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By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1' to 10' of arc, but values of UP to 20' have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By C. F. Austin

lined-cavity shaped charge is an explosive mass with a cavity at one end and the detonator at the opposite end. The cavity is lined with a dense material, such as metal, glass, or a ceramic. Such an explosive device can be a useful drilling tool. Lined-cavity shaped charges are constructed to do just one thing — create a high-velocity jet of liner particles that can bore a hole in a target. The liner must be smooth and symmetrical, and high-velocity, high-brisance explosive must be used rather than ordinary commercial dynamites. Since the depth of target penetration is related to jet length, a standoff distance should be provided to hold the charge a short distance from the target. This allows the jet to lengthen prior to target impact. The best results are obtained when the jet is perpendicular to the target surface. Charges can be positioned for firing by taping them to a stake or simply laying them on a flat surface at the proper distance and angle with respect to the target. EFFECTS ON THE TARGET When a jet strikes a rock target, the jet and target particles at the jet-target interface move outward radially with respect to the jet axis to create a tremendous compressive load on the target material immediately below the target surface. The result is a shallow crater formed by spalling at the point of target entry. After cratering ceases, the steadily deepening hole continues to form as a result of the jet's imparting radial motion to the target particles at the jet-target interface. These radially moving particles collide with one another and with the hole walls, the net motion of the spent jet particles and target particles being back out of the hole in an axial direction (the backblast). The backblast keeps the penetration free of debris during penetration, al- though loose surface rock often falls into the hole after penetration ceases. The sudden stress relief after penetration ceases sometimes results in minor hole-wall rebound, which can partially fill the hole. The hole bottom will taper as the jet velocity decreases, until the jet velocity is too low to maintain the backblast. At this point the remaining jet and the following slug material are simply packed into the hole bottom. HAZARDS INHERENT IN USE Air blast from the highly brisant explosives used in shaped charges can damage nearby structures

Jan 1, 1961

By P. A. Beck

ACCORDING to a recent hypothesis of Sully,' xY. binary CT phases are characterized by 1.7 bonding 3d electrons per atom, which completely fill the first Brillouin zone. This hypothesis appears to imply that there are no empty 3d orbitals in the u phase, and that, correspondingly, this phase must be dia-magnetic, or at most weakly paramagnetic. On the other hand, Bowen and Hoar' reported that a u phase extracted electrolytically from an alloy steel became ferromagnetic when cooled to about —113°C. In view of the fundamental interest of the problem from the point of view of the electron structure of the u phase, it seemed worthwhile to study the magnetic properties of massive u phase specimens of various known compositions. Sigma specimens of the following compositions were tested: 1—40 atomic pct Fe, 40 atomic pct Cr, and 20 atomic pct Mo 2—35 atomic pct Fe, 35 atomic pct Cr, and 30 atomic pct Mo 3—48.7 atomic pct Fe, 50.2 atomic pct Cr, and 1.1 atomic pct W 4—40.7 atomic pct Co and 59.3 atomic pct Cr All specimens were found to be strongly paramagnetic at room temperature, particularly alloy No. 1. At liquid nitrogen temperature, alloy No. 1 be- came ferromagnetic; the other u alloys remained paramagnetic. Even though apparently not all u alloys become ferromagnetic at liquid nitrogen temperature, in view of their strong paramagnetism it is probable that the electron structure proposed by Sully is not correct. Similar qualitative studies were made with the p, P, and 8 phases." A p phase specimen of 57.2 atomic pct Co and 42.8 atomic pct Mo; a P specimen of 19.9 atomic pct Cr, 37.8 atomic pct Ni, and 42.3 atomic pct Mo; and a 8 specimen of 50.4 atomic pct Ni and 49.6 atomic pct Mo were tested at room temperature, and all were found to be paramagnetic, although considerably weaker than the u phase specimens described above. A test at liquid nitrogen temperature gave similar results for all specimens; none became ferromagnetic. Thanks are due to D. K. Das for preparing several of the alloys and to Pol Duwez of California Institute of Technology for kindly loaning four specimens of cr alloys. References 1 A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, p. 173. - K. W. J. Bowen and T. P. Hoar: Low Temperature Ferromagnetism of Sigma Phase in an Alloy Steel. Research (1950) 3, p. 484. 3 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951).

Jan 1, 1953

By Jack L. Henry, R. D. Holliday

GASEOUS products of an aluminum reduction cell consist mainly of carbon dioxide and carbon monoxide. Sulfur dioxide, hydrogen fluoride, and hydrogen sulfide have also been conc~usively identified. Carbon tetrafluoride has been observed only during the period when the anode is polarized.' This period, known as anode effect, occurs when the alumina content of the molten bath approaches depletion.= Increased resistance at the polarized anode results in a voltage rise from a normal 5 volts to as

Jan 1, 1958

By G. D. Hobson, I. Mrosovsky

Material balance relationships for expansion-type reservoirs above the bubble point have been discussed in recent years by H. N. Hall and M. F. Hawkins, Jr. The former drew attention to the effects of rock compressibility, and the latter to the effects of the compressibility of any interstitial water. Hawkins derived a general relationship which took note of oil, water and rock compressibilities, and then by assuming first, the absence of interstitial water and secondly, no effects due to interstitial water or rock compressibility, obtained relationships symbolically of the same form as those previously derived directly by Hall. Hawkins defined his terms clearly, and noted an approximation, due to the omission of a term involving the product of two compressibilities, made in reaching his final equation. There is, however, possible ambiguity with regard to Hall's written definition of the oil production term. One interpretation would mean that the produced oil and initial oil-in-place, if both required as stock tank barrels, would be obtained by using different formation volume factors in the conversion in order to satisfy the conditions implicit in Hall's formulae. The other would involve an approximation which, if used, was not stated. In both Hall's and Hawkins' studies the effect of the approximation or inconsistency is very slight. Nevertheless, it may be justifiable to give a somewhat more consistent derivation, since the complexity of the final relationships is not thereby greatly increased. Let the initial pore volume be Vi and the volume after a pressure drop of Ap, V. Then V = V, (1 - ?p . cr), where c, is the rock compressibility expressed as change in pore volume/unit pore volume/unit pressure change, and is defined with the initial pressure as base. Suppose that the interstitial water saturation under the initial conditions is Sw. The total volume of interstitial water under those conditions will be ViSw. If the volume of the water after dropping the pressure by ?p is V., this will be given by Vw = ViSw (1 + ?p.c,w), the compressibility of the water being c, which is ex- pressed using the volume at the initial pressure as base. If Boi is the reservoir volume factor of the crude oil for the initial reservoir conditions, and B. the equivalent factor when the pressure has dropped by ?p, with N the initial amount of oil expressed as stock tank barrels. N.Boi = Vi - V,Sw If n is the amount of oil produced (in terms of stock tank barrels) as a result of the pressure drop ?p, the remaining subsurface volume of oil at the lower pressure will be Bw, and Bc can be related to the compressibi:ity of oil and the pressure drop, and if c, is the compressibility factor based on the initial conditions, The relationship derived by Hawkins was case to a standard at the lower pressure, while a term (Ap) had been dropped, because of its smallness arising from its dependence on the products of two compressibility factors. When there is no interstitial water and rock compressibility can be ignored, Eq. 1 reduces to:

Jan 1, 1957

By J. C. Fisher

C. S. Smith has described a method for measuring the relative values of different solid-solid and solid-liquid interfacial tensi0ns. When a polyphase alloy is held at an elevated temperature, individual particles of each phase adjust their shapes and minimize the interfacial energy. Wherever three interfaces meet, the dihedral angles are such that the three interfacial tensions, considered as forces, are in equilibrium. When the angles between three forces in equilibrium at a point are known, it is possible to determine any two in terms of the third. In this way ratios of interfacial tensions have been .obtained. The value of a given interfacial tension ratio was found to be independent of the alloy system from which it was determined. Smith also has employed the method when one of the phases is liquid. When equilibrium is reached with respect to In the course of work on grain growth in high purity aluminum a simple optical method was developed for detecting the presence or absence of preferred orientation in annealed specimens. The specimens were prepared by grinding, polishing and "deep etching." The etching reagent used for high purity aluminum has been described.* The resulting etch pits produced selective

Jan 1, 1949

By Nicholas J. Grant, H. C. Chang

EMPHASIS on the importance of grain boundary sliding as a mode of deformation at elevated temperatures has been presented elsewhere.' The extent to which boundary sliding occurs under certain creep conditions has been determined for high purity aluminum2,3 and aluminum alloys.' In general, boundary deformation extends quite far into the adjoining grains, resulting in a rather wide band of deformation along the grain boundaries. This has led some investigators to doubt that grain boundary sliding consists of shearing along the boundary surface; it has been contended instead that boundary sliding is a result of concentrated slip in the neighborhood of the deformed grain boundaries."' The purpose of this note is to present evidence that grain boundary sliding takes place by a bulk shear process. gh purity polycrystalline aluminum, wherever and whenever there is grain boundary sliding, boundary migration and concentrated deformation along both sides of the deformed boundary are associated with it. Therefore, it has been rather difficult to obtain unambiguous evidence of boundary sliding. On the other hand, it would be expected in certain alloys of aluminum, when tested under particular conditions. that the severity of the interfering effects of boundary migration and concentrated deformation along the deformed boundary might be reduced. Current research in this laboratory' shows that a 20 pct Zn-A1 solid solution alloy fractures in an intercrystalline manner during creep at 500°F with a small total elongation of not more than about 14 pct, and that it does so with extremely limited grain boundary migration. Accordingly, this alloy was chosen for the present study. The experimental procedure was similar to that used in previous work and has been presented elsewhere.' Two parallel flat surfaces were milled from a round specimen. The gage portion of the specimen was 1 in. x .09 in. x .17 in. The specimens, which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar. The specimens were subjected to creep at 500°F at stresses of 2000 to 5000 psi. The rupture times were from 10 sec to 3 hr. Appreciable boundary sliding occurred in all the tests. A typical example of boundary sliding is shown in Fig. 1. (The tension axis is vertical in the micrographs.) Sliding has taken place along the boundary between grains A and B unaccompanied by important boundary migration. The sharpness of the offset at the triple point can be clearly seen in grain C. As a result of sliding along the boundary between grains A and B, a new boundary surface between grains A and C was created. The offset at the triple point is about 0.07 mm. This boundary sliding is accompanied by the formation of rather sharp kinking bands and, of course, slip on several slip systems in grain C. This type of deformation has been referred to as fold formation' in previous work with high purity aluminum.

Jan 1, 1957

By H. E. Stauss, J. Hino

INTEREST in silicon has arisen again in the past decade as a result of improvements in crystal rectifiers.' Although the preparation of silicon was first reported by Berzelius in 1880, the early product was of relatively low purity, and only the need for rectifiers in World War II led to the production of a 99.9+ pct pure powder. This material in crystalline form was consolidated into massive silicon for use, and the method developed was to melt it with selected added constituents as "doping" agents. Melting techniques, therefore, are of great importance. There are two basic problems in producing silicon ingots free of doping additions; one is the prevention of spitting and the other is prevention of cracking of the ingot during freezing. The most satisfactory arrangement yet developed for producing massive silicon is to melt and freeze in a cylindrical quartz crucible surrounded by a concentric heating element and concentric radiation shields or insulation. For example, use can be made of a tubular heater with a high frequency generator as the source of power and reflecting shields of alundum cylinders. The spitting of silicon is related to gas evolution, and the gas comes from two primary causes—adsorbed gas and the reaction products of silicon and the crucible. Gas is also released from bubbles contained in the quartz crucible walls. Improved removal of adsorbed gas can be achieved by means of controlled melting and freezing. The seriousness of the problem in vacuo is reduced with an electrically operated mechanical movement of the high frequency power coil. The upper portion of the powder charge is melted first and the high frequency coil lowered until the powder is completely molten. During cooling the high frequency coil is raised slowly. These means also reduce the final nonviolent extrusion of large beads of metal through the ingot top during freezing. Better control of spitting and bead extrusion is obtained when melting is done under helium at. atmospheric pressure instead of in vacuo. The problem of reaction between silicon charge and crucible in practice is confined to the reaction between silicon and quartz. This2 apparently is: Si + SiO2 + 2SiO The part that this reaction plays in spitting has not been isolated for separate study. SiO is a volatile vapor at the melting point; of silicon and is released freely during melting in vacuo, but hardly at all in helium at atmospheric pressure. The cracking of ingots is a major difficulty in melting silicon, and its prevention requires special melting techniques or the addition of "toughening" agents such as aluminum or beryllium.' The cracking of the ingots has been explained as being the result of the expansion that occurs upon freezing; although direct observation of freezing ingots reveals visible cracks on the surface only after a red heat has been reached, suggesting that cracking is the result of differential contraction of silicon and quartz. Silicon wets quartz, and the ingot adheres tightly to the crucible. Therefore as ingot and crucible cool, the two either have to pull apart, or at least one must crack. Surprisingly, in spite of the relative thinness of the quartz and the thickness of the ingot, the ingot and the crucible both crack. Microscopic and X-ray4 studies fail to show any plastic flow other than twinning in the ingots. Slow cooling fails to prevent cracking. Another possible solution to cracking is to weaken the crucible. Use of thin-walled crucibles finally led to success with fused quartz crucibles with a wall thickness of 0.25 to 0.50 mm. With such thin-walled fused quartz crucibles consistently uniform success is secured in producing sound ingots 30 mm in diam from the purest available grade of silicon (99.9+) without the use of any type of addition. Melts are made in the size range of 50 to 100 g. Omission of a deliberately added doping agent is not sufficient to insure pure ingots. The reaction of silicon with crucibles and the resultant solution of impurities in the silicon is well-established." In this laboratory, the presence of Al, Be, and Zr has been found spectroscopically in ingots melted in contact with alumina, beryllia, and zircon. The best crucible materials reported in the literature are MgO and SiO2. Use of MgO in this laboratory has resulted in a heavy deposit of magnesium on the furnace walls, showing that a reduction of the magnesia occurred and the resulting magnesium removed from the melt by volatilization. In the case of quartz, the silica is reduced and SiO liberated to deposit on the equipment walls. There probably is real danger that oxygen is dissolved in the ingot when either magnesia or silica is used as the crucible material. Preliminary analyses by Dean Walter in his vacuum unit in this laboratory6 indicate the presence of oxygen in undoped silicon melted in quartz.

Jan 1, 1953

By L. D. Jaffe

IN previous metallographic work on titanium and its alloys, difficulty has been encountered in distinguishing spheroidal particles of titanium hydride, dispersed in a-titanium, from other phases that may be present, such as p-titanium. This problem is common in examination of commercial unalloyed titanium.' In the course of an investigation of the Ti-H phase diagram, it was noted that titanium hydride, dispersed in a matrix of a-titanium, showed strong optical anisotropy when examined under polarized light. With sensitive tint illumination, particles of the hydride, when the stage is rotated, changed from bright yellow to bright blue in color. Since P-titanium is cubic, it showed no color change on rotation, remaining dark gray or blue-gray. Although a-titanium is hexagonal, it showed only a minor color change, going from pale pinkish-blue to pale purplish-blue. These colors could be modified somewhat by adjustment of the illumination. They were observed in specimens mechanically polished, both without etching and after etching with hydrofluoric acid-nitric acid mixtures in either water or glycerine. The strong color change of the hydride seems to offer a simple method for its metallographic identification. Optical anisotropy of titanium hydride is inconsistent with its accepted face-centered-cubic structure.' Samples of iodide titanium containing 6 to 40 atomic pct deuterium were prepared for diffraction studies. After deuterating and slow cooling' the samples were held 21 % hr at 400 °C, water quenched, held 61 hr at 100°C and quenched, then held 64% hr at 255 C and quenched. Debye ex-posures with MoKa X-rays and 1.111A neutrons were made at room temperature of samples as-deuterated and after the 100" and 255°C treatments. Table I shows the lines observed, in addition to those attributable to a-titanium. These data show that the hydride phase was not cubic, but probably tetragonal. The titanium atoms appeared to form a body-centered-tetragonal lattice complex, two titanium atoms per cell, with approximate dimensions: a = 3.12A, c = 4.18A, and c/a =1.34A. This is equivalent to a face-centered-tetragonal complex, four titanium atoms per cell, with approximate dimensions: a = 4.42A, c = 4.18A, and c/a - 0.946A. The presence of the 2.98 and 1.81A neutron lines indicates that the true Bravais lattice is not identical with this lattice complex, but may be primitive tetragonal with dimensions some multiple of those of the complex. The relative intensities of the hydride and a-titanium X-ray lines as functions of overall composition indicated that the hydride, presumably in equilibrium with the a at 100" to 255"C, contained more than 62 atomic pct H. Acknowledgments The experimental work covered in this report was done at Brookhaven National Laboratory, through the courtesy of D. Gurinsky. The cooperation of J. Sadofsky, 0. Kammerer, A. McReynolds, and A. Cendrowski is gratefully acknowledged.

Jan 1, 1957

By R. Bakish, W. D. Robertson

IN the course of a study of stress corrosion cracking of AuCu,, it was necessary to develop new electropolishing and metallographic etching methods. The techniques are generally useful for Cu-Au alloys, including the AuCu composition in which transformation markings are well delineated. For electropolishing, the only satisfactory electrolyte and procedure that has been found1 has the composition given in Table I. The solution must be vigorously stirred while polishing and the temperature maintained in the range of 55" to 62°C. The electrolyte is very unstable and can be used only for 10 to 15 min after which its color changes and a dark-brown precipitate forms. The polishing time is between 1 and 4 min depending on the initial surface preparation. The use of a hood is recommended to avoid the danger of cyanide gas which may form at one of the electrodes even though the solution is alkaline. The optimum current and voltage conditions for vertical anode and platinum cathode are on the plateau shown in Fig. 1, in which voltage is measured across the cell terminals. At voltages below the plateau, etching of grain boundaries occurs and under some conditions, which have not been clearly defined, octahedral etch figures are observed. For general purpose grain-size determination in polycrystalline alloys, a 3 pct solution of iodine in methyl alcohol is used with excellent results. However, when it is necessary to reveal small orientation differences or concentration gradients in an alloy, the iodine etch is not satisfactory. For this purpose, a highly satisfactory etching procedure was developed during this investigation. It involves the use of the vapor given off by freshly prepared aqua regia. The solution employed is 3HC1 to lHNO, which decomposes in accordance with the reaction HNO, + 3HC1 = NOCl + 2H,O + Cl,. The polished specimen surface is held about 1 to 2 cm above an aqua regia solution for 2 to 10 sec depending on the intensity of the contrast required and the surface is not subsequently washed. The results obtained with a coarse grained cast structure are shown in Fig. 2. Subgrain boundaries in a single crystal and concentration gradients within the boundaries are developed by the same treatment with the results shown in Fig. 3. Obviously, any conclusions regarding structure-dependent properties will be modified by the pronounced heterogeneity, which is not clearly evident when more conventional methods are used. Interesting structural details are also revealed by treatment for 4 hr at 850°C in unpurified tank argon. Fig. 4 shows a pattern characteristic of orientation-dependent oxidation.

Jan 1, 1956

By Nicholas J. Grant, Italo S. Servi

SPECIAL polishing and etching techniques were developed during an investigation of the high temperature mechanical properties of high purity aluminum (99.995 pct Al).* Electrolytic polishing was done successfully in the following electrolyte: 5 ml perchloric acid (72 pct), and 95 ml glacial acetic acid. No special precautions need be taken during the preparation of the electrolyte since no appreciable heat of mixing is evolved. Although the electrolyte is not an explosive, it is recommended that Jacquet's safety rules' be followed during the polishing operation. A voltage of 25 to 60 v gives a good polish in about 2 min at room temperature after preparation on 3/0 metallographic paper. Most of the grain boundaries are visible under the microscope after polishing. Since the current is controlled essentially by the resistance of the bath, it is necessary to keep the anode-to-cathode distance as constant as possible. Accordingly, polishing of irregularly shaped pieces will be difficult. A cooling bath and a stirring system are advisable in order to keep the temperature of the bath uniform and constant. Coarse-grained samples can be macroetched in a few seconds by lowering the voltage below 10 v. This is done after electrolytic polishing, without removing the sample from the bath, Fig. 1. The specimen can be repolished in less than 1 min by raising the voltage above 25 v. The "galvanic etching" technique, which has been described elsewhere,' was found to be helpful not only for macroetching, but also for microetching coarse-grained specimens. In fact, the different orientations of adjacent grains provide good contrast at the grain boundaries, when the sample is observed under polarized light. If the specimen is only partially etched, Fig. 2a, the grain boundaries can be located without completely destroying the appearance of the surface of the specimen. The unetched surface appears black under polarized light. Excellent color contrast is obtained by using a "sensitive tint" plate in the optical system of the microscope. In this case, the unetched surface has a magenta color, while the etched part of the sample assumes different colors varying from green to brown, according to the orientation of the grains. Etch pits were produced on high purity aluminum by using the technique suggested by Lacombe and Beaujard." Good results also were obtained by substituting 70 pct nitric acid for the fuming nitric acid recommended. This gave an etching reagent of the following composition: 70 ml nitric acid (70 pct), 50 ml hydrochloric acid (37.5 pct), and 3 ml hydrofluoric acid (48 pct). An example of the results is shown in Fig- 2b. The outline of the etch pits is revealed sharply if the specimen is observed under polarized light, as shown in Fig. 2c. These metallographic techniques are not suitable for the examination of commercially pure (2s) aluminum. References 'P. A. Jacquet: Metal Finishing (Nov. 1949) 47, p. 62. 21. S. Servi: Metal Progress (1950) 58, p. 732. 3 P. Lacombe and L. Beaujard: Journal Inst. of Metals (1947) 74, p. 1._________________________

Jan 1, 1952

By P. R. Sperry

A METHOD was recently devised to indicate two or more successive stages of the migration of grain boundaries in aluminum, and to record the direction of the migration. This technique was used for the study of the various types of boundary migration occurring in high purity aluminum.' The method employs alternate annealing and electrolytic etching treatments, repeated as many times as desired. All successive sets of grain boun- dary positions revealed by the various etches appear superimposed on each other. The last etch is designed to leave an oxide film on the surface which is optically anisotropic. The orientation of the oxide film at each point is determined by the orientation of the underlying aluminum grain. When viewed with polarized light using crossed nicols and a Biot-Klein quartz plate, grains with differing orientations appear in different colors, as described by Hone and Pearson.' The last boundary positions are revealed by these color differences. The first step of the process is to obtain a desired starting grain size by annealing, for example, if high

Jan 1, 1951

By L. D. Jaffe

IT is now well established that quenched and tempered titanium alloys have much better ductility when the quenching is from a two phase a-B structure, rather than from an all B structure. The corresponding microstructural differences, however, have not been shown in previous publications. Accordingly, specimens were cut from a % in. rod of commercial RC-130A, containing 7.9 pct Mn and 0.12 pct C, which had been previously hot rolled, heated 1 hr at 1100°F, and air cooled. (The same heat has been studied by others." 7 Samples about 1/4 in. cube were heated in helium 1/2 hr at 1450' or 1700°F, quenched in brine, tempered in helium 1 hr at various temperatures up to 1250°F, and quenched in brine. They were then sectioned and metallo-graphically examined, using an etchant of HF-HNO, in glycerine. As quenched from 1700°F, the microstructure observed was clear /3. (Probably also present was U, as the hardness was 400 Vhn, but w is not yet reliably revealed by any metallographic technique.) When the /3 quenched alloy was tempered at a high temperature, a precipitated as a grain boundary film

Jan 1, 1957

By R. C. Troxell, S. C. Sun

EFFORTS to obtain definite quantitative data when employing the currently used bubble pick-up method1,2 as a pre-flotation investigation tool led to the adoption of the magnifying mirror method and the microscopic method modifications. Quantitative data obtained by these two methods were converted into bubble pick-up indices and bubble pick-up coefficients. Rough correlations were established between the calculated indices and the results of contact angle testing as well as actual flotation under the same conditions. The basic steps of the magnifying mirror method are as follows: 1—mixing 200 ml distilled water, sized and cleaned mineral particles of approximately 0.5 g, pH regulator, and flotation reagents in a glass beaker; 2—swirling the mineral particles to the center of the beaker to leave a clear circumference; 3—pressing an air bubble against the mineral particles for about 1 sec, and then moving the mineralized air bubble to the clear part of the beaker; and 4—dropping all the attached mineral particles of the air bubble by tapping the bubble holder, and counting the number of the dropped particles by looking at the magnified image in the mirror positioned beneath the beaker. This method is impractical for mineral particles which are transparent in water or finer than 200 mesh. The microscopic method is essentially similar to the above described magnifying mirror method, with the exception that the mineralized air bubble was drawn up into the bubble holder and subsequently discharged onto an externally placed watch glass, where the number of pick-up particles was counted with the aid of a microscope or hand lens. Drying was necessary when the discharged liquid interfered with the counting. The results of the bubble pick-up tests can be simply expressed in the form of the actual count. However, this can be misleading because the number of pick-up particles varies not only with the size of bubble but also with the size of particles. This short-coming is largely remedied by the use of the bubble pick-up index. as calculated from the following equation: PI = (pn/p) 100 [1] in which PI and pn are respectively the pick-up index and the number of pick-up particles under any test conditions, and p is the maximum number of pick-up particles of the same mineral under optimum flotation conditions, with the same size holder and particle. The bubble pick-up coefficient is a term coined to denote the difference between the bubble pick-up index of mineral particles in a liquid and that of the same mineral-liquid mixture plus a chemical reagent at the same pH value. For example, the difference between the pick-up index of a naturally floatable bituminous coal in a solution of water and kerosene and that of the same coal in water alone is a bubble pick-up coefficient. Compared with the contact angle method, the quantitative bubble pick-up method is inferior in accuracy but superior in sensitivity. Other advantages of the bubble pick-up method are that the apparatus can be easily assembled, the mineral sample is conventionally prepared, and the test procedure is relatively simple. References S. R. B. Cooke: The Flotation of Quartz Using Calcium Ion As Activator, Trans. AIME (1949) 184, p. 306. 'G. A. Last and M. A. Cook: Theory of Collector-Depressant Equilibrium at Mineral Surfaces. Paper presented at St. Louis Meeting, AIME (February, 1951).

Jan 1, 1954

By G. Vaux, M. L. Fuller

AN apparatus and procedure for the determination by X-ray reflection of preferred orientation of crystals in rolled metal with the Geiger counter X-ray spectrometer was described by Schulz.' This is an excellent procedure and we have used it continually for several years. In our use of the procedure, two modifications have been made and used during most of this period. One of these provides for automatic scanning and recording of the reflections, and the other makes possible the application of the procedure to coarse-grained specimens and permits measurement of almost all orientations without resort to the transmission technique. The automatic scanning and recording are accomplished by a motor drive of the inner ring of the Schulz apparatus (see R, in Fig. 2 of his paper and R2 in Fig. 1 of this note) in synchronism with the chart recorder of the North American Philips 90" X-ray spectrometer. A rate of 10" per min is used. A scan of 180" is obtained corresponding to poles on the stereographic projection whose locus is a great circle. The modification for coarse-grained material is accomplished by allowing a larger area of the specimen to contribute to the X-ray diffraction. In the Schulz apparatus the incident X-ray beam is confined by a slit system to rays in the plane of the spectrometer. Schulz demonstrated that this restriction of the X-ray beam permits a survey of the X-ray reflections without correction up to about 80" on either side of that specimen position in which the specimen is perpendicular to the plane of the spectrometer. This is the angle + of rotation of the inner ring R2. One of these slits is horizontal and extends across the X-ray source side of the specimen. In the modification this slit is removed, thus permitting greater divergence in the X-ray beam and the irradiation of a larger area of the specimen surface. Fig. 1 shows the apparatus with the motor drive and with the slit removed. Discontinuities in the recorded X-ray intensity plot due to the few participating crystals in coarse-grained metal are much lessened. The increased divergence does not cause reflections from other crystal planes to enter the Geiger counter slit. An important advantage of the original Schulz scheme is thus lost and a system for correction is required. To do this, a compact of atomized copper powder was prepared and tested by the original Schulz method for the absence of preferred orientation. The horizontal slit was then removed and a curve recorded showing the variation of intensity with angle +. In our arrangement the intensity was uniform within the range + equals ±30°. Beyond this the intensity fell off rapidly reaching zero at ±90°. The curve thus produced is then used to correct measurements made on preferred orientation specimens. In practice this is accomplished by constructing from this calibration curve a family of curves which, as a transparency, can be superimposed on the recorder chart to read corrected intensity directly. Not only does this method permit the handling of coarse-grained material but it also makes possible the plotting of intensities almost to the circumference of the stereographic pole figure projection. Thus, nearly the entire pole figure can be plotted without the necessity of using the transmission technique. Moreover, intensities are much greater, an advantage when surveying crystal planes of poor reflecting power.

Jan 1, 1954

By I. Havenaar

EXPERIMENTAL DATA In an article by C. K. Ferguson and J. A. Klotz,1 experiments on the filtration of drilling muds under borehole conditions are discussed. Experimental data on mud filtration through the wall and the bottom of the hole are presented. From the data on bottom-hole filtration it was concluded that the filtrate does not flow freely into the formation, but that the pores of the formation are plugged by the mud. A quantitative interpretation of the data can be civen, by using a formula for bottom-hole filtration, dehved below. This formula is based on the following assumptions, 1. Each time a blade of a drag bit, or a cone of a roller bit, moves along the bottom of the hole, the mud cake is completely removed. 3. A new mud cake is immediately formed on the freshly produced surface, and losses of "whole" mud into the formation are negligible (this is equivalent to an immediate plugging of the pores). 3. The filtration of the mud on the bottom of the hole follows the classic law: V = A +1—(Eq. I), where t is the time required to yield a volume of filtrate V, A is the surface area of filter cake, and C is a constant. The application of this equation means that any eroding effect of the mud stream on the mud cake is neglected. The formula for the calculation of the volume of filtrate, Q,, flowing in one second through the hole bottom (diam. d cm), when using a bit with n cones or blades rotating at a rate of rn revolutions per second, is derived as follows: The mud cake is formed on the bottom of the hole in the time t =1; the filtrate volume V which passes n through the bottom In this time 1s given by Eq. 1: After1/nmsec the mud cake is removed. In one m second this process takes place nm times. Therefore the volume of filtrate, obtained in one second is given by This equation has now been applied to the experiments of Ferguson and Klotz. The constants C were derived by means of Eq. 1 from the API filter losses of the muds used by the authors (t = 1,800 sec; A = 45.16cm2). A three-cone bit was used (n = 3) at 90 rpm (m = 1.5). The calculated figures are compared with the experimental data in the table below. The calculated values of Q, are usually lower than the experimental values. This may be due to the following causes. 1. The value of C used in the calculation is based on the API filter test (filtration pressure of 100 psi), whereas the experimental data were obtained with a filtration pressure of 200 psi. Although the effect of the pressure on C is not large, C decreases somewhat with increasing pressure, and this leads to a higher filtration rate. 2. Mud losses and the eroding action of the mud stream on the cake are not entirely negligible. 3. The values of Q, derived by Ferguson and Klotz from their experiments are too high, because of their assumption that all pore liquid within the formation drilled is picked up by the drilling mud. It is found, however, that the calculated values of Qf, except in the case of oil base muds, are of the right order of magnitude. ACKNOWLEDGMENT The author wishes to thank the management of the Koninklijke/Shell-Laboratorium, Amsterdam, for permission to publish this note.

Jan 1, 1957

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By H. E. Stauss, G. Sandoz

THE purpose of this note is to draw attention to the possibility that a melt may be contaminated by a material not in direct contact with it by means of gaseous intermediate agents. In recent years silicon has assumed a position of importance because of its use in rectifiers and transistors and close attention has been required to control of both purification and contamination during all stages of preparation.' This note reports the observation that a graphite heater may have contaminated silicon ingots without direct physical contact through reactions that developed gaseous products. Several ingots made with the equipment of Hino and Stauss,2 using a graphite heater in a dried helium atmosphere, were found to have a small amount of a very hard substance on the free surface. X-ray analysis by F. W. von Batchelder showed the sub- stance to be Sic. Similar contamination was not found when the heater was tantalum, indicating that the carbon had not come from an original impurity in the silicon powder. One source of the carbon could have been volatile matter released from the graphite heater. This heater had been used about ten times at the time of the observations. A second source of carbon could have been a direct reaction between the quartz crucible and the graphite heater to form CO, or an indirect reaction involving a crucible-melt interaction and volatile SiO as an intermediate product. Such reactions should have developed Sic on the heater; and in fact a yellow powder did form on the inside of the graphite heater although its composition could not be determined. References 'H. C. Torrey and C. A. Whitmer: Crystal Rectifiers (1948) Chapter 10. New York. McGraw-Hill Book Co. 2 J. Hino and H. E. Stauss: Trans. AIME (1952) 194, p. 656; Journal of Metals (June 1952).

Jan 1, 1954

By N. Cabrera

IN a recent paper Kuczynski' studied the rate at which the crack between a metallic plane and a spherical particle of the same material is filled up gradually when heated at temperatures near the melting point. If x is the radius of contact between plane and sphere (fig. I), Kuczynski shows experimentally that x5 = At [1] where t is the time. Assuming that the mechanism of transport of matter is the volume diffusion of vacant lattice sites, he is also able to prove Eq 1 theoretically. The constant A contains as a factor the self-diffusion coefficient of the metal and he shows that the values for this coefficient deduced from his experiments yield the same activation energy as that calculated by other methods, which is a confirmation of this point of view. Kuczynski has also considered theoretically the law of growth of x which would be expected if surface diffusion were the important mechanism. He suggests that x should then obey a law of the form x7 = At, and claims to be able to decide the mechanism involved from the observed law of growth., The purpose of this note is to prove this incorrect. On the contrary, when the mechanism is surface diffusion Eq 1 is also obeyed, but with a different constant A. Following Kuczynski, we suppose the bottom of the crack (surface A A) to have an average radius of curvature p. As a result of this curvature the concentration of adsorbed atoms in this surface, n(p) per cm2, will be smaller, and the concentration of vacant lattice sites in the neighborhood, N(p) per cm3, will be larger than the corresponding concentrations, n(w) and N(w), for a flat surface. For all practical cases we can write Thomson's formula in the form n(co)— n(P) N(P)—N(cc) _ 2a-a" n(oo) JV(co) kTp [2] where u is the surface energy of the metal and a the interatomic distance. 1. Let us now consider the mechanism of surface diffusion. We suppose the concentration of ad-

Jan 1, 1951