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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 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 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 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 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. 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 P. Dayal, L. S. Darken

THE migration of carbon in austenite under the influence of an electric current has been observed qualitatively several times.14 Lebedev and Guterman5 recently have reported quantitative measurements; their method consisted of welding a low-carbon to a high-carbon wire, passing current, and later estimating the carbon distribution metal-lographically. We believe the method reported in this paper is superior in principle since electrolytic migration and ordinary diffusion are not necessarily coupled as in the weld method; also for the first time the extent of migration is determined by combustion analysis for carbon. A uniform tubular specimen (S.A.E. 1045 or 1095) was mounted as illustrated in the figures. the whole assembly being in an atmosphere of purified nitrogen. Direct current (129 to 226 amp at 0.65 to 1.0 v) served as source both of heat and of potential gradient for carbon migration. The duration of experiment was 7.5 to 12 hr, during which time the temperature was controlled (±10°C) manually. The experimental conditions are indicated in the first five columns of table I. With this experimental arrangement, the temperature initially has a maximum value at the central plane. Also, in this vicinity (by virtue of the symmetry), the carbon entering any volume element is equal in quantity to that leaving; the loss or accumulation of carbon occurs near the electrodes since the carbon moves uniformly near the center and is "frozen" at the cold ends. Hence, providing the time of experiment is not sufficiently long to seriously influence the conditions at the central plane, carbon crosses this plane only under the influence of the electrical potential gradient and not under the influence of temperature or concentration gradient. The amount of carbon which has crossed this plane was determined by combustion analysis of the two halves of the specimen. The results of these analyses are shown in the sixth and seventh columns of table I. It will be noted that substantial amounts of carbon migrated from the anode portion to the cathode portion (except at 920°C, which temperature was too low to exhibit the effect in the allotted time). In spite of precau-tions taken, considerable decarburization occurred as may be seen by comparing cols. 8 and 5. In three cases (indicated by asterisks in table I) the specimen was ground on one side, polished, and examined metallographically before analysis. One specimen was normalized and re-examined. Micrographs of selected areas in specimens 4 and 6 are shown in figs. 1 and 2, respectively. Evidence of carbon migration from the anode toward the cathode is quite apparent. Fig. 2 shows abundant graphite as well as cementite in a region near the cathode. The temperature of this zone is estimated at about 800°C. In fig. 1, particularly in the micrograph on the extreme right (the right side of which is of unaltered carbon content), there is evidence of slight depletion of carbon in the immediate vicinity of the cathode as contrasted to the general increase in carbon of the cathode half of the specimen. Although this may be attributed in part to decarbur-ization, it is believed that it is occasioned also by thermal diffusion—migration (of carbon) from a cool to a hot zone4—a phenomenon superimposed upon the electrical migration. Evidence of carbon migration was visible particu-larly during the course of the high-temperature,

Jan 1, 1951

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 N. E. Grosvenor

Several methods have been proposed for determining the tensile strength of rock. These have been tried out over the past several years, but the results have been erratic and of doubtful value. The tensile strength of rock is its weakest property, and this property apparently enters into all failure phenomena, whether underground or on the slope of an open pit. Therefore, it is essential that detailed quantitative information is known about the tensile strength of rock if the design engineer is going to select the proper pit slope, pit orientation, or orientation of underground workings so as to give the most economical and safest mining condition. This quantitative information may be used to orient the pit in such a manner as to allow steep slopes along two sides. This information possibly may be used to orient the direction of either underground workings or open pits so as to decrease powder consumption and to increase blasting efficiency. Hence it is of prime importance that a method of determining accurately the tensile strength of rocks be developed. The U. S. Bureau of Mines states' that no standard methods have been proposed by the ASTM for testing the tensile strength of rock. The method described in the Bureau publication is said by them to be unsatisfactory. A similar test that has been used in our laboratory in place of the USBM test is shown in Figs. 1 and 2. h this test the core is placed in a set of grips that has been designed for one particular size core. The grips are designed to distribute the stress around the core if they are tightened correctly. A universal joint or a flexible cable may be used in conjunction with the apparatus to prevent bending or twisting of the specimen. The main difficulty encountered with the system shown is the failure of the specimen within the grips. The possible cause of the failure within the grips may be due to a stress concentration set up by the uneven tightening of the grips. This method can be used only for tests on cores, and even then has been found to be totally unsatisfactory because of the failure within the grips. The U. S. Bureau of Reclamation has been using a test similar to the sketch shown in Fig. 3. Sulfur is cast around each end of the specimen to form a bearing surface and then a ring grip is used to apply a tensile stress. The grips are in contact with the sulfur cast and do not touch the specimen. This method is unsatisfactory, apparently because a large number of the specimens appear to break within the sulfur cast. Professor Wuerker of the University of Illinois uses the test shown in Fig. 4.' Professor Wuerker states2 that this method has given definite and reproducible results with the weakest as well as with the strongest rocks. The test is a supplement in all cases where cores cannot be obtained. The principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar. Soft

Jan 1, 1961

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

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By R. R. Morral, F. M. Krill, K. T. Aust

THE occurrence of twins in aluminum ingots cast under certain conditions has been well established. For instance, Herenguel and Lacombe1,2 have observed a twinned columnar structure in 99.5 and 99.9 pct Al, solidified by continuous or semicontinuous casting. The structure, which they termed "basaltic," appears in the form of elongated crystalline fibers of alternating luster. Herenguel and Lacombe2 found sections of flat crystalline plates composed of twin crystal plates, in which the twin plane (111) and a [I121 direction contained in the twin plane are parallel to the principal heat gradient. This orientation relationship is different from the usual orientation texture observed in cast face-centered cubic metals, where the [100] direction is approximately parallel to the long columnar axes lying in the direction of growth." A large amount of twinning has also been observed by the present authors in semicontinuous cast aluminum of 99.2 pct purity, Fig. 1. Mondolfo4 has suggested that the twinned cast structure forms by a deformation twinning process as the result of uneven cooling stresses within the ingots. This suggestion appears to be inconsistent with the large amount of twinning observed in the semicontinuous cast ingots and with the large difference of dendritic

Jan 1, 1953

By Tormod Forland

FROM equilibrium measurements on the system NaF-Na 3A l Fo-A 1 2 O 3-Na CO 3-CO 2 with high contents of NaF, Forland, Storegraven, and Urnesl concluded that complexes are formed containing two oxygen, three aluminum, and a less defined number of fluorine per complex. The same number of oxygen atoms per complex was also found by cryoscopic measurements for mixtures high in NaALF 6. In a recent paper by Stokes: some other complex ions, Al2O2F42- and AlOF2-, have been suggested. Here an additional argument in favor of the complex ALO2F. suggested by Forland, Storegraven, and Urnes will be given. When fused Na3AlF6 containing some A12O3, is cooled slowly, the solid phase will consist of the two components as separate phases. The melting point and the heat of fusion of Al2O3 are so high that this component will form the stable solid phase even though in the liquid state the complex may have a high stability. If, however, the fused mixture is quenched, the decomposition of the oxygen-containing complex and the formation of solid Al2O3 does not proceed fast enough, and a solid solution of A12O3 in Na3AlF6 is obtained. Zintel and Morawietz3 obtained cryolite containing 10 pct AL2O3 in this way. The density and the lattice parameters of the A12O3 containing cryolite were also measured, and from this it was concluded that the Al2O3 enters the cryolite lattice as Al3AlO0 groups replacing Na3AlF6 groups. However, the experimental data could as well be explained by assuming that one Na+ ion and two of its neighboring F- ions are replaced by one Al3+ ion and two O2- ions. This may be pictured schematically as: F F F F F F F Al F Na F Al F ,-Na+ + Al8+ F Al 0 A1 0 A1 F F F F —2 F- + 2O2- F F F solid cryolite cryolite-alumina solid solution This means that the complex in the solid solution, derived from X-ray and density measurements, is the same as that which Forland, Storegraven, and Urnes derived from equilibrium measurements in the liquid state. References IT. Forland, H. Storegraven, and S. Urnes: Ztsch. fur anorgan-ische und allgemeine Chemie, 1955, vol. 279, p. 205. 2J. J. Stokes: AIME Trans. To be pubhshed. s E. Zintel and W. Morawietz: Ztsch. pubhshed.fur anorganische und allgemeine Chemie, 1939, vol. 240, p. 145.

Jan 1, 1958

By W. H. Smith

IN the course of an investigation on chromium containing minor amounts of alloying elements, the information herein has been obtained on the crys-tallographic orientations resulting from arc melting, rolling, and annealing. The chromium used in this investigation was electrolytic flake obtained from the Electro Metallurgical Co. This material was heated for 20 hr at 1600°C in hydrogen with a dew point of about — 100°C. The oxygen and nitrogen content of the chromium after this treatment was 0.0003 pct 0 and 0.005 pct N. Five pounds of this chromium were arc melted in a water-cooled copper crucible. After arc melting, the oxygen and nitrogen contents were 0.002 and 0.025 pet, respectively. A section of this ingot is shown in Fig. 1. By means of a back-reflection Laue technique, the crystal habit of the cast ingot was determined. As expected, it was found that the [loo] was approximately the axis of the columnar grains. In this respect, chromium behaves like other body-centered-cubic metals in that a cubic axis is normal to the cold surface of the mold. A slab cut from this ingot was rolled at 600°C as follows: four 30 pct reductions were made with intermediate anneals at 1200°C for 15 min. Rolling was done with the [loo] of the columnar grains in the rolling direction. Following the final anneal, an 80 pct reduction was taken at 600 °C. The final sheet thickness was ten mils. By polishing and etching, the thickness was reduced to four mils and the grain orientation determined by the transmission Laue method using molybdenum radiation with a zirconium filter. Fig. 2 is the (110) pole figure for this material with the ideal (100) [011] and (111) [112] orientations indicated. The orientation is typical of most cold rolled body-centered-cubic metals having the [llO] of the grains approximately in the rolling direction and the (100) planes approximately in the plane of the rolled sheet. There is also evidence of some 10) [1 orientation. The grain orientation of sheet rolled 40 and 80 pct in the same direction as before at 600°C followed by recrystallization at 12000 C for 15 min was determined by a back-reflection Laue technique. A random texture was found in both cases. This 1200°C 15 min anneal was found to give complete recrystallization and some grain growth.

Jan 1, 1956

By R. E. Maringer, A. Schwope

IT has been recognized that oxygen in minute quantities is extremely detrimental to the room-temperature ductility of molybdenum. Early fracto-graphic studies' of the cast metal indicated that oxides are formed preferentially at the grain boundaries. Additional verification of this preferential segregation has been obtained from internal friction studies on poly crystalline molybdenum (average grain diameter varied from 0.039 to 0.065 mm) and from observations of the effect of oxygen on specimens of extremely large grain size. Specimens A, B, and C, of 0.040 in. diameter commercial molybdenum wire (Lot FW 13-40) were heat treated in the vacuum furnace described by Few and Manning according to the specifications given in Table I. Internal friction studies of these specimens were carried out using a low frequency (approximately 1 cycle per second) torsional pendulum completely enclosed in a vacuum tank. As the pressure of oxygen in the heat treating atmosphere changed, the portion of the internal friction vs temperature curves ascribed to grain boundary relaxation changed correspondingly, Fig. 1. The decrease in the damping capacity at high temperatures as the pressure of oxygen in the heat treating atmos-

Jan 1, 1955

By W. Rostoker, S. Spachner

A N alloy of 50 pct Ni-50 pct Fe is currently manu- factured in tape thickness down to 1/8 mil. In the annealed form, this alloy produces an almost square hysteresis loop. This has generally been related to the fact that by proper rolling and annealing practice a sharp cube, (100) [OOl], texture can be developed. As part of a program directed toward an understanding of the relationships between magnetic properties and structure of tape core materials, analyses were made of preferred orientations in tapes of various thicknesses. Annealed tapes of this alloy in 2, 1, 1/2, ¼, and Y' mil gages were acquired from commercial sources. Pole figures constructed for the 2 and 1 mil tapes showed the expected sharp cube texture. However, the ½, ¼, and ? mil annealed tapes showed no evidence of any preferred orientations. A comparison of two transmission patterns is shown in Fig. 1. The origin of the absence of texture in the tapes of less than 1 mil thickness was explored in some detail. The basic questions were whether the heat treatment for the thinner tapes was wrongly selected, whether the initial cold worked textures were different, or whether the actual thickness of the tape exercised some influence on its annealing characteristics. Quantities of the five gages of tape were acquired in the as-rolled condition just prior to the final anneal. Pole figures of the cold worked textures were constructed for each of the tapes. Eye estimates of in-

Jan 1, 1956