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By John C. Shyne, Eric R. Morgan

BORON as a hardenability agent of commercial importance has been the subject of extensive study in recent years. It has been suggested in the past that boron increases hardenability by combining with nitrogen, thus rendering it innocuous.&apos; More recently it has been proposed that boron increases hardenability by reducing the free energy of sites of ferrite and pearlite nucleation.&apos; The segregation of boron to grain boundaries, the primary site of nucleation, would account for the large hardenability effect of minute additions of boron in steel. This grain boundary theory has found general acceptance while the concept of boron as a nitrogen scavenger has been disregarded. However, the interaction of boron and nitrogen in steel is considered to be important to hardenability because boron may be made ineffective by combination with nitrogen.". * The present work was undertaken to examine some of the effects of boron and nitrogen arid their interaction in steel. A base composition of moderate hardenability was chosen. This was a 0.35 pct C steel containing 2.50 pct Ni and 0.30 Mo. This composition was used because it contained no strong carbide, nitride, or Table I. Composition of Steels by Analysis, Wt Pct Steel C Ni Mo 0&apos; B N* Base 0.35 2.50 0.30 0.0012 nil <0.0001 Boron 0.35 2.50 0.32 0.0012 0.0022 <0.0001 Nitrogen 0.33 2.60 0.35 0.0015 nll 0.0052 Boron plus nitrogen 0.35 2.48 0.30 0.0006 0.0020 0.0040 * Obtained by vacuum fusion technique. boride-forming elements. The other alloys examined were modifications of the base composition and contained nitrogen, boron, or nitrogen plus boron. The compositions of the four alloys used are listed in Table I. The alloys were vacuum melted from electrolytic iron, electrolytic nickel, ferromolybdenum, and fer-roboron. When required, nitrogen was added by admitting a partial pressure of nitrogen over the melt after vacuum melting. The alloys were cast into 21h-in. diam ingots and hot rolled to %-in. sq bars. No ingot pattern was discernible on the polished and etched cross sections of the hot-rolled bars. The alloys were normalized at 1650°F, then machined into standard %-in. diam end-quench hardenability test bars. Four different austenitizing treatments were used: 60 rnin at 1550°F, 45 rnin at 1800°F, 30 rnin at 2000°F, and 20 rnin at 2000°F followed immediately by 30 rnin at 1550°F. The 1550" and 2000°F treatments were carried out in duplicate for each of the four steels. In order to prevent surface oxidation the bars were austenitized while buried under charcoal in an atmosphere of argon. After quenching the bars in a conventional end-quench fixture, the hardness surveys were made in the usual fashion on parallel flats ground along opposite sides of each bar. These were ground 0.050 in. deep rather than the conventional 0.015 in., to avoid decarburized or deboronized regions.5 The austenite grain sizes which resulted from each heat treatment were observed metallographically using Vilella&apos;s etch for martensite. The criterion used as a measure of hardenability was the distance from the quenched ends of the bars at which a hardness of RC 35 was observed. This hardness represented the inflection point on the hardness vs distance plot. Fig. 1 shows the hardenability of each steel after the several heat treatments. The duplicate tests demonstrated excellent reproducibility; the distance to Rc 35 was reproduced within 1/16 in. for duplicate test bars. All four alloys had the same grain-coarsening characteristics. Neither boron nor nitrogen had any observable effect on grain size. The grain sizes resulting from the various austenitizing treatments were ASTM 7 at 1550°F, ASTM 4 at 1800°F, and ASTM 2 at 2000°F. The small amount of boron in the boron steel greatly enhanced hardenability when the samples were austenitized at 1550°F. The low hardenability of the boron plus nitrogen steel showed that nitrogen eliminated the boron contribution to hardenability. Both steels containing nitrogen, with and without boron, exhibited lower hardenability than the base composition when quenched from 1550°F.

Jan 1, 1958

Jan 1, 1965

By Stanley J. Gasior, Albert J. Forney, Joseph H. Field

Most bituminous coal mined near Eastern industrial areas requiring high-Btu pipeline gas is caking and therefore unsuitable for fixed-bed pres- sure gasification by present techniques. If the caking property of such coal can be destroyed, the resulting fuel can be gasified in a fixed bed at pressure with steam and oxygen as a preliminary step in making a high-Btu gas. To find a practical way to convert strongly caking coals of granular or small lump size to noncaking fuel was the object of this study. In previous work, strongly caking coals of 1/8- to 1½ -in. size were converted to a noncaking coal char by treatment in a static bed in about 3 hours1 and coal of 18-100 Tyler mesh in a fluidized bed in about 5 min.2 An inert gas such as steam, nitrogen, carbon dioxide or a mixture of all three with a small amount of oxygen was used in both studies. In our work a strongly caking bituminous coal from the Pittsburgh seam of 4-8 Tyler mesh size was converted to a noncaking form in free-fall in about 2 sec by dropping it through a countercurrent flow of steam containing 4% to 7% oxygen at 1150º-1200°F and 300 psig. This method should also be applicable to smaller-sized material.

Jan 3, 1965

By John D. Sullivan

ALUMINUM and magnesium plants in the United States underwent enormous wartime expansion which made many wonder if ghost plants would result when industry swung back to a peacetime basis. Production capacity of primary aluminum ingots was stepped up from 150,000 tons annually to about 1,150,000 tons; magnesium production increased from 2500 tons in 1936 to nearly 200,000 in 1943, with a production capacity of some 300,000 tons. Not only was primary metal production enlarged but also the capacity of prime fabrications such as castings, forgings, extrusions, and sheets was correspondingly increased. In mid-December it was estimated that production of primary aluminum ingots in the United States in 1946 will be about 410,000 tons while consumption will be about 500,000, close to half of the wartime consumption. The 1946 estimated consumption of secondary aluminum is 200,000 tons. The critical shortage of soda ash is hindering production of primary metal, and the outlook for an early relief of this shortage is dark.

Jan 1, 1947

By L. C. Glenn

The account of oil and gas production in Tennessee, and of the geological factors related to such production, as given by the writer&apos; a few years ago needs to be supplemented by brief statements as to production and development to bring it up to date. Activity in searching for favorable geological structures or in drilling given areas has never been comparable to the intensive work done in states of large production. It is not possible, therefore, to prepare a statement giving the details that may be readily available in such states, but instead one must be content with more general statements. In the past 10 or 12 years there has been a moderate amount of drilling for both oil and gas widely scattered over the state. Of much of this there is no available record. Morgan, Clay, Scott and Pickett counties have had more oil-drilling activity than any other counties, and likewise they have had almost all of the oil production. In Scott and Morgan counties production centers about Sunbright and Glenmary, the oil coming from the St. Louis limestone at a depth of 1200 to 1500 ft. Wells usually are small but generally hold up well. In Clay, Pickett, Fentress, Overton, Macon and Sumner counties there is a large area in which there are many small structural domes, some of which have been drilled. Wells vary from a few barrels to several hundred flush production and last for some years. The oil comes from porous weathered zones, mostly in the Trenton division of the Ordovician, though some comes from lower horizons beneath one or more bentonite beds that serve as horizon markers and are known as the "pencil cave." Wells recently drilled in the Central Basin and in the Western Highland Rim have been dry or have had only shows of oil. The horizons tested are also usually Ordovician in the Central Basin and usually either Ordovician or Mississippian; occasionally also Devonian on the Highland Rim. In the Gulf Embayment area of West Tennessee there has been but little activity. A well near Ridgely said to be over 2200 ft. deep is supposed to have entered Upper Cretaceous sands and clays in the lower

Jan 1, 1934

By J. E. Schaefer

A summary of oil and gas development in Ohio for 1936 is necessarily brief and, in some details incomplete, owing to the lack of a central state agency for the collection of data and statistics on well drilling and production. The information used in this report was compiled from the records of the several companies operating in the state. Drilling activity in Ohio increased during 1936 as compared to the two preceding years. During the year 1157 wells were completed, as compared to 1022 wells in 1935 and 1055 wells in 1934. However, in spite of this increase in drilling activity, both oil and gas production declined for the year. Activity by Fields Trenton Sand Field.—The Trenton sand field is located in 15 counties of northwestern Ohio, trending from Toledo on the north, south and west through Findlay into Indiana. About 40 years ago the Trenton field was one of the most important oil-producing fields in the United States, but it has declined to a position of minor importance. During the year 1936 there were 52 completions in this field—29 gas wells, 19 oil wells and 4 dry holes. Clinton Sand Field.—The Clinton sand is by far the most important gas-producing field in the state. Production is located in small pools separated by nonproducing areas, on a band of varying width reaching from Cleveland on the north to Lawrence County on the Ohio River on the south. During 1936 a small pool of patchy character was developed in Butler township, Knox County. Seventeen wells were completed in the Clinton sand, of which 13 were gas wells and 4 were dry holes. The average initial production secured per well drilled, including dry holes, was 1,288,000 cu. ft. The average depth of the Clinton sand was 3000 feet. A gas well was completed in lot 9 of Franklin township, Tuscarawas County. Production was found in the first Clinton sand at a depth of 4354 ft. The initial open flow after shot was 828,000 cu. ft. and the rock

Jan 1, 1937

By Kendall E. Born

Production of crude oil in Tennessee during 1937 was slightly over 37,000 bbl., an 85 per cent increase over the preceding year and the highest since 1928. Closer cooperation between the operators and the State Division of Geology has resulted in more accurate data than have been possible for the past few years. Such cooperation is most desirable, especially in this state, which has no law requiring the filling of drilling permits, logs, and production figures. The increased production for the year has resulted from discoveries of four small pools in the shallow district of Clay and near-by counties. The most promising of these began production late in 1937 and consequently has had little effect on the 1937 total. These discoveries, along with renewed activities in some of the older areas, have increased the production for Clay and adjoining counties from less than 5000 bbl. during 1936 to over 21,000 bbl. in 1937. The Mississippi lime production in Scott and Morgan Counties declined from 16,335 bbl. in 1936 to 14,644 bbl. during 1937. While the decline curve on this production has been gradual, some of the wells are over 20 years old, and it becomes necessary to look for other favorable structures in this general region if increased production is to be obtained or past production maintained. The only natural gas marketed off the lease in Tennessee during 1937 was in Morgan County, where a small amount was furnished for the town of Sunbright and its immediate vicinity. The gas occurs with the oil in the Boone Camp field and small amounts were put on the line from the near-by Coon Hollow and Seabolt pools. Development There were 59 wells spudded in during 1937, of which 18 were drilling or only temporarily shut down on Dec. 31, 1937. Of the 41 completions, 17 produced oil, 5 were gas wells of undetermined quantity, and 19 were dry or near-dry holes. The flush production on the new wells totaled about 1300 bbl. per day. The more important wildcats are listed in

Jan 1, 1938

By C. R. Boyd

The sulphuretted ores of Carroll and Grayson Counties, Va., Ore Knob, Ashe County, N. C., and Ducktown, Tenn., in their general position, are in the prolongation of the same massive deposits. The existence of the extensive ore-bodies has been well-established, not only in a practical way, but by the careful research of a number of men of science, including Dr. T. S. Hunt, Professor Kerr, Dr. Genth, Rogers, Safford, Professor Egleston, Dr. H. E. Colton, the writer, and others, and described in one or more of the volumes of our Transactions, as well as in other publications. The greater quantity of&apos; these ores being pyrrhotite, although much of them carry nonmagnetic disulphide, their reduction on the gronnd will probably lead to better results than an attempt to mine and ship them to distant places; and their use as sulphuric acid producers, to be employed in the cheap manufacture of valuable fertilizers, will be chiefly the subject of this paper. The great deposits of Carroll County, Va., are now nearer to railway transportation than any of the others, being six to eight miles from the Cripple Creek extension of the Norfolk and Western Railway, now being constructed, the grading of which is in an advanced state of completion. I am not able to state what are the present prospects of an early completion of the contemplated line of railway to Ducktown. For a long while, during the time those deposits were mined and reduced for their copper, the works were forty miles from any railway ; and the same may be said of Ore Knob, N. C. The deposits in Carroll and Grayson Counties, Va., being now the most accessible to cheap transportation, will naturally claim the greater part of our attention ; though it may be pertinent to remark, just here, that the ores of Ducktown, like those of Carroll and Grayson, Va., exist in the undecomposed levels as iron and copper sulphurets, much of which is a non-magnetic disulphide, as stated, with occasional exhibits of sulphides, such as covellite, erubescite, etc. There are, now and then, small quantities of silver, lead, and zinc,

Jan 1, 1886

By J. M. Vetter, W. F. Bowman

The Gulf Coast area of Texas and Louisiana produced a total of 47,070,650 bbl. of oil during 1928, a decrease of 7,401,173 bbl. from the previous year. Of this amount Texas produced 39,353,950 bbl., or a decrease of 9,689,296 bbl. from the 1927 output. The Louisiana Gulf Coast produced 7,716,700 bbl., which is an increase of 2,288,123 bbl. over 1927. The decrease in the Texas Coastal area is due principally to the decline at Spindletop. Production at the beginning of the year in this field averaged 53,400 bbl. daily. At the end it had declined to 35,850 bbl. The increase in Louisiana was due to development in new fields at Kelso Bayou (East Hackberry), Sulphur, Sweet Lake, Bayou Boullion and Sorrento. This production was maintained by the drilling of 984 wells. Of this number 736 were located in Texas and 248 in Louisiana. Of the 984 wells drilled, 571 were reported as producers. Distribution of the various completions is listed in the accompanying tables compiled by Oil Weekly. New Developments New developments of particular importance in Texas were the finding of a 5000-bbl. well in formations of Cook Mountain age in the Clay Creek field located in northern Washington County by the Sun Oil Co. ; the discovery of oil at Dewalt in Fort Bend County by the Humble Oil & Refining Co.; the development of commercial production at Raccoon Bend in Austin County by the same company; and the finding of oil in formations of Oligocene age in the Refugio gas field of Refugio County. The most important development in Louisiana was the finding of oil at Sorrento, east of the Mississippi River, by the Gulf Production Co. The importance connected with these finds is not so great in that they opened up new fields, but in the new territories which they open as possibly productive of oil. Eastern Louisiana has been looked upon with considerable doubt on account of the theory which has prevailed among most geologists that the nature of the formations was not such as to produce oil. The actual finding of oil in that area upsets this theory and

Jan 1, 1929

By J. French Robinson

A review of production in the Eastern District for 1930 is necessarily brief. Drilling operations were curtailed, due to economic conditions, which in turn reduced production. However, in spite of these conditions, there have been a few outstanding developments which surpass any of recent years. The development of a field in Chautauqua and Cattaraugus counties, New York, has been rapid and probably reached its peak of production in 1930. The gas in this field comes from the White Medina Sand (Silurian), at an average depth of 2600 ft. Some of the wells had an open flow of 20,000,000 cu. ft. of gas per day,&apos; with an original rock pressure of 965 pounds2 per square inch. Another area developed during 1930 was the Tyrone field, in Tyrone Township, Schuyler County, New York. This field was discovered 2nd is practically controlled by the Belmont Quadrangle Drilling Corpn. of New York. The production is from the Oriskany Sand (Devonian), which is found at an average depth of 2100 ft. The field covers approximately 2000 acres, and to date has 14 producing gas wells. The largest well had an open flow of 15,000,000 cu. ft. and an original rock pressure of 740 Ib. The gas from this field is impregnated with sulfur, and requires washing before it is marketed. Because little is known of the Oriskany Sand, a brief description may be of interest. This sand outcrops at Oriskany Falls, New York, and has a thickness of 10 to 12 ft. Its texture is coarse grained, it is composed mostly of quartz and is a regularly bedded sandstone. At Yauger&apos;s Wood, in Cayuga County, New York, it is exposed and shows a thickness of 26 feet. The discovery of the Tyrone field led to much prospecting in the New York and the northern part of Pennsylvania, and as a result of this search, the Allegany Gas Co. struck a large gas well in Farmington Township, Tioga County, Pennsylvania, which created considerable excitement through the Eastern District. The gas was encountered at a depth of 4010 ft., and tested 20,000,000 cu. ft. open flow, with a shut-in pressure

Jan 1, 1931

By L. C. Glenn

In the preparation of this paper the writer has drawn freely upon the writings of Orton, Munn, Shaw, Mather, Miller, Hoeing, St. Clair, Jillson, and others, as well as upon his own personal knowledge of the fields of both states. It is to be regretted that certain data gathered by him and his assistants last fall are not available for publication. Oil in Tennessee A few wells drilled for brine for salt making in Tennessee between 1820 and 1840 obtained oil, but no definite search was made for oil until just after the close of the Civil War. Active drilling was then begun in Overton and counties southwest of it on the eastern half of the Highland Rim. A number of strikes were made at shallow depths in the basal part of the Mississippian but the wells were soon exhausted and abandoned. Drilling was revived, about 1892, when the Spurrier district in Pickett County was developed and was followed by the Riverton district in the same county in 1896. A pipe line was laid from the Wayne County, Ky., fields and about 60,000 bbl. of oil were run before a very heavy slump in the production, a failure to find an extension of the field, and excessive local taxation caused the removal of the pipe line in 1906. There was then no production in Tennessee until the discovery, in 1915, of oil near Oneida, Scott Co., at about 950 ft. (289 m.) in fissures in the Newman or St. Louis limestone. This field, however, soon failed and was abandoned. In 1916, oil was found at Glen Mary, Scott Co., in the Newman limestone at a depth of 1232 ft. (375 m.) A number of wells have since been drilled there, some of which were dry while others, close by, were produccrs. The largest one yielded, at first, about 340 bbl. per day and produced for several months, when it suddenly went dry. Several of the first wells began at 6 or 8 bbl. per day and are still maintaining that output. Production is from a fissured part of the limestone and varies greatly in accordance with the size and extent of the ramification of the

Jan 1, 1921

By Frederick Prime

THE Great or Cumberland Valley, which (under a variety of names) extends from Canada, through Vermont, Massachusetts, Connecticut, New York, Pennsylvania, Maryland, Virginia, and East Tennessee, to Alabama, is composed in part of limestones lying immediately above the Potsdam sandstone. Geologically, they belong to the era between the Potsdam and Trenton, and are commonly termed Calciferous. A peculiarity of these limestones is their great richness in limonite or brown hematite ores, which form a large part of the charges of the many blast-furnaces situated on their outcrops. The mines from which the ores are obtained are (properly speaking) only pits or quarries, from which the ore is extracted by means of picks or shovels, powder being rarely employed. The ore does not occur casually at any point in the limestone, but forms regular lines, following apparently the &apos;outcrops of certain beds. In Lehigh County, Penn., where I have been engaged on the Geological Survey of&apos; the State, during the past season, there are three or four of these lines. During the progress of the survey I was much struck by the fact that the two most important and promising lines of outcrop were, one at the base of the crystalline schists (forming the South or Lehigh Mountain), and overlying the Potsdam sandstone conformably; the other, near the line of junction of the calciferous limestone with the slates of the Cincinnati epoch. The mines along these two lines, following the topography of the country, were in place, richer and more permanent than those of the belts between, which were generally leaner. A peculiarity of these two lines of outcrop, and one to which I particularly desire to draw attention, is the occurrence of what I at first mistook for a highly altered slaty limestone, but which subsequent analysis proved to consist in great part of damourite (hydrated potash mica). The following are analyses of this damourite slate I. From Fogelsville, Lehigh County, within a few hundred feet of the contact of limestone and slate, by Dr. F. A. Genth. II. From Hensingerville, Lehigh County, within 300 feet of gneiss, by Mr. Sydney Castle, of the University of Pennsylvania. III. From Allentown, Lehigh County, within 150 feet of con-

Jan 1, 1875

By C. M. Young

The following paper has been prepared with the object of placing on record in the Transactions some facts concerning the present condition and future prospects of the coal industry of Illinois. In presenting it, the writer wishes to say that a considerable amount of the material contained is taken from the publications and records of the Illinois Coal Mining Investigations, the annual Coal Report of the State Mining Board, and the work of the State Geological Survey. Coal Beds and Mining Methods According to the latest maps of the State Geological Survey, there are only 19 of the 102 counties of the State some portion of whose territory is not within the borders of the coal measures. If outlying areas in Calhoun and Whiteside Counties are considered, the number is reduced to 17. This does not mean that all of the 85 counties that are partly or wholly underlain by coal measures will become producers, as there are some portions of the State in which the coal does not occur in beds of such thickness as to warrant the hope that it can be mined. The mining of coal is widespread, however, for in 1916 there was production from 61 of the 102 counties of the State, There seem to be no cases in which operations will be limited by depth, as none of the coal measures lie at depths much greater than those at which it has been proved that coal may be profitably mined in this field. In fact, the deepest shaft reaching a bed of bituminous coal in the United States is located in this State at Assumption, where coal only 3 ½ ft. (1.07 m.) thick is worked at a depth of 1004 ft. (306 m.). The coal beds occur in the form of a basin which is deepest along a line extending through the central part of the State and bearing a little west of north. The northern, western and southern borders of this basin lie within the boundaries of the State, but on the eastern side the Illinois field is continuous with the Indiana field. The glacial drift covers all except the extreme southern end of the State and the visible outcropping

Jan 1, 1918

By D. D. Pollock

Many constitution diagrams do not indicate the limits oJ solid solubility of the silver-rich solid solutions below 200°C. Thermoelectric measurements were employed to determine this limit in the nieighborhood of room temperature. The appearance of a second phase causes a discontinuity to occur in the tkevtrroelectric power as a function of cornposition at constant temperature and pressure. This discontinuity was employed to determine the limits of the silver-rich terzinal solid solutions of the Ag-A l, Ag-As, Ag- Bi, Ag--Ge, Ag-In, Ag-Pb, Ag-Sb, and Ag-Sn systenls at 30°C. CONSIDERABLE work has been done on the constitution of binary alloys of silver. The available data have been compiled by Hansen1 and Elliott.2 However, many of the binary diagrams do not show the limits of solid solubility of the silver-rich solutions below about 200° C. This work was undertaken in an attempt to extend these limits to the neighborhood of room temperature . PREPARATION OF ALLOYS All of the alloys were made with silver containing less than 0.014 pct (by weight) of impurities. The materials were weighed out into 225-g heats and melted in a high-frequency induction furnace. The indium, tin, and antimony alloys were melted in A1203 crucibles, under a boric anhydride cover, and were poured into split graphite finger molds. The aluminum, germanium, arsenic, lead, and bismuth alloys were melted in machined graphite crucibles; they were also covered with boric anhydride and poured into split graphite finger molds. The $-in.-diam ingots were heated to 750°C and were forged and hot-rolled down to 0.1 by 0.1 in. The wires were pickled in a 25 pct HNO3-75 pct H2O solution to remove any oxygen-rich surfaces. The wires were then annealed at 550°C for 2 hr in a dissociated ammonia atmosphere. They were then furnace-cooled for 20 hr to room temperature in this atmosphere. The wires were cold-drawn to 0.0808 in. diam. The finished wires were again annealed at 550°C in the same manner as in the first anneal. Thermoelectric Power. The thermoelectric power of a single specimen of each alloy was determined against pure silver which contained a maximum impurity content of 0.014 pct by weight. The wire specimens were straightened and then cleaned with ethyl alcohol. They were then reannealed in the same way as the finished wires to assure that any residual stress would be at a minimum level. Previous work has shown that the presence of small amounts of stress has the effect of decreasing the thermoelectric power. The alloy specimen was soldered to the pure silver wire to form the measuring junction. A standard set of copper leads was then soldered to the reference junctions of the thermocouple. These junctions were maintained in separate dewar flasks which contained finely shaved melting ice during the test. The thermal electromotive forces of the thermocouples were measured at four temperatures between 15° and 45°C. A known source of electromotive force was balanced against the output of the thermocouple until a null balance was reached. The data were then expressed in terms of the thermoelectric power at 30°C. The results were then converted to absolute thermoelectric power, s303.3 These data have an average error of less than ±0.2 pct. RESULTS AND DISCUSSION All of the experimental data are given in Table 11. Since the electromotive forces of the binary alloys of silver were determined against the pure silver from which they were made, the resultant thermoelectric powers are only a function of the intentionally added binary elements at the constant test temperatures. This provides a direct measure of the effects of the alloying elements. The absolute thermoelectric power of an alloy of silver is given4 by:

Jan 1, 1968

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,&apos; Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith&apos;s recent thermodynamic measurements and Zener&apos;s theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa&apos; - Fao1 = RT In an1 pure A&apos; Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na&apos;Fa1 + Nb&apos;Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma&apos;+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas&apos; in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By T. O. King, Y. P. Gupta

The self-diffusion of sodium in two sodium silicate liquids was measured in the temperature range 850" to 1500°C by the capillary-reservoir technique. Radioactive Na 22 was used as the tracer. The total count and autoradiographic methods were used for determination of the total Na 22 depletion and diffusion profiles of the dqy-used specimens. The diffusion coefficients obtained by the autoradiographic technique are slightly smaller than those obtained by a total count method. Error analysis of the two methods suggests that more confidence be placed in the results of the total count method. The experimental results were analyzed in terms of the existing activated rate process theory. The activation energy for diffusion was shown to decrease markedly as the temperature increased. This was attributed to a variation in the heat of activation with temperature, probably related to a change in the distribution of anions associated wilh the cation. In terms of a model, suggested for diffusion in liquid silicates, differences in the aclivation energies for diffusion and electrical conduction may arise from the effect of the electric field applied in conduction measurements. It is generally accepted that liquid silicates consist of cations and an equilibrium distribution of complex anions determined by temperature and composition. Transport properties in molten silicates are of interest, not merely because of their relevance to the kinetics of pyrometallurgical reactions and glassmak-ing processes, but also because they are useful to development of the theory of such ionic liquids. Self-diffusion is one such transport process that may, if studied for liquid silicates of widely varying compositions, indicate structural changes through changes in the activation energy for diffusion. The self-diffusion of calcium, silicon,&apos; sulfur: aluminum, 4 and oxygenS in lime-alumina-silica melts and of iron6 in molten iron silicates have been measured. Unfortunately, the errors in some of the reported activation energies for diffusion are too large to allow firm conclusions concerning structure and the mechanism of the diffusion process to be drawn. The research reported here was a study of the self-diffusion of sodium in liquid sodium silicates. The soda-silica system was chosen since: i) a reasonable composition range can be covered in the binary system at moderate temperatures; ii) suitable isotopes of sodium (radioactive Na 22 and NaZ4) can be obtained; iii) data on the electrical conductivity and viscosity of sodium silicate liquids are available. However, the range of composition actually used in diffusion experiments was limited, to 20 to 35 wt pct soda, by the relatively high viscosity of silica-rich compositions and by evaporation of soda from basic melts. EXPERIMENTAL PROCEDURE The capillary-reservoir technique was used, wherein a radioactive tracer, Na 22, incorporated in the capillary melt, was allowed to diffuse out of the platinum capillary tube into a large reservoir of silicate liquid containing a chemically identical melt, but without radioactive tracer. After a specific diffusion time, both the total depletion in the tracer concentration and concentration-distance profiles of the diffused samples were measured by procedures to be described later. The diffusion cell assembly was similar to that used by Koros and King.&apos; The temperature of the diffusion cell was measured with a calibrated Pt, Pt-10 pct Rh thermocouple located at the center of the liquid reservoir. The same thermocouple was used to obtain the temperature profile in the reservoir. The temperature at the top of the reservoir was slightly higher (2°C) than that at the bottom, to minimize convection in the capillary tubes, which were placed, open end up, in the reservoir. Convection was not expected to be a problem since the length-to-diameter ratio of the tubes was about 12:1 and the maximum capillary diameter was 1 mm. The diffusion cell was heated in a molybdenum-wire resistance furnace, previously used by Koros and King, but somewhat modified. A Pt, Pt-10 pct Rh thermocouple enclosed in an alumina tube and located near the furnace winding was used in conjunction with a preamplifier and Micromax proportional controller for temperature control, within 4°C, at temperatures near 1500°C. Before starting a diffusion run, the furnace was heated to the desired temperature and an alumina guide assembly for the capillaries was slowly lowered to within 2 cm of the liquid reservoir. The capillaries were thus heated to about the temperature of the bath. The run was started by lowering the assembly till the open ends of the capillaries were about 1 cm below the surface of the liquid. The run was ended by raising the assembly to about 15 cm above the liquid bath. Later, the sample assembly was slowly withdrawn from the furnace. Six diffusion samples were usually run at the same time. Three runs made with the open ends of the capillaries down were discarded because in the majority of these samples air bubbles trapped at the open end were observed. Some glass adhered to the outside of the capillary on withdrawal. This was carefully removed and used to check that the Na 22 activity in the sink remained at a low level. Materials. Nonradioactive sodium silicates were prepared by melting, in a platinum crucible, weighed quantities of sodium carbonate and powdered silica. To prepare radioactive sodium silicates, Na2 obtained in HC1 solution, was first checked for radioactive impurities by obtaining a y-ray energy spectrum, then the chloride ions were removed by anion-ex-

Jan 1, 1968

By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

By H. O. Hofman

(Canal Zone Meeting, November, 19]0.) THE sudden decease, April 1, 1910, in Chicago, of Dr. Franklin R. Carpenter was a shock to his- many friends. He died in his sixty-second year, of heart paralysis. To most fellow-members of the Institute who have followed the progress of the. last twenty-five years in the mining and treatment of non-ferrous ores, the work of Dr. Carpenter in that line is familiar ; but very few, even of those who knew him well in the later years, are acquainted with his earlier struggles to satisfy an inborn hunger for knowledge. The story of his life resembles that of the pioneer who opens up new country; overcoming hardships with indomitable courage, meeting doubts and difficulties with an alert and open mind, and exercising in the face of reverses an unconquerable perseverance. It seems appropriate to place on record in the Transactions a brief outline of the life and work of this eminent engineer. During the past 15 years of his life Dr. Carpenter was much interested in genealogy. In the pursuit of this study as an avocation, he traced his own ancestry to the time when ?Hugh," called "le Charpentier" on account of the dexterity with which he had swung his battle-axe as a crusader, settled in Sussex on lands received from William the Conqueror. The Carpenters came to this country with William Penn. A prominent member of the family was Joshua Carpenter, the founder of Christ Church, Philadelphia. Dr. Carpenter&apos;s branch of -the family moved from Pennsylvania into that part of Virginia which is now West Virginia, where his grandfather settled in Harrison county, while the grand-uncle went further west, and built the first iron-furnace at Hanging Rock, Lawrence county, Ohio. In fact, since early times, the Carpenters appear to have been iron-masters. Franklin R.. Carpenter was born, Nov. 5, 1848, in Parkers-

Aug 1, 1910

By AIME AIME

As already announced, the XCIIId meeting of the Institute will be held at Toronto, beginning July 23, 1907. Hotel Headquarters will be at the King Edward Hotel, in which also the sessions will be held. The Queens, Rossin, Wallen, Iroquois and Palmer are good hotels not far from the King Edward. Members must secure their hotel-accommodations beforehand, by direct correspondence with the hotel they select. For those who neglect this precaution, the Local Committee will doubtless do what it can, but is unable to promise anything. Correspondence concerning this meeting (including notices of intention to attend it) should be addressed hereafter exclusively to Mr. W. G. Miller, Provincial Geologist, Bureau of Mines, Toronto, who is the representative of the Local Committee. The excursion to Cobalt, Lake Tenagami, Sudbury, etc., arranged by that Committee, involves the use of a special Pullman train for meals and lodging. After waiting a reasonable time to hear from members, the Local Committee has made its contract for Pullman cars. According to its latest report, there was still room for additional excursionists. Under this head, application made immediately to Mr. Miller may not be too late. Sessions for the presentation of papers, etc., will be held at the King Edward Hotel on Tuesday afternoon, July 23, and Wednesday morning and afternoon, July 24. The following papers have been accepted: 1. Sonic Reflections on Secrecy in the Arts, by James Douglas, New York, N. Y. .2. The Wilfley Table, by R. H. Richards, Boston, Mass. 3. The Tar-Sands of the Athabaska District, by&apos; Robert Bell, Ottawa, Can. 4. The Occurrence of Nickel in Virginia, by Thomas L. Watson, Blacksburg, Va. 5. Coal-Briquetting in the United States, by E. W. Parker, Washington, D. C.

Jul 1, 1907