilily. INTRODUCTION Previous exploration has revealed that contained nu-clear explosions create cavities which generally collapse, resulting in rubble-filled chimneys and annular fractured zones. These geometries have been shown to result in complex flow regimes which should increase the production rate from hydrocarbon reservoirs.' Empirical scaling equations have been developed for estimatina chimney radii and heights for a variet; of rock media.' The exten; of the annular fractured zone has been documented and associated permeability changes have been observed qualitatively for several explosions. This study was begun to establish the nature and magnitude of the permeability of the latter region. It is anticipated that results will be useful in estimating permeability changes and consequent production stimulation which might ensue from a contained explosion in a hydrocarbon reservoir. The post-shot environment of the Hardhat event (a 5-kt contained nuclear explosion in granitic rock) was c'hosen for the experimental measurements. The Hardhat device was detonated at a depth of 939 ft, and subsequent exploration revealed a chimney of broken rock with a radius of 65 to 70 ft and a height above shot point of 281 ft.' BeFore the explosion, the Hardhat medium was highly jointed and fractured (Fig. I). Jt was expected that differential rock motion along these and other weaknesses induced during cavity growth and collapse would significantly alter the permeability of the rock mass. EXPERIMENTAL METHOD Initially, three 2-in. diameter holes (Nos. 10, 12 and 19) were drilled about 25 ft outward through the walls of the 500-ft level drift (elevation 4,253 ft, Fig. 2). One was drilled near the chimney and two holes, one vertical and the other horizontal, were drilled near the shaft. Order-of-magnitude differences in permeability obtained by pressurization measurements indicated further: investigation was warranted. A series of 3-in. diameter holes was then drilled with water as a coolant into the walls and roof of the drift (Fig. 2). An 11-in. long packer was set from 1 to 8 Et inside each hole and air was injected at measured Row rates. Hole pressures were monitored at the collar. Permeability was low enough in the holes near the access shaft that pressure could be maintained long enough to obtain good pressure decay rates. In the vicinity of the chimney, however, permeability was so high that this was not possible and air was injected under steady-state conditions. About one year later, these same holes were retested to

Jan 1, 1967

By R. Al-Hussainy, H. J. Ramey

Previous gas well test analyses have been based mainly upon linearizations of ideal gas flow results, although a method for drawdown analysis based upon real gas flow results has been proposed. Linearizations based upon ideal gas flow require estimation of gas physical properties at Tome sort of average pressure, and implicitly involve the assumption that pressure gradients are small everywhere in the reservoir. A new real gas flow equation has been developed by means of a substitution which couples presTure, viscosity and gas law deviation factor. This sub-stitution has been called the real gas pseudo-pressure. Use of the real gas pseudo-pressure leads to simple equations describing real gas flow which do not contain pressure-dependent gas properties, and which do not require the assumption of small pressure gradients everywhere in the flow system. Equations required to determine flow capacity, well condition and static formation pressure from pressure drawdown and build-up tests with the real gas pseudo-pressure concept are presented. Also shown are applications of the real gas pseudo-pressure to back-pressure testing, the gas materials balance and rigorous determination of average gas properties for previous gas flow equations. Included are sample calculations for well test analyses. INTRODUCTION A recent study' of the flow of the transient flow of real gases in ideal radial systems showed that it is possible to consider gas physical property dependence upon pressure by means of a substitution called the real gas pseudo-pressure. The substitution has the advantage that it enables engineering solutions for steady and transient flow of real gases that are more accurate and general than those previously available. The solutions are particularly important for the case of gas flow in tight, high-pressure formations under large drawdowns. Even for more ideal flow conditions, the real gas pseudo-pressure concept leads to important rules for finding average gas physical properties pertinent for older well test analyses. Ref. I provides a detailed study of the theory behind the real gas flow correlations to be used in this paper. The purpose of this paper is to provide necessary engineering forms for use of the real gas flow results, and to illustrate applications. The following considers flow of real gases in an ideal radial flow system. It is assumed that: (1) formation thickness, porosity, water saturation, absolute permeability, temperature and gas composition are constant; (2) gas compressibility and density are functions of pressure as described by the gas law pv = znRT; (3) gas viscosrty is a function of pressure; (4) effective permeability to gas may be a function of pressure to account for liquid condensation; (5) condensate is immobile; and (6) the formation has no dip.

Jan 1, 1967