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By G. K. Dumbauld, B. E. Morgan

A satisfactory well-cementing composition must retain its fluidity long enough to be pumped into Place; then it must develop within a reasonable length of time sufficient strength and impermeability to anchor the casing in position and to form an effective seal between the casing and the formations. These properties may be evaluated by pumpability, strength (compressive or tensile), and permeability tests. Laboratory test procedures for the determination of pumpability time and strength development have been outlined previously and are readily available,1 but a satisfactory and convenient laboratory procedure for the measurement of the permeability of set cement has not been developed heretofore. some permeability data have been obtained previously by passing air through dried cement specimens.2 such a procedure is unsatisfactory because the drying of set cement alters it physical and chemical properties and subjects it to conditions dissimilar to well conditions. A more realistic method would be one wherein the cement remains water-saturated durin

Jan 1, 1952

By Rudolph G. Wuerker

THE scarcity of values of tensile strength of rocks has been explained by the lack of successful testing procedures. In the case of mine rock a description is given' of the difficulties encountered in testing a cylindrical specimen, such as a core, by conventional methods. Over a period of years the following method has given definite and reproducible results with the weakest as well as with the strongest rocks. It does not completely supersede the use of cores with special fixtures but is a supplement in all cases where cores cannot be obtained, as from soft rocks, or in cases where it is less expensive to prepare test specimens by cutting them out of the rock instead of drilling cores. Principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar.' The test specimen, Fig. 1, has the shape of a briquet. While in the original cement mortar test the briquet is cast in a special mold, it is prepared from rocks in different ways, depending on how easily they can be cut and shaped. Soft rocks, which cannot be core-drilled with a carboloy or diamond bit, are simply hand-cut. Only two dimensions need be watched. The first is the 1-in. diam at the narrowest cross-section of the briquet. The other critical measure is the radius of curvature of the waistline, as the roller supports in the grips have a fixed distance. This radius is ground out of the solid by means of a carborundum grinding wheel having a 3/4-in. radius. Medium hard rocks can be core-drilled with a carboloy bit. The resulting core can be used for nondestructive sonic testing first, and after that for any destructive test. By using an EX-bit and by carefully placing the coreholes, preferably by using a tenplate such as shown in Fig. 1, it is possible to obtain from the rock a punched sample from which numerous tensile briquets can be made. The outside radius of the EX-bit differs from the radius of curvature of the briquet by 1/8 in., but this still permits placing and aligning the specimen in the grips. In the case of bedded rocks the core might have bedding planes normal to the plane of the briquets, and rocks can be tested in any arrangement of the bedding planes desired. Hard rocks, limestones, igneous, and metamor-whic rocks can only be diamond-drilled or diamond-cut. Here the method of getting the tension briquets by accurate placing of EX-drill holes is especially economical. The tops of the briquets made from hard rocks cannot be rounded; they are straight cuts made with a diamond cut-off saw and rounded off on a polishing wheel. Results: As long as specimens broke over the waistline the results were considered acceptable. Further statistical treatment of the tests' showed a satisfactory percentage of standard deviation. The tensile strength values obtained by this method do not represent true values because of the stress concentration caused by the curvature of the side of the piece and because of the closeness of the grips. The ratio of maximum to average stress at the plane of failure has been determined to be about 1.75." All tensile strength values listed in Table I are corrected accordingly. To avoid this stress-concentration, if there are a sufficient number of cores, tensile strength can be measured by imbedding the cores in mortar in the two outer briquets in the gangmold.4 Strain-Measurements: The applicability of the briquet specimens for strain observations was tested in the case of sandstone and shale. Two element Rosette SR-4 strain gages were used. Young's modulus and Poisson's ratio, both in tension, were computed and found to be different from those in compression, determined during the same test series and from the same rock, see Table I. References 1 L. Obert, S. L. Windes. and W. I. Duvall: Standardized Tests for Determining the Physical Properties of Mine Rock. U. S. Bur. Mines R.I. 3891 (1946). 2 Test for Tensile Strength of Hydraulic-Cement Mortar, ASTM Standard C 190-44. S F. O. Auderegg, R. Weller, and B. Fried: Tension Specimen Shape and Apparent Strength. Proc. ASTM 11939) 39, pp. 1261-1269. 4 API Code 32.

Jan 1, 1956

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 J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

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 J. W. Putman, N. J. Grant, D. S. Bloom

SEVERAL recent determinations of the melting S point of pure chromium have been reported which give values of 1845°C1; 1895°C,² 1930°C,³ 1860°C,' and 1890°C.5 because of this wide spread of values, it appeared desirable to make one additional attempt to obtain a more accurate, reliable figure. bloom and Grantx recently reported a phase transformation in chromium:.--- it was desired to check this, too, in the course of checking the melting point. To accomplish this, a much higher purity chromium was required. Electrolytic chromium containing about 0.5 pct 0 was crushed to a finer size and was then annealed in highly purified, dried hydrogen at 1375°C for 100 hr. This treatment produced chromium with about 0.008 pct 0, 0.002 pct N, and negligible carbon. The balance of the impurities was 0.3 pct Fe, 0.03 pct Si, 0.004 pct S, and less than 0.001 pct Mo. This chromium was melted in a stabilized zirconia crucible under pre-purified argon, using induction heating. Temperature measurements were made with annealed wolfram-molybdenum thermocouples and a Leeds and Northrup Speedomax Recording Potentiometer. The thermocouples were annealed for 1 min in hydrogen at a temperature of about 2400°C. Each leg of the thermocouple was immersed in an ice-water mixture using mechanical connectors to the lead wires. The thermocouple tip was immersed in the molten chromium in a zirconia protection tube which introduces an error of about 3°C as a temperature drop through the walls of the tube. The weight of chromium was about 183 g. The dimensions of the melt in the crucible were about 1.25 in. diam x 2 in. high. The tip of the thermocouple was held about ½ in. from the bottom of the crucible. Two new thermocouples were used with the above set-up giving the results shown in Table I. Since this chromium is purer than that used by Greenaway, Johnstone and McQuillan,' by Carlile et al.,4 and other investigators,²,3 it is believed to be the more accurate. Thermocouple aging effects which are believed responsible for the high value of 1930°C³ were avoided in this work. This value of 1903°C is correct to about ±10°C. The right hand column lists the temperature of the a ? ß transformation on heating and the ß ? a on cooling.3 A sample curve is shown in Fig. 1. The value so determined is 1840°C + 15°C. Fig. 1 gives adequate evidence that there is a transformation in chromium at high temperatures.' References 'H. T. Greenaway, S. T. M. Johnstone, and M. K. McQuillan: High Temperature Thermal Analysis USing the Tungsten-Molybdenum Thermocouple. Journal Inst. Metals (November 1951) 19, p. 109. ²J. W. Putman, R. D. Potter, and N. J. Grant: The Ternary System Chromium-Molybdenum-Iron. Trans. A.S.M. (1951) 43, p. 824. ³D. S. Bloom and N. J. Grant: Chromium-Nickel Phase Diagram. Trans. AIME (1951) 191, p. 1009; Journal of Metals (November 1951). ' S. J. Carlile, J. W. Christian, and W. Hume-Rothery: The Equilibrium Diagram of the System Chromium-Manganese. Journal Inst. Metals (1949) 76, p. 169. 5G. Grube and R. Knabe: Ztsch. Elektrochemie (1936) 42, p. 793.

Jan 1, 1953

By P. Breidt, E. S. Greiner

THIS note reports a determination of the melting point of germanium, and the liquidus of the Ge-Ga alloys; lattice constants of the a phase are given. The alloys were prepared by melting germanium (>20 ohm-cm resistivity) and gallium (99.6 pct) in evacuated silica tubes. The materials (50 to 70 g) were heated at 1000°C, held in the liquid state for about ¾ hr, and then cooled rapidly in the tubes. Points on the liquidus were obtained by thermal analysis which consisted of obtaining time-temperature data during heating and cooling the materials in high purity graphite crucibles and a helium at- mosphere. Temperatures were determined with a Pt—Pt-Rh thermocouple protected by a silica sheath. The couple was calibrated against a National Bureau of Standards calibrated couple and also against the freezing points of copper, silver, aluminum, and the 28.1 wt pct Cu, 71.9 wt pct Ag alloy eutectic. The samples for X-ray analysis were prepared by heating small pieces of the ingots in evacuated glass or quartz tubes at temperatures between 600" and 900°C for periods ranging from 2 hr to 22 days, periods deemed sufficient for equilibrium to be attained, followed by quenching in water. The heat-treated samples were ground to powder for X-ray analysis. The lattice constants of the germanium-rich phase (a) were determined with a baok-reflection focusing camera. The X-ray reflections (331 and 422 Cr Ka, 422 and 333 Cr KB) were corrected

Jan 1, 1956

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 S. C. Carapella, E. A. Peretti

DURING a literature survey of the indium-zinc phase diagram, controversial reports on the composition of the eutectic point were encountered. The value reported in the investigation of Wilson and Perettil and in a later investigation by Valen-tiner' was 4.0 wt pct zinc. The most recent work recorded on this system consisted of an exhaustive survey of alloys by Rhines and Grobe8 in which they indicate a value of 2.8 wt pct zinc for the eutectic composition. To clarify this aspect of the diagram, a series of alloys were prepared by melting the respective constituents in a glass test tube under a covering of mineral oil and slowly cooling the melt in a furnace. The zinc used was Baker's C.P. and had the following analysis: insoluble in H2SO4—0.0l pct; pb—0.001 pct; Fe-—0.001 pct. The indium, which was supplied by the Indium Corporation of America, had a purity of 99.9'7 pet with the following impurities: Cu—0.002 pct; Pb—0.006 pct; Sn—0.01 pct; Zn—0.01 pct. The alloys were prepared for metal-lographic examination using a technique already reported' and a new value of 2.0 ± 0.1 wt pct zinc was observed. An alloy containing 2.00 wt pct zinc was also made by melting the constituents under a vacuum. In both of these methods of alloy preparation the losses can be kept extremely small. Again, the characteristic eutectic structure was obtained, assuring confidence in this value. The accompanying micrographs are presented in support of this point. Fig. la represents an alloy containing 4.00 wt pet zinc, and reveals excess zinc particles, which precludes the value of both Wilson and Peretti, and Valentiner. Fig. lb, gives the structure of an alloy containing 2.2 wt pct zinc, also showing the presence of excess zinc. Fig. lc is a micrograph of a typical structure of the eutectic observed in several sections of the 2.0 wt pct alloy. In the 1.8 pet zinc alloy, fig. id, the definite presence of the primary indium can be noted. From these re-

Jan 1, 1951

By Edward A. Loria

A SERIES of papers on the study of austenite grain A size in cast steels has been published recently.'" These studies show that in the as-cast state, the austenite grains are quite large, for they form as the steel freezes at a very high temperature, but a simple reheating above the critical range produces a new set of austenite grains which, in many instances, is finer than ASTM grain sire No. 8. Furthermore, there is no apparent relationship between as-cast austenite grain size and subsequent grain size produced by heat treatment. The as-cast austenite grain size can be determined easily in plain carbon and low alloy steels which produce a continuous grain boundary f errite envelope in the as-cast structure. In the case of cast steels whose alloy content produces greater hardenability and suppresses the proeutectoid ferrite transforma-

Jan 1, 1952

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 Riki Kobayashi, Donald L. Katz

The dew point of natural gas which has been in equilibrium with gas hydrates has been reported to be lower than that obtained for natural gas in equilibrium with water1,? Hammerschmidt' reports a lowering of the dew point of 13 F for a natural gas in equilibrium with hydrate at 380 F and 525 psi. Records and Seely2 likewise show that the dew point of gas leaving hydrate separators' is as much as 150 F below the separator temperature. This paper presents the reasons for the observed differences between the equilibrium temperatures and the dew point temperatures. Descriptions of the dew point determination by the Bureau of Mines and ASTM tester3 indicate that the dew point is taken as the temperature at which liquid water droplets first begin to appear on the cooled mirror surface even though the temperatures involved are below that required for the formation of gas hydrates or ice. PRESSURE-TEMPERATURE DIAGRAM FOR METHANE-WATEK SYSTEM Fig. 1 presents a schematic pressure-temperature diagram for the methane-water system" for some constant pressure between the critical pressures of pure methane and pure water i.e., pressures frequently encountered in pipeline operations. The possible equilibrium relations are shown by the heavy solid lines. Curve AE represents the saturated water content or dew point of gas in equilibrium with a water-rich liquid solution while curve EF represents the dew point of gas in equilibrium with hydrates. In addition the dotted line DE labelled "metastable dew point" is introduced to explain the apparent discrepancy betwceen the dew point determination and gas-hydrate equilibria. Thermodynamics place certain restrictions on the location of line DE6, namely, that (1) the concentration of water along the line DE be greater than the concentration of water along EF or that the metastable line split the angle formed by the intersection of line GE and EF

Jan 1, 1956

By C. C. Harris

The 3-parameter equation* was introduced1 as having the necessary form and flexibility for describing the major features of size distribution curves. Also, Eq. 1 was shown to contain most of the widely used 2-parameter equations as special cases. Special methods are necessary in order to determine the parameters of 3-parameter equations by graphical means. The procedure given previously required double graphical interpolation followed by regraphing the interpolated data. The theoretical basis of the method was a difference equation eliminating y. Several other methods for obtaining the parameters have been under development and one method appears to overcome the disadvantages of the earlier method and satisfies several procedural requirements. The points in favor of the new method as compared to the earlier method are as follows: 1. Estimation of the quality of fit is direct, and is in fact an essential part of the procedure. 2. The data is plotted directly without the necessity of interpolation from a graph. 3. The method makes use of Rosin-Rammler2 paper which because of expanded scaling in the coarse sizes leads to improved accuracy1 as compared with the log-log plot for the Gates3-Gaudin4-Schubann5 representation. 4. There is a gain over the earlier method in overall accuracy and in simplicity.

Jan 1, 1970

By R. E. Bish

IN an effort to distinguish experimentally between the radically different limits of two-liquid im-miscibility reported for the Cu-Pb system by Borne-inann and Wagenmann and by Briesemeister (see Fig. I), it was found that the high temperature homogeneous liquid containing between 41 and 93 pct Pb could not be frozen without separation into two liquids with the fastest cooling technique that could be devised. Thus, the two-phase state could not be distinguished with certainty from the one-phase state by the examination of quenched samples. To overcome this obstacle the following method for detecting the presence of an interface between two immiscible conducting liquids at temperature was developed. Measurements made by the new method substantiate the Briesemeister diagram in its general form. The method consists essentially in the measure-

Jan 1, 1953

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 A. A. Burr, D. Caplan

IN carrying out experiments in metal-gas systems, it is often difficult to estimate how long a reaction period must be allowed for equilibration. This is especially true in systems for which the diffusion coefficient is not known. In an investigation of the Cr-O system, the necessary information was obtained in the way described subsequently. Two pieces of chromium sheet of different thicknesses were packed in mixed powders of chromium and Cr2O3 and sealed into an evacuated metal capsule by welding. Austenitic stainless steel proved suitable as a capsule material up to 1350°C and molybdenum at higher temperatures. The capsule then was heated at a specific temperature for a time sufficient to saturate with oxygen the thinner but not the thicker specimen. The time is readily estimated from a preliminary experiment if a sufficient thickness differential is chosen. Under these experimental conditions, the metal sheet is exposed to a partial pressure of oxygen equal to that of the dissociation pressure of the oxide and hence can become saturated with oxygen without developing any second phase. After cooling, both samples were analyzed for oxygen by the vacuum fusion technique. Assuming that the surface of the specimens is kept saturated with oxygen throughout the experiment, the diffusivity can be calculated by application of the appropriate solution to Fick's second law. This is most conveniently accomplished by use of a plot of mean fractional saturation (Cm-Co) / (Cs-Co) vs (Dt) ½/L as given by Darken,' where t is time, L the half-thickness of the sheet, and D the diffusion coefficient. Cm, the mean concentration at time t, is given by the oxygen percentage in the thicker specimen; Cs, the constant surface concentration, is the oxygen percentage in the thinner specimen; Co is the oxygen content of the original chromium sheet. (Cm-Co) / (Cs-Co) is calculated and the corresponding (Dt) ½/L is read from the graph and D thereby calculated. By performing the experiment at two temperatures and plotting log D vs 1/T, the D for any temperature is established. (The activation energy for diffusion may be obtained from the slope of the line.) Once D is known as a function of temperature, it is a simple matter to estimate the correct reaction time for experiments with single specimens at other temperatures by equating (Dt) ½/L to its value for effective saturation. Darken' points out that this is approximately unity. The solubility of oxygen in chromium, as determined from the thin samples at each temperature, proved to be approximately 0.03 pct at 1350°C and less at lower temperatures. Due to low solubility and to the known difficulties of the vacuum fusion method in this low range, the values obtained for D (5x10-0 sq cm per sec at 1350°C) are estimated to be correct only within an order of magnitude. Nevertheless, the method has proved useful in estimating reaction times. Its usefulness will be greater in metal-gas systems where the solubility is appreciable. A second function of the method is to permit the determination of diffusion coefficients in systems for which the conventional techniques are experimentally difficult or impossible.

Jan 1, 1956

By I. Sheinhartz, H. M. McCullough

DURING the course of a lubrication study in relation to the compacting of metal powders, it became desirable to measure the thickness of sprayed graphite coatings on steel dies for hot pressing. The thickness of these lubricant coatings ranged between 0.0001 and 0.002 in. In their particular case, the authors were interested in a method for measuring the lubricant thickness on tapered die inserts having curved surfaces. The lubricant was sprayed on the inserts at an elevated temperature and it was desirable to measure the thickness as soon as possible after application. Various standard types of commercial equipment were tried. Most of the available devices operated on either a mechanical or magnetic principle. The mechanical devices, such as micrometers, dial indi-

Jan 1, 1956

By L. G. Schulz

THE possibility of using reflected X-rays to produce images of crystals was explored by Barrettl who developed simple experimental procedures for X-ray microscopy and who showed by numerous examples the great range of information that could be made available. In his method characteris radiation is used to produce an image of a limited area of the sample on fine-grained film, this image subsequently being enlarged approximately X100. A somewhat different method will be described here;' white radiation from a fine-focus X-ray tube-"' is used to produce an image of a relatively large area of a single-crystal surface. part of the sample; therefore, white radiation is needed. The resolution in the image formed on the photographic film will depend on the size of the focal spot of the X-ray tube. If the sample is made

Jan 1, 1955

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