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By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,'-!' other investigators have encountered difficulty with the method."'. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

By S. Floreen

Seven iron alloys ranging from 5 to 12 pct Ni and 5 to 14 pct Cr were studied. All alloys transformed to bcc massive martensites. Tempering increased the strengths , probably because of relief of residual stresses generated by the martensite transformation. The major strengthening mechanism appeared to be solid-solution hardening by nickel and chromium. Studies of the work-hardening behaviw, of the effects of prior austenite grain size, and of the effects of changing strain rate and test temperature gaue results very similar to iron or low-alloy steels. Increasing nickel contents markedly improved the toughness at subzero temperatures. Studies of the flow properties did not, however, indicate the reason for the beneficial effect of nickel on toughness. The marine atmosphere corrosion resistance of the alloys was improved primarily by chromium additions, but increasing nickel contents were also beneficial at low levels of chromium. J\ number of maraging and PH stainless steels are strengthened by precipitation hardening in a low-carbon Fe-Ni-Cr martensite matrix. To some extent the resultant properties of these steels must depend upon the properties of this matrix. The present study therefore was conducted to evaluate the transformation characteristics and mechanical properties of a series of Fe-Ni-Cr martensitic ternary alloys. A limited evaluation of the corrosion resistance of the alloys in marine atmosphere was also made. ALLOY PREPARATION Seven 100-lb air induction melts were prepared using electrolytic iron, nickel, and chromium metal additions. The initial Fe-Ni charge also contained 0.05 wt pct graphite to produce a carbon boil during melt down. After melting of the base charge, the heats were refined with 0.1 wt pct additions of manganese, silicon, aluminum and titanium and poured into cast-iron molds. The ingots were homogenized at 1250°C and uni-directionally hot-rolled to 2-in. plate. They were then homogenized another hour at 1250°C, and unidirection-ally hot-rolled to %-in. plate at a finishing temperature of approximately 1050°C. The compositions of the heats are given in Table I. Two additional heats were prepared as 40-lb vacuum-induction melts using electrolytic iron, nickel, and chromium metals, and commercially pure molybdenum chips. A carbon boil, and 0.1 wt pct additions of aluminum and titanium were again employed, but manganese and silicon were not added. The heats were converted to %-in. plate using the procedure described above. The compositions of these heats are included in Table I.

Jan 1, 1967

By J. A. Ede

The object of the writer is to call attention to a rather unique aggregation of economic products distributed over a line of succeeding formations about 3 mi. long, to be seen within a few miles of La Salle, Ill. Fig. 1 is an ideal section of the stratification exposed and exploited along a distance of 3 1/5 mi. in a southwesterly direction from the quarry of the Utica Hydraulic Cement Co. located near the historic site of Kaskaskia village to the Oglesby shaft at Oglesby. No attempt has been made to cover the whole field, special mention only being made (with the exception of two places) of the operations found along the course or parallel to the direction assumed in the ideal section. I have used Fig. 2, after J. R. Bent and De Witt Kelly, to locate the relation of the La Salle anticline to the coal mines of this district and to show the operation of No. 1 and 3 mincs of the Illinois Zinc Co. Anticline and the Rock Formations Owing to the structural deformation between La Salle and Utica, the older rocks of the state are exposed to the surface along the northern embankment and the bottoms of the Illinois River valley near the latter place. At; the Illinois Zinc Co. works, Sec. 16, Tp. 33, R 1, a well for water mas sunk 1828 ft. and samples taken every 10 ft. of the ground penetrated; duplicates were sent to Mr. Cady of the Illinois Geological Survey. A general compilation or synopsis study of this section is here presented. As the well is over 1 mi. west of the Western limb of the anticline, the section affords some reliable data. These samples were studied and interpreted by H. M. DuBois as Lower Magnesian, and by G. H. Cady as the Lower Magnesian. The results are given in Fig. 3. The most interesting geological feature of this district is the La Salle anticline. In 1865, Leo les Quereux, looking at Split Rock, asked how it happened that the upper coal measures overlie strata of the Lower Silurian and what has become of the formations which are generally found intermediate—the Upper Silurian, the Devonian and sub-carboniferous, and the lower member of the coal measures?

Jan 1, 1920

Some Things We Don't Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

Some Things We Don't Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

The Diamond mechanical soot blower system, manufactured by the Power Specialty Co., Detroit, Mich., consists of a permanent installation of units arranged in groups to fit the design of the various boilers to which they are attached. The units are so arranged as to effect the cleaning of the fire surfaces of the boiler, particularly the tubes, by means of steam jets. When this steam is released among the tubes at a velocity of approximately 2700 ft. per sec. (assuming a pressure of 150 lb.), a perfect whirlwind of currents is created, reaching all the nooks and crannies of the boiler, and thoroughly removing the particles of soot and fine-ash accumulation. This operation requires but a moment's time-from 20 to 50 sec. per unit¬and is performed from two to four times a day, while the boiler is under full load, using a greatly decreased amount of steam and labor as compared with the hand hose or any other system of blowing. Moreover, this cleaning is effected without admitting air, with its cooling effects, to the boiler setting. The Diamond model "G" blower consists of five principal elements as follows: 1. A head through which the steam passes from the main supply line when the valve is opened. The head is the foundation element to which the other elements are attached. 2. A wall box which is bricked into the setting. The box supports the unit, and is so constructed that the blower can be turned freely without admitting air to the inside of the setting. 3. A blower element running cross-wise of the bank of tubes, and consisting of a small header with nozzles so placed as to discharge steam between the boiler tubes. 4. A sheave or hand wheel by means of which the blower element is rotated. 5. Bearings attached to the boiler tubes which support the blower element and permit it to revolve freely. The nozzles from which the steam issues are designed on the principle of the Venturi tube, and vary in design for different pressures. The expanding walls of the Venturi nozzle increase the velocity of the steam over 200 per cent., as compared with a nozzle having a straight orifice. Thus, the velocity of the steam issuing from a straight nozzle at 150 lb. pressure is 912 ft. per sec., whereas, at this pressure the velocity of the steam issuing from a Diamond Venturi nozzle is 2795 ft. per second.

Jan 5, 1918

By W. H. Blauvelt

W. H. BLAUVELT, Syracuse, N. Y. (communication to the Secretary*).-I have read Mr. Howland's paper on Calculations with Reference to the Use of Carbon in Modern American Blast Furnaces with much interest, and believe that his method of analysis of the subject will be of material assistance in our study of the action of coke in the blast furnace. Mr. Howland quotes Professor Richards' statement that from the standpoint of the generation of the maximum quantity of heat in the furnace, Grüner was right in saying that all the carbon burned in the furnace should be first oxidized at the tuyères to CO and all reduction of oxides above the tuyères should be caused by CO, which thus becomes CO2. It is clear that the maximum quantity of heat is generated in the furnace when the greatest amount of carbon is burned to CO2 irrespective of whether it is burned at the tuyères or further up the furnace. So it would appear that Grüner's theory is sound regarding the maximum production of heat only because if all the carbon is burned to CO at the tuyères the reduction of the ores will have to be effected by the further oxidation to CO2. Whereas, if the reduction of the ores is effected in part by solid carbon, part of this carbon might be oxidized only to CO, resulting in a higher percentage of CO in the escaping gases than from Grüner's "ideal conditions.? But in studying the combustion of coke in the furnace, it is clear that the production of the maximum quantity of heat is not of the first importance in blast-furnace operation, or in the utilization of the fuel charged into the furnace. To my mind the production of a high thermal head at the tuyères is of the first importance, and the best coke is that which reaches the tuyères in proper condition to produce the highest temperature at the tuyères, and in just sufficient quantity to do the amount of work required there under the conditions produced by this maximum temperature. The combustion of a much larger amount of fuel at the tuyères, under conditions that will fall short of producing the highest possible temperature, cannot produce as good results, either in fuel economy or output. If this statement is correct, does it not correspond with Mr. Howland's statement that too much wind is inimical to low coke consumption? Nothing is more fatal to obtaining the highest temperatures than an excess of air for combustion. In the blast furnace an excess of air dilutes and cools the products of combus-

Jan 10, 1916

By John L. Boardman

Because of the attention that has recently been given to the health and safety of miners by various organizations such as the A.I.M.E., The American Congress, Mining Section, National Safety Council, as well as the Bureau of Mines and various state mining departments, your committee on health and safety deemed it best to call attention this year to the mine-accident cause that is by far the most important; namely, injuries due to falls of ground, rock, roof and coal. Each of several members of the committee contributed a brief outline of the importance of this accident cause in his district. While these papers were brief, it would require too much time and space to give them in full, therefore we present an outline of each and summation of all. Report of M. D. Cooper, Hillman Coal and Coke Co. M. D. Cooper, Division superintendent, Hillman Coal and Coke Co., Pittsburgh, Pa., contributed the following: During the period from 1930 to 1939, accidents from falls of roof in bituminous mines average 54.3 per cent of all accidents. In mechanized mining, there is a tendency toward reduction in this class of accidents because the operator of the machine is usually at a distance of 10 to 20 ft. from the face, whereas in hand load- ing the miner is close to the face during most of the shift. No doubt the use of aluminum and light steel beams supported at regular intervals by jacks, a common practice in mechanical mining, has contributed to the favorable record so far developed. Report of M. H. Fies, De Bardeleben Coal Corporation Milton H. Fies, Vice-President, DeBar-deleben Coal Corporation, Birmingham, Ala., says: With reference to the types of mining, it is suggested that a clear understanding be had as to the character and thickness of the directly overlying strata, with especial consideration to the strength and in some cases an analysis of it. In coal mining, generally speaking, overlying strata higher in silica than others is stronger. In changing from narrow to wide places, the procedure should be experimental, both as to the width and depth of places and as to the nature of the necessary timbering. Since most of the accidents in coal mining particularly are due to falls of roof and coal, this phase of mining should be attacked with vigor There is no substitute for discipline and, in this connection, under present conditions it is important that cooperation by the labor ornanizations- be sought and that a spirit of fairness prevail. Frequent and thorough inspection of all active working places should be made.

Jan 1, 1943

By John L. Boardman

BECAUSE of the attention that has re¬cently been given to the health and safety of miners by various organizations such as the A.I.M.E., The American Congress, Mining Section, National Safety Council, as well as the Bureau of Mines and various state mining departments, your committee on health and safety deemed it best to call attention this year to the mine-accident cause that is by far the most important; namely, injuries due to falls of ground, rock, roof and coal. Each of several members of the committee contributed a brief outline of the importance of this accident cause in his district. While these papers were brief, it would require too much time and space to give them in full, therefore we present an outline of each and summation of all. REPORT OF M. D. COOPER, HILLMAN COAL AND COKE CO. M. D. Cooper, Division superintendent, Hillman Coal and Coke Co., Pittsburgh, Pa., contributed the following: During the period from 1930 to 1939, accidents from falls of roof in bituminous mines average 54.3 per cent of all accidents. In mechanized mining, there is a tendency toward reduction in this class of accidents because the operator of the machine is usually at a distance of 10 to 20 ft. from the face, whereas. in hand loading the miner is close to the face during most of the shift. No doubt the use of aluminum and light steel beams supported at regular intervals by jacks, a common practice in mechanical mining, has contributed to the favorable record so far developed. REPORT OF M. H. FIES, DE BARDELEBEN COAL CORPORATION Milton H. Fies, Vice-President, DeBardeleben Coal Corporation, Birmingham, Ala., says: With reference to the types of mining, it is suggested that a clear understanding be had as to the character and thickness of the directly overlying strata, with especial consideration to the strength and in some cases an analysis of it. In coal mining, generally speaking, overlying strata higher in silica than others is stronger. In changing from narrow to wide places, the procedure should be experimental, both as to the width and depth of places and as to the nature of the necessary timbering. Since most of the accidents in coal mining particularly are due to falls of roof and coal, this phase of mining should be attacked with vigor. There is no substitute for discipline and, in this connection, under present conditions it is important that cooperation by the labor organizations be sought and that a spirit of fairness prevail. Frequent and thorough inspection of all active working places should be made.

Jan 1, 1941

By A. J. Shaler, J. Prieto Isaza, J. Wulff

Tantalum metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involwing high temperatures in vacuo some of the refractory metals 6ecome brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element colum-bium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum-columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen-containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides; one of the authors undertook4 an investigation of the thermochemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exo-thermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the Drocess should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonly made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tanta-

Jan 1, 1949

By John L. Boardman

Because of the attention that has recently been given to the health and safety of miners by various organizations such as the A.I.M.E., The American Congress, Mining Section, National Safety Council, as well as the Bureau of Mines and various state mining departments, your committee on health and safety deemed it best to call attention this year to the mine-accident cause that is by far the most important; namely, injuries due to falls of ground, rock, roof and coal. Each of several members of the committee contributed a brief outline of the importance of this accident cause in his district. While these papers were brief, it would require too much time and space to give them in full, therefore we present an outline of each and summation of all. Report of M. D. Cooper, Hillman Coal and Coke Co. M. D. Cooper, Division superintendent, Hillman Coal and Coke Co., Pittsburgh, Pa., contributed the following: During the period from 1930 to 1939, accidents from falls of roof in bituminous mines average 54.3 per cent of all accidents. In mechanized mining, there is a tendency toward reduction in this class of accidents because the operator of the machine is usually at a distance of 10 to 20 ft. from the face, whereas in hand load- ing the miner is close to the face during most of the shift. No doubt the use of aluminum and light steel beams supported at regular intervals by jacks, a common practice in mechanical mining, has contributed to the favorable record so far developed. Report of M. H. Fies, De Bardeleben Coal Corporation Milton H. Fies, Vice-President, DeBar-deleben Coal Corporation, Birmingham, Ala., says: With reference to the types of mining, it is suggested that a clear understanding be had as to the character and thickness of the directly overlying strata, with especial consideration to the strength and in some cases an analysis of it. In coal mining, generally speaking, overlying strata higher in silica than others is stronger. In changing from narrow to wide places, the procedure should be experimental, both as to the width and depth of places and as to the nature of the necessary timbering. Since most of the accidents in coal mining particularly are due to falls of roof and coal, this phase of mining should be attacked with vigor There is no substitute for discipline and, in this connection, under present conditions it is important that cooperation by the labor ornanizations- be sought and that a spirit of fairness prevail. Frequent and thorough inspection of all active working places should be made.

Jan 1, 1943

By John L. Boardman

BECAUSE of the attention that has recently been given to the health and safety of miners by various organizations such as the A.I.M.E., The American Congress, Mining Section, National Safety Council, as well as the Bureau of Mines and various state mining departments, your committee on health and safety deemed it best to call attention this year to the mine-accident cause that is by far the most important; namely, injuries due to falls of ground, rock, roof and coal. Each of several members of the committee contributed a brief outline of the importance of this accident cause in his district. While these papers were brief, it would require too much time and space to give them in full, therefore we present an outline of each and summation of all. REPORT OF M. D. COOPER, HILLMAN COAL AND COKE CO. M. D. Cooper, Division superintendent, Hillman Coal and Coke Co., Pittsburgh, Pa., contributed the following: During the period from 1930 to 1939. accidents from falls of roof in bituminous mines average 54.3 per cent of all accidents. In mechanized mining, there is a tendency toward reduction in this class of accidents because the operator of the machine is usually at a distance of 10 to 20 ft. from the face, whereas in hand loading the miner is close to the face during most of the shift. No doubt the use of aluminum and light steel beams supported at regular intervals by jacks, a common practice in mechanical mining, has contributed to the favorable record so far developed. REPORT OF M. H. FIES, DE BARDELEBEN COAL CORPORATION Milton H. Fies, Vice-President, DeBardeleben Coal Corporation, Birmingham, Ala., says: With reference to the types of mining, it is suggested that a clear understanding be had as to the character and thickness of the directly overlying strata, with especial consideration to the strength and in some cases an analysis of it. In coal mining, generally speaking, overlying strata higher in silica than others is stronger. In changing from narrow to wide places, the procedure should be experimental, both as to the width and depth of places and as to the nature of the necessary timbering. Since most of the accidents in coal mining particularly are due to falls of roof and coal, this phase of mining should be attacked with vigor There is no substitute for discipline and, in this connection, under present conditions it is important that cooperation by the labor organizations be sought and that a spirit of fairness prevail. Frequent and thorough inspection of all active working places should be made.

Jan 1, 1941

By C. L. Burrill

The forecasts presented in this paper constitute an attempt by the writer to predict the pattern of the consumption of petroleum products in the United States during the period of transition from war to peace. Although, in preparing the estimates, secular trends were not overlooked, greater emphasis was placed upon considerations of a cyclical character, or upon influences which might be peculiar to parts of the period. The estimates do not extend beyond the year 1950 because by then conditions in the industry should have returned to normal. The consumption of petroleum products is affected, of course, by changes in the condition of business in general. Before estimates of petroleum consumption could be prepared, therefore, it was necessary to predict the pattern of general business during the period under review, particularly the economic series that in the past have shown the closest relationships with petroleum consumption. It is the writer's view that business activity in this country (as measured by industrial production) will be higher on the average during the period between the end of the war and the year 1950 than it ever was before during a peacetime period of the same duration. When the war is over, consumers will have saved amounts of money that will be very large as compared with any previous accumulations. There is little question, therefore, as to the financial ability of consumers to purchase goods. The production of many durable consumers' goods, such as automobiles, refrigerators and radios, has been completely stopped since early in the war; also, many semidurable and nondurable consumers' goods have not been available in the quantities or the qualities desired. There is considerable needi therefore, for consumers to purchase goods after the war. The important question is whether consumers will purchase goods in "1arge enough quantities to keep our economy running at a high level. The writer answers this question in the affirmative. The mere existence of very large consumer savings lends considerable support to this view because, with such backlogs of " security," consumers can afford to spend more of their current earnings than they otherwise could. Also, several polls have been taken, which indicate that consumers expect to buy large quantities of a variety of goods. Some of the savings, therefore, probably will go into current consumption. Even though this percentage is relatively small, so that the bulk of the funds accumulated by consumers during the war continues to remain as savings during the period under review, spending should be great enough to start the production cycle and keep it

Jan 1, 1945

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By R. M. Brick

SEGREGATION can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming. steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-12 per cent Si alloys. The phasial condition implicitly described above-solidification over a range of temperatures with a compositional difference between solid. and liquid-is found in nearly all solid solutions or combinations of solid solutions and eutectics. Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually determinable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be. described first because it is an essential part of the picture. CORING Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus 1, 3, 7 and solidus 2, 5, 8, and where the vertical 1, 4, 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. 1b) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1944

By George Krauss, Seth R. Thomas

One complete cycle, allstenite to martensite to aus-tenite, of Martensitic transformation was induced in a commercial 18 Cr-8 Ni stainless steel. Transmission electron microscopy showed that the reverse transfarmation, martensite to austenite, perpetuated the dense defect substructure of the martensite produced by the direct transformation, austenite to 'martensite, and reproduced the retained austenite matrix orientation. A general precipitation of lathlike M,,C, particles was noted to be present in, and is suggested as cause for, regions of martensite that Izad formed after a complete cycle of transformation. The habit plane of the precipitate particles was found to be within 5 a plane previously established as the habit of nitride precipitates of similar morphology in bcc iron. The direct transformation of austenite (y) to martensite (a) in metastable 300 series stainless steels has received considerable attention in the past,'-8 and the martensite product given special emphasis in recent years,9"*u but little information has been published about the reverse martensitic transformation during which bcc a martensite is converted to fcc y austenite."-" The reversal mechanism and the resulting crystallographic relationship between parent and product austenite are of fundamental concern. The reversal product, fully austenitic, and hereafter referred to as reversed austenite, exhibits a defect structure far different from its virgin counterpart. Some studies have been reported in which the structure of reversed austenite in iron nickel alloys is compared to annealed austenite with respect to austenite strengtheningM and Stabilization.' The martensite in these Fe-Ni alloys, however, shows a basic difference from that produced in stainless steels. Structurally, the Fe-Ni martensite is profusely twinned," while the (low-carbon) Fe-Cr-Ni martensite contains a high density of tangled dislocations and is apparently twin-free.I0 reediis" has recently shown in an Fe-16 Cr-12 Ni stainless alloy that this typical martensitic defect structure and the reverse transformation directly influence the structure of the reversal product. He found that much of the reversed austenite had returned to the orientation of the virgin austenite and that fine twins were formed in the austenite after the reverse transformation. This investigation was undertaken in order to describe as completely as possible the structural changes produced by a cycle of transformation in a typical 18-8 stainless steel. EXPERIMENTAL PROCEDURE The 301 stainless steel under investigation (17.44 Cr, 7.75 Ni, 0.80 Mn, 0.60 Si, 0.40 Mo, 0.40 Cu, 0.08 C, 0.03 N, bal Fe)was received as 0.060-in.-thick

Jan 1, 1968

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors' laboratory, methods have been devised for preparing pure rare earths and many of their properties'- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett' showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By R. F. Mehl, B. Lustman

THE formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.1 It is necessary here only to enumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type-i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained-the isothermal growth of the phase follows a simple parabolic equation: [1 = ki [I]] where X is the thickness of the alloy layer, k the reaction rate constant, and [t] the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.3 In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varies with temperature according to the Arrhenius equation: [k = Ae-QIRT [2]] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942