Search Documents

For convenience, we tabulate below the weight systems contained in the Probierbüchlein: [Pound and centner weights used by merchants for ore, lead, and copper I frother = 20 or 50 centners (depending on locality) I centner (Stolberg & Eisleben) = 112 pounds. I centner (Nuremberg) =100 pounds I pound =2 marks =32 lot =128 quintlein-512 pennyweights =1024 beller I mark -16 lot -.64 quintlein =256 pennyweights = 512 beller 1 lot= 4 quintlein= 16 pennyweights= 32 beller I quintlein = 4 pennyweights= 8 beller I pennyweight = 2 beller Netherlands mintmasters' weights for silver I mark =12 pennyweights=288 grains I pennyweight - 24 grains Assay weights for gold I mark= 24 carats 96 carat-grains. I carat = 4 carat-grains] The assayer's weights were miniature copies of the legal weights of his locality, intended, like the modern assay ton, to eliminate calculation. Each assayer made his own, not usually bothering about a given proportion between the true weights and the assay set, but maintaining the correct ratio between all the weights in any one set. The weights were quite small, to permit the use of less sample, but the exact size is nowhere stated in the Probierbüchlein. Even the legal pound varied considerably from place to place, depending on locality, and assayers would use different factors depending on the sensitivity of their balances, among other things. Agricola makes the assay centner equal to one actual drachma, by which term he means the German quintlein, or 1/12,800 of the full weight of the 100-pound centner. Schreittmann says that the 100-pound centner on the assay scale should be less than half a quintlein, i.e., the factor should be at least 25,600. Biringuccio says the assay centner might

Jan 1, 1949

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.'-' A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By J. D. Sudbury, J. E. Landers, D. A. Shock

The external corrosion of casing is one of the most important problems facing the present day production man. A 1953 NACE report' estimated the annual cost of casing corrosion at $2,200,000 in 22 fields studied. The fields represented only 10 per cent of the wells in the United States. It was significant that 77 per cent of the failures reported were due to external corrosion. A variety of means for combatting the casing corrosion problem have been discussed in papers such as the NACE survey' mentioned previously. No attempt to revicw these will be made in this paper. Thc scope of this paper has been limited to a discussion of the following major items: (I) an instrument for studying external electrolytic corrosion; (2) use of this instrument to determine the quantity of protective current required to prevent corrosion of casing; and (3) problem of accelerated external corrosion of the oil string at the base of the surface string. ELECTROCHEMICAL MECHANISM OF CORROSION It IS gcncrally belleved that one major cause of external corrosion is the existence of electrolytic cells operating between various formation waters. A theoretical discussion of the role of earth potentials in casing corrosion has been presented by L. de Witte and F. J. Radd.2 A brief picture of the electrolytic corrosion action between two differcnt formations (A and B) is presented in Fig. I. This picture is a review to many but is given to insure clarity. In the anode area, oxidation takes place as iron ions go into solution in formation A as a product of corrosion. In the cathode area. reduction takes place and hydrogen atoms are formed at the boundary between the pipe and formation B. The flow of electrons. as indicated. is into the pipe at the anode or corroding area and out of the pipe into the formation at the cathode. In order to conform with regulations of this journal, the flow of a conventional current (I! is also indicated in this sketch. All subsequent references will be to this so-called conventional current flow and will be indicated by the symbol (I). As this action takes place the layer of hydrogen developed on the cathode offers a resistance to the flow of current in the cell. It is said (hat the cathode has been polarized. This polarizing film can be rcmoved by addition of a so-called dcpolarizing agent which reacts with and removes this hydrogen film. Such an agent must be present in ordcr for this corrosion reaction to go at a rate sufficient to cause a severe corrosion problem. The two common depolarizing agents are: (I) oxy-sen. which readily reacts with hydro gen to form water, and (2) certain bacteria which use atomic hydrogen as part of their life process. It is not difficult to explain the presence of these agents. Oxygen may be present in some very shallow formations. Sulfate reducing bacteria are found to exist in nearly any ground where mud pits might be dug. THE CASING POTENTIAl-PROFILE Instrumentation A sketch of the equipment* uscd in determining casing potential profiles is shown in Fig. 2. The tool is run in the hole using a hoist truck with a three-conductor cable. This tool must be run with tubing and rods out of the hole and should be run with the flow line disconnected. By proper choice of electrode size it can be run in any size casing. The electrodes must be run in an open hole or a hole filled with oil. Measurements cannot be made while immersed in water. The tungsten carbide-tipped knives serve as the electrical robes and arc spaced 25 ft apart. The potential difference along a 25-ft section of casing is measured with a potentinmeter to an accuracy of about 5 mv. Current flowing in the pipe can then

Jan 1, 1956

By G. W. White

Over the past several years, the steady progress of gas lift from a mysterious art into a developing science has been traceable through the many fine papers that have appeared in Journal of Petroleum Technology. Consequently, this magazine has rightly become a standard for the serious students of gas lift all over the world. The following discussion is offered in a sincere attempt to accurately present certain topics covered in the subject paper in the light of acknowledged state of the art procedures. INSTALLATION DESIGN The first point to be questioned is the author's installation design, beginning with Eq. 6. The use of 1,200 psi in the spacing equation instead of the 1,275 psi noted as available seems, at first glance, to be a simple arithmetic error. Upon further examination, it appears evident that both this 75 psi plus the 100-psi safety factor must be subtracted from available kickoff pressure because of conditions imposed by the characteristics of the ASC valve (see Fig. B-1). Pressure-charged valve design is incorrectly penalized by spacing the first valve using only 1,100 psi. The use of such a high back-pressure makes it appear that a typical ASC installation would require no more valves than a comparable conventional valve installation. Using a value of 100-psi tree pressure, the well could be valved to 11,000 ft very conservatively with seven pressure-operated valves, but would still require 11 ASC valves. The use of 400-B/D spacing gradient for a 140-B/D rate is not an accepted practice using precharged valves. The author would have done well to note the advantages to be gained by reducing the 500-psi tree pressure, which is clearly explained by Beadle, Harlan and Brown.' In Step 1 of Part III of the continuous flow discussion, the author incorrectly applies the Poettmann and Carpenter curves.2 Item 2 is an incorrect statement. An excellent reference on this point is the paper by Baxen-dell and Thomas.' VALVE MECHANICS The next topic relates to the mechanics of precharged valves. Eq. 2 for the ASC valve can be used to describe the condition of equilibrium, wherein the valve is closed with opening pending. When this equation is used to determine relative values of casing, dome and tubing pressure with conditions approaching the transition value, some strange results are obtained. The following uses the author's symbols and values given on page 689. Fig. B-1 shows the condition that exists at the moment an ASC valve has been uncovered during the unloading process (Condition I). The obvious result is a locked condition. The basis for the curve is shown on the figure which includes 1,000 psig casing pressure to uncover the valve. If injection gas is not bled off the casing until the pressure is decreased by an amount exceeding the stabilizer discharging valve pressure, upward adjustment of the casing pressure is mandatory for the valve to open and unloading operations to continue. In Condition I the dome pressure exceeds the casing pressure by 20 psi, and the tubing pressure required to open the valve is 1,212 psig. This tubing pressure would not exist under the assumed conditions. In Condition I1 the casing pressure is increased to the dome pressure, and the tubing pressure required to open the valve is 1,102 psig. It is apparent that the casing pressure must be increased to a value exceeding the dome pressure before unloading operations could continue. In Condition I11 a maximum casing pressure of 100 psi (stabilizer charging valve set pressure) above the dome pressure is reached, and the tubing pressure required to open the valve is 549 psig. The author's statement after Eq. 5 that "the minimum tubing pressure required to open an ASC valve is equal to the casing pressure at depth less the transition pressure of the valve" is incorrect except for Condition I11 only. Otherwise, the equation is invalid.

Jan 1, 1965

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

By Henry Louis

The present paper comprises two parts, which have but little con nection with each other. The first is practically a continuation of the investigation on the specific gravity of gold liberated by means of acids from its alloys, on which subject I had the honor of presenting a brief note to the Institute in 1893 (Trans., xxii., 117); the second describes a series of experiments on the behavior of amorphous gold under the action of heat. By the kindness of Prof. W. C. Roberts-Austen, C.B., F.R.S., chemist to the Royal Mint, I have been permitted to conduct these experiments in the mint assay-office, all the splendid resources of which institution were freely placed at my disposal. I desire at the outset to express my obligations to Prof. Roberts-Austen and to all the staff of the mint assay-office for their kind assistance at all stages of my experiments. I.—The Specific Gravity of Gold in Alloys. In the note already referred to, I published my discovery that the gold left on dissolving out the silver from an alloy of gold and silver (which I shall here term " residual amorphous gold ") has a higher specific gravity than ordinary molten gold. I also pointed out that I had worked on very small quantities of material and with balances and weights on the accuracy of which I could not implicitly rely, and that in so far my numerical data were inconclusive, although I had but little doubt of the correctness of the broad fact. The experiments now recorded were made under the most advantageous circumstances and with various refinements. Particularly, I found that the ordinary form of specific-gravity bottle was responsible for several small sources of error; and I accordingly designed an improved form (Journal of the Society of Chemical Industry, April 30,1894, vol. xiii., p. 322), which I used for this work. The

Jan 1, 1895

By Douglas R. Piteau

Douglas R. Piteau (Engineering Geologist, De Beers Corp., Kimberley, South Africa; Presently Consulting Specialist at Nchanga Mine Open Pit, Chingola, Zambia)-Mr. Lutton is to be commeneded on his analyses and presentation of such practical data which can be used for predicting a preliminary optimum slope angle in rock. It appears that he assumes all slopes analyzed to be straight. Although there are overriding factors which affect the general slope configuration, such as structural discontinuities, ground water, and other environmental factors such as weathering conditions, regional stress, etc.,8 the affects of plan geometry under certain conditions also can be of outstanding importance. In investigation of natural slopes, for example, the effects of plan geometry are not entirely appreciated and it is in this respect that discussion is given. Experience in southern Africa has shown that the overall geometry of surface openings in rock, particularly those with dimensions of the order of 1500 ft or less, i.e., where radii of curvature of the slopes are less than, say, 700± ft, must be considered in rational slope-stability analyses. That is, the slope angle is not only a function of slope height, strength of the mass, and geometry of structural discontinuities, but also is dependent upon the plan geometry of the local slopes and the plan shape of opening. Technically speaking, adequate analysis of the slope must be three-dimensional, the third dimension being that of overall plan configuration and the analysis must incorporate its subsequent effects. However, current theories of slope stability all deal with the slope as a two-dimensional problem, i.e., a slice of unit length of an infinitely long slope is considered for a condition of plane strain. In this the tacit assumption is made that the plan radii of the crest and toe of the slope are infinite and no attention is given to the plan geometry of the slope. Clearly this is not the condition encountered in practice, particularly in open pit mining where excavations, relatively speaking, can be small and where these radii of curvature accordingly can have important affects on the slope stability. This is illustrated by the analyses of Piteau and Jennings 9 of the natural slopes which had developed around pipes of four diamond mines in the semiarid Kimberley area of South Africa. Although these slopes consist of dolerite overlying shale, the values of the slope angles of all the pits were corrected for a height of slope of 320 ft assuming that no dolerite occurred. This brought the data onto a comparable basis. These data were analyzed statistically and a clear empirical relationship, as is shown [in Fig. 4], is seen to have formed between angle of slope and curvature of slope, i.e., the angles of slope are greatest where the radii of curvature are least. Also, it can be seen that the slope of each line is different, indicating that the plan shape of the open pits also are significant, the curve being steepest for the open pits which are more circular in shape in contrast to those which are more elongated. The effect of slope curvature on the average angle of slope for the two extreme radii of 200 ft and 1000 ft for all four open pits is 39.5° and 27.3°, respectively. Hence, the concave curvature effect represents an average increase in slope angle of 12.2° from the essentially straight slope. In quantitative terms in Mr. Lutton's Fig. 2, this represents displacing the curve for a 320-ft pit from the second curve from the bottom (i.e., shale in subtropical climate) to that of the third from the bottom (i.e., quartzite in temperate environment).

Jan 1, 1972

By C. R. Sandberg, L. S. Gournay, R. F. Sippel

The effect of fluid-flow rate and fluid viscosity on oil-water relative permeability determinations was studied using the "dynamic flow technique." In this work relative per-nleability curves were obtained for homogeneous small core .samples from several sandstorle outcrop form-utions. Radio-tracers were used for the determination of fluid saturation and for the detection of saturation gradients. Cobalt-60 in the form of cobaltous chloride was used as a water-phase tracer in some of the experiments. Iodine-131 in the form of iodobenzene and Mercury-20-3 in the form of mercury diphenyl were used as oil-phase tracers in other experiments. Flow rates for each phase were varied within a range of 2.5 to 140.6 ml/hr. Oil-phase vis-cosities under flowing condition,> were varied from 0.398 to 1.683 cp. The relative permbilities ob-tained were found to he solely a function of saturation and independent of flow rare, provided there was no .Saturation gradient induced in the core sample by "boundary effect." Even though equilibrium with re-sped to flowing conditions was obtained at the lower flow rates, where a saturation gradient exists, this equilibrium is of a "contingent"-type rather than the "steady-state" equi-librium implicit in the relative per-meability concept. The only effect of increasing the oil or non-wetting phase viscosity was to decrease the flow rate required for the elimina-tion of the boundary effect. Fairly good agreement between experimentally determined and calculated values of the boundary effect was obtained when the non-wet-ring oil phase was the only Flowing phase. INTRODUCTION In the characterization of reservoir rock, as well as in the solution of reservoir production problems, it is most desirable to have reliablc rela-tive permeability measurements for the rock and fluids of interest. Many techniques have been developed for the laboratory determination of the relative permeability of both large and small core samples. In varying degree, difficulties attend the use of all of the methods. Each of the methods requires the metered flow of fluids of known viscosity through the core sample under conditions wherein the pressure drop in the individual flowing phases can be measured or closely approximated. Since the relative permeability is a function of the saturation and distribution of the flowing fluids, some means of obtaining such information is also required. The laboratory determination of the relative permeability of a sample should give the same relative permeability saturation relationship that would exist if the sample were in place in the oil reservoir. The attainment of this objective is complicated by the fact that the use of small core samples for laboratory measurements is usually necessary. As a result, errors in measuring the relative permeability arise from boundary effects at either the fluid input or output ends of the sample; no significant boundary effect is anticipated at the sides of the sample normal to direction of fluid flow. At the input end of the sample a boundary effect exists if the flow fluids are not com- mingled as they would be in the reservoir. At the output end of the sample a boundary effect exists as a result of discontinuity of the capillary properties of the system. Here the flowing fluids leave the small flow channels and enter a collecting system having much enlarged flow channels. Thus, there is a tendency for the wetting phase to be retained by the core sample because of the attraction of the core sample for the wetting fluid. No reference is made to these boundary effects in either Darcy's equation or in the relative permeability concept. As a consequence the saturation effect peculiar to the input end of the core sample may cause an error in the effective permeability measurement, since some portion of the core sample must be utilized for commingling of the flow fluids. At the output portion of the core sample a saturation gradient or a saturation change along the axis of flow results. Since relative permeability is a function of fluid saturation, this saturation gradient may cause a variable permeability measurement, especially since extent and character of the saturation gradient can vary with fluid-flow rate. The most convenient method of minimizing the boundary effect, especially at the output end of the sample, is to flow the fluids of interest through the core sample at such high rates that the capillary forces arc insignificant as compared to the viscous forces involved in the fluid flow. Since recent work of a preliminary nature has indicated that fluid dispersion in the porous medium increases with the flow rate, the high flow minimizes the boundary effect at the input end of the core sample by enhancing the mixing of the fluids.

Discussion of the paper of Ernest Stütz, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1257 to 1265. H. 0. HOFMAN, Boston, Mass.:-I have hunted in vain for a figure which gives a dehydration temperature of cement. I was wondering if Mr. Stütz had a figure of that kind. E. STÜTZ :-No, I am afraid I have not. H. 0. HOFMAN :-I believe some figures have been published that cement disintegrates at 400° or 500° C. It seems tome a very low temperature. Mr. Stütz just made the statement that the disintegration of this briquette begins at the temperature at which the briquette begins to sinter. E. STÜTZ :-Above the sintering point. H. 0. HOFMAN :-The sintering point would be about 1,200° C. E. STÜTZ :-Yes, roughly speaking. I am afraid I have no information about the exact degree of dehydration. H. O. HOFMAN :-I have looked a great deal for such a figure and I have not been able to obtain it. Professor Howe says I might have tried myself. But my interests were directed in another line; although-that is, perhaps, a good suggestion. CHAIRMAN RICHARDS:-Is not Portland cement sometimes used for the test in a cupellation furnace and a drying-out furnace ? H. O. HOFMAN :-Yes, it is used, but that is a higher temperature, of course. But I have been trying to get a figure as to where it loses all its water. I understand it begins to lose water at 500° C. But there are different silicates or hydrosilicates in the cement, so that one would have four or five or sit figures to show the different stages at which the cement loses its water. CHAIRMAN RICHARDS :-I would ask whether the use of this material in blast furnaces has shown increased capacity of furnace or decreased consumption of fuel.

Jan 12, 1913

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

I HAVE now traversed for you in the small and fragile bark of my writing all the shores of the deep and spacious sea embracing the uses of material fires, drawn on by my own desire to enrich you with more learning and with the procedures of these things, as much as to satisfy your demands. Having through the grace of God arrived at the appointed end of my voyage and neither knowing nor perceiving a way of going farther, I had decided to furl the [167] sails and cast die heavy anchors into the water in order to enjoy in tranquillity respite from my sailing, when I was warned by my pilot that before I could disembark I should turn my glance backward and reexamine my work in detail to see if there were any part that had by chance remained undescribed in the obscurity of silence. When I did this there immediately appeared in my mind's eye the many sublimates and smoky tinctures that had been made by the burning and most powerful fire of love. I need not say that I knew of it in far-off countries or from the knowledge of others, but I knew it in my own breast and as my very own and can therefore surely esteem it as hotter than all the other fires that the world calls by that name. Although today its sparks and living flames are spent because of my cold and hoary season, nevertheless it is true that the memory of acts of love of long ago still remains with some smoke and warmth. Therefore, since in this work of mine I wish to describe for you the effects and powers of fires, I should logically have spoken of this before any of the others, because of its actual nearness and the great acquaintance I had with it. But since I have had the glance of my intentions directed at distant things, I have behaved as one does who does not see where he places his feet because he is looking at the sky, or as one who thinks about the affairs of others and forgets his own. But now I do not wish to pass over this thing and I wish to correct my error, particularly in order to provide a happier ending to my written work than by remaining among the horrible uproar of guns, powder, and saltpeter, which would be a harsher ending than speaking of love. Never-

Jan 1, 1942

By E. N. Aqua, C. M. Owens

The microstructure in cold-rolled Zircaloy-4 sheet has been characterized by transmission electron microscopy and X-ray diffraction line-broadening techniques. The rate of work hardening is measured in terms of microstrains, particle sizes, micro hardness, the tensile yield strength. The tensile yield strength of Prestrained (less than 10 pet) Zircaloy-4 sheet is found to be a linear function of the square root of the dislocation density, us predicted by work-hardening theories. ZIRCALOY is one of the most important structural alloys for nuclear reactor applications.''2 In order to understand the effects of the nuclear environment on Zircaloy structural members, the preirradiation microstructure must be characterized. This report will describe the substructure existing in cold-rolled Zircaloy-4 sheet as observed by electron microscopy and by X-ray diffractometry. I) EXPERIMENTAL PROCEDURE Commercial Zircaloy-4 strip was cold-rolled and annealed in argon at 760°C for 1 hr. The annealed sheet was again cold-rolled to a maximum of 50 pct reduction in thickness with segments of the strip being retained after 2.5, 5, 10, and 20 pct reductions. One-inch-square portions were chemically polished (50 parts HNO3, 50 parts H2O, 10 parts HF) and mounted onto lucite blocks using double-sided tape to prevent bending during handling. Thin foils suitable for transmission electron microscopy were prepared from each of the sheet samples. The sheets were mechanically polished through 600-grit paper to a 3 to 4 mil thickness and were chemically polished by immersion for 1 to 2 min in a solution containing: 50 parts HNO3, 50 parts H2O, and 10 parts HF, and rinsed in distilled water. The final metallographic procedure was to electropolish for less than 10 sec with an electrolyte of 10 parts perchloric acid and 90 parts glacial acetic acid, at 20 v, at room temperature using stainless-steel point cathodes and a vigorous stirring action. These foils were examined in a Philips EM 200 electron microscope using a 100-kv accelerating voltage.

Jan 1, 1968

By E. Miller, J. M. Eldridge, K. L. Komarek

Activities of magnesium in liquid Mg-Sn alloys have been determined between 5 and 90 at. pct Sn and 990" and 1290°K by an improved isopiestic method wherein tin specimens, heated in a temperature gradient and contained in crucibles of special geometry, were equilibrated with magnesium vapor in a closed titanium system. The crucibles were designed so that the equilibrium compositions of the specimens were satisfactorily preserved on termination of the experimental runs by quenching. The activity values are in excellent agreement with those predicated on the phase diagram and allowed a delineation of the solidus curve of the compound Mg2Sn near its melting point. EQUATIONS have been recently derived relating the chemical potentials of the components to the liquidus and enthalpy data for binary systems exhibiting one congruently melting compound.' The liquidus curve of the Mg-Sn system between the eutectics was carefully redetermined and the thermodynamic properties thus calculated were in reasonably good agreement with values derived from electromotive-force measurements of an,' but differed greatly from the iso-piestically determined values of Ashtakala and Pid-geon.3 The present study was initiated: a) to resolve the discrepancies; b) to develop a method for measuring activities in systems having volatile (and possibly highly reactive) components; and c) to use the method in a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVb systems, i.e., Mg-Pb, Mg-Sn, Mg-Ge, and Mg-Si. This paper describes the results for the Mg-Sn system. An isopiestic technique, originally developed by Herasymenko 4 and adapted for alloys having a component of high reactivity and low volatility,5-8 was modified in this study by using crucibles designed to preserve the equilibrium composition of highly volatile liquid specimens on quenching from high temperatures. Tin specimens, contained in tightly covered graphite crucibles and heated in a temperature gradient, were equilibrated with magnesium vapor of fixed pressure from a magnesium reservoir kept at constant temperature in a previously evacuated and sealed titanium tube. During equilibration magne-

Jan 1, 1967

By J. R. Long, C. E. Armantrout, A. H. Roberson, T. R. Graham, R. S. Dean

THE general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing 10 to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heusler1 recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and io per cent Al but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 [ ] has drawn a hypothetical boundary for the alpha field with few data to support such construction. The binary systems involved have received considerable attention by numerous investigators, and their general features are well established. The hopper-aluminum system (Fig, I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smiths established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig. 2) has been recently reviewed by Dean and co-workers.7 Using high-purity alloys, they place the solubility of alpha man-

Jan 1, 1946

By R. S. Dean. J. R. Long T. R. Graham, Roberson A. H., Armantrout C. E.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By Armantrout C. E., R. S. Dean. J. R. Long T. R. Graham, Roberson A. H.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By W. C. Ellis, E. S. Greiner, M. E. Fine

C. H. Samans and W. R. Ham (Chicago, Ill., and Dix-field, Maine, respectively)-—For several years we have been studying transitions of this basic type in metals, alloys, glasses, etc. Usually, however, they are not so clearly marked as those which the authors have found, and hence are much more difficult to determine accurately. Since our studies indicate that most of them occur virtually unchanged (as far as temperature is concerned) regardless of the form in which the element appears, we believe that they are a characteristic of the atom. Specifically, we believe that there is an additional rotational degree of freedom possessed by the nucleus which has not been considered heretofore. This nuclear rotation is made up of several components, each related to the several quantum shells of electrons. In chromium there are four of these shells and hence four separate series of characteristic transition temperatures. The lowest temperature at which any transition occurs, based on the present state of our computations, is 125°K, 4° higher than the authors' value of 121°K. A convergence of this series, we believe, shows up at the higher temperature of 2085 °K, surprisingly close to the transformation temperature of 2103°K recently announced by N. J. Grant of M.I.T. for a body-centered to face-centered transformation in chromium. Likewise, our computations indicate a temperature of 311°K for the second transition temperature, reported by the authors as 310 °K. A convergence of this series, we believe, shows up at a higher temperature as the melting point at 2163°K. Although our work on these series must, in a sense, still be regarded as empirical, since we do not understand fully as yet just what the series mean, it is based on a reasonably firm picture. The individual constants, from which the various series are computed for each element, comes directly from the X-ray K absorption limit. Furthermore, the same basic method has accounted for transformation and melting temperatures in about 50 of the chemical elements, which is all we have tried thus far. In many cases the only known transformation is the melting point, but in others the occurrence of transformations or other transitions, equally as well marked as those of the authors, has been pointed out by others. These observations have assisted us greatly. Consequently we were very pleased to see the authors' excellent work in finding these two transitions in chromium. With these confirming data, our picture of this element is clarified considerably, so we expect that at least some of our work can be published in the near future. R. C. Ruder (E. I. du Pont de Nemours & Cu., Wilmington, Del.)—The authors' interpretation of these transitions in terms of 3d to 4s electronic structure transitions is most interesting. It would be interesting to have additional experimental evidence of such transitions from the temperature dependence of the Hall coefficient in the neighborhood of the property changes discussed in this paper. Simple theory15 suggests the Hall coefficient as a measure of the free electron (or s electron) concentration per unit volume. It has been shown that for paramagnetic'" and ferromagnetic1? metals the simple theory is in fact too simple. However, the existence of a discontinuity in the Hall coefficient would provide information which should aid both in our understanding of these transitions and the significance of the Hall coefficient in these metals. It was rather surprising that no significant paramagnetic effects were observed. In this connection the recent work of McGuire and Kriessman18 is cited. They measured the magnetic susceptibility of chromium from 20" to 1460 °C. They also observed no large change in the susceptibility although there might be a change in slope in the vicinity of the 40 °C transition. The existence of these 3d to 4s electronic transitions has been discussed in connection with the paramagnetic susceptibility behavior of nickel and nickel alloys.'"-" Assuming a correspondence principle between classical and quantum mechanical paramagnetic theory and using classical theory to calculate the effective Bohr magneton number from the Curie constant for substances obeying the Curie-Weiss law," it is found that the effective magneton number is a function of temperature. The process of calculation involves the inverse of the differential of the 1/x4 vs. temperature curve so that good and numerous data are necessary to obtain significant results. The data of Fallot23 show a discontinuous increase of about 12 pct in the effective magneton number between 850" and 900 oC, followed by a continuous increase up to the melting point. The data of Sucksmith and Pearce24 show a possible 8 pct increase. The older data of Terry25 and Weiss and Foex26 show a continuous increase. It is possible that small amounts of impurity atoms change these electronic transitions significantly. Fallot's23 data on a nickel alloy with 4.5 atomic pct Fe indicate that the discontinuity occurs around 1300 °C. Systematic investigation of the transition metals for transitions of this nature should provide information which would be very valuable for our understanding of these metals. The absence of antiferromagnetic structures in chromium has been shown by Shull27 using neutron diffraction techniques. M. E. Fine, E. S. Greiner, and W. C. Ellis (authors' reply)—The remarks by Drs. Samans and Ham are certainly very interesting, in particular those pertaining to the close agreement between the theoretically calculated values for transition temperatures in chromium and the experimental values reported by a number of investigators. This is a remarkable achievement and we shall look forward to a more detailed presentation of the method followed in their calculations. We do not believe that the transition in pure chromium near 40 °C remains temperature invariant with alloying, as was reported by Samans and Ham for a number of the substances that they studied. We have not done any work with alloys but base our belief on the results of earlier studies in which less pure chromium was included and considerably lower transition temperatures were observed. The transition tempera-

Jan 1, 1952

By C. Bezemer, I. Havenaar

An investigation was carried out on the dynamic liltration behavior of drilling fluids. In a set-up consisting of a porous pipe through which the drilling mud was circulated, dynamic liltration rates and cake thicknesses were determined as a function of flow rate and filtration time. Eventually, a state of equilibrium was reached; i.e., both cake thickness and filtration rate attained constant values. Concurrently, dynamic filtration tests were carried out in a simple dynamic filter apparatus where mud flow was similar to that in a rotational vismmeter. In both arrangements the relation between equilibrium liltration data and rate of shear at the cake surlace was studied. Filter pipe and dynamic filter apparatus were lound to give identical relations. It was therelore concluded that the latter apparatus, which is suitable lor routine measurements on small amounts of mud, could be used to determine the dynamic liltration behavior of mud under borehole flow conditions. Some data are presented on the effect of filtration pressure and temperature on equilibrium filtration rate and cake thickness. INTRODUCTION In oil well drilling, the drilling fluid used generally forms a mud cake on the permeable sections of the borehole wall while filtrate is lost into the formation. As to the conditions under which this filtration process takes place, a distinction should be made between static mud filtration (mud is not circulating) and dynamic mud filtration (mud is circulating). In recent years several investigatorsl-5 have studied the process of dynamic mud filtration about which little had previously been known. This type of filtration is the subject of this paper which confirms several findings of previous investigators. It differs from already published works, however, in the following respects. 1. It contains a description of a simple laboratory apparatus developed for dynamic filtration measurements on small amounts of mud. 2. The effect of rate of shear at the cake surface on dynamic filtration has been studied. As a result of this study, dynamic filtration data pertaining to the borehole conditions of mud flow can be found from laboratory tests. 3. Some data are presented on the effect of filtration pressure and temperature on dynamic filtration. The work was limited to a small number of muds. No attempt was made to compare data on API filtrare loss with dynamic filtration rates. Previous workers have clearly shown that no correlation exists between static and dynamic filtration rates. EXPERIMENTAL ARRANGEMENT To establish whether the effect of mud flow conditions on dynamic filtrations is governed by the rate of shear at the cake surface, two different types of mud flow were used. In this connection the experiments were partially conducted by means of a porous pipe through which mud was circulated, partly in a dynamic filter apparatus which somewhat resembles a rotational viscometer. In both cases the flow conditions of the mud were well defined, thus making it possible to-calculate rates of shear at the cake surface. The filter pipe was 200 cm long with an internal diameter of 3 cm. Its perforated wall was covered on the inside with filter cloth on which the mud cake could form. Mud was pumped through the pipe at linear rates varying from 20 to 186 cm/sec. The required filtration pressure was obtained by means of a lack-pressure valve downstream of the filter pipe. In this arrangement the type of flow existing in the borehole is reasonably well simulated. The dynamic filter apparatus (Figs. I. and 2) consists mainly of two concentric cylinders with a clearance of about 0.5 cm. The outer cylinder (rotor) can be rotated at rates up to 1,000 rpm. The outer surface of the inner cylinder (radius about 2.5 cm) is covered with filter cloth or paper supported by copper gauze. The two cylinders are mounted inside a pressure

Jan 1, 1967

Henry C. Carlisle: This is a husband-and-wife act, in which Mary Carlisle is going to listen, and break in as often as she feels like it. I am going to describe my career as a mining engineer. We are at Nantucket, in the 75 Main St. house; The year is 1959. Q: This is something the boys and I have wanted you to do for a long time. Carlisle: After leaving Columbia in 1910, I arrived at Ray, Ariz., January 1, 1911, and rustled a job from Louis Cates, Ralph Nowland and Sprott Boyd, who were running the Ray mine. I went to work as a surveyor's helper, made $90 a month, and paid $35 a month board. I lived in a dormitory where about 25 other engineers, graduates from different colleges, were living. It was very social and you made a lot of young friends early in the game. I did not think much of the idea of being a surveyor, or even a surveyors, helper; the higher-up surveyors only got $125 a month, and had been there quite a long time. So, I asked to be changed to underground sampling, where I would see the mine faces every day and learn more about mining. In about three months, I became an underground sampler and remained at this for a year, but in three months I was promoted to head sampler, with six people under me.

Jan 10, 1963

Discussion WEDNESDAY AFTERNOON, FEBRUARY 21, 1951 Ralph E. Grim presiding R. E. GRIM, CHAIRMAN-Has anyone a particularly fruitful point to make or question to ask on any of the papers that have been presented at the two sessions held on Monday and one held this morning? GENESIS OF ENDELLITE T. S. LOVERING-I think we are all a little bit embarrassed when we are asked if we have any particularly fruitful point for discussion; I just have a point. I believe that yesterday Bates said that he had found endellite in only hydrothermally altered rocks-he did not find it in sedimentary rocks-but this morning I heard Victor Allen say something about it as the normal product of weathering, and I am confused. My question concerns the genesis of endellite. I want to know whether endellite is found as a normal product of weathering. I understood from the paper by Bates that it was not a product of weathering and in the paper by Victor Allen* endellite was said to be a product of normal weathering. Did I misinterpret these two papers? T. F. BATES-I did not intend to state or imply that endellite is formed only under hydrothermal conditions. We have been studying the North Carolina deposits extensively and I feel that they illustrate very well the result of normal weathering processes acting on pegmatitic material. The resulting clay seems to be largely endellite or halloysite, almost to the exclusion of kaolinite. I may have misled you in the statement I made toward the end of my talk, to the effect that of all the kaolinic clays we have investigated with the electron microscope, we have not yet found halloysite or endellite in samples from clay deposits that are definitely sedimentary in origin. R. E. GRIM, CHAIRMAN-Professor Allen, have you anything to say on the matter of bauxite?

Jan 1, 1952