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APPROXIMATELY 26 percent of the total ore production to date from the largest single deposit of copper-bearing material in the world was mined during the war years, 1942 to 1945, at Chile Exporation Company's great open-pit mine at Chuquicamata, Chile. About 18 percent of the total waste removed during the life of the mine was handled in the same period. The total of ore and waste represents approximately 24 percent of the total material that has been excavated from the pit. This is more than was removed in the first fourteen years of operation from 1914 through 1927. The pit at Chuquicamata is 17/8 miles long, 1/2 mile wide, and has a present vertical extent of 817 ft between the top of the highest bench and the lowest bench being worked. However, when

Jan 1, 1948

By J. Fred Johnson

MORE ORE is mined in the Bingham District than in any other mining district in Utah. In addition to the open-pit operations of the Utah Copper Co., there have been, many large underground mines. Until recent years the principal production was from the Jordan and Commercial limestones, but in the last eight years valuable ore deposits have been developed in the so-called alphabetical or "A," "B," "C," and "D" limestones, mainly by the U. S. Smelting, Refining & Mining Co. The value of these developments has led the company just mentioned to acquire large holdings in the district and within the last year to install at the Niagara shaft a hoist capable of going to a vertical depth of 4000 ft., or 1800 ft. deeper than the present lowest level. Ore from Bingham has been the chief factor in enabling the

Jan 1, 1934

By AIME AIME

EVEN the weather man joined in a friendly conspiracy to make the fall meeting of the Industrial Minerals Division at Rolla, Mo., Oct. 23-25. the splendid surges that it was. Following weeks of rain, the foliage of the Ozarks was still green, merely enlivened here and there by splashes of autumn coloring. In contrast to the tranquil beauty of the School of Mines campus under smiling Indian summer skies, the pace of the meeting was lively. Registration was larger than at any previous meeting and included an unusual number of prominent names and delegates from all over the country. From 125 to 150 were present throughout the three technical sessions, at the Thursday evening smoker, and also at the banquet on Friday; when students trooped in to the technical sessions the audience was augmented occasionally to over 200.

Jan 1, 1941

By AIME AIME

BUFFALO, Queen City of the Lakes, singularly accessible by land, water and air, will be the mecca for metallurgists throughout the United States and Canada during the week of the National Metal Congress, Oct. 3 to 7. Headquarters during the National Metal Congress will be the Hotel Statler and there on Wednesday and Thursday, Oct. 5 and 6, the Institute of Metals and Iron and Steel Divisions, A.I.M.E., will hold a series of technical sessions, the annual Science Lecture, a dinner and executive committee meetings. The American Society for Steel Treating, American Welding Society, Production Division of the Society of Automotive Engineers, the Iron and Steel and Machine Shop Practice Divisions of the American Society of Mechanical Engineers, the Wire Association and the American Drop Forging Institute will present a carefully planned program extending throughout the week.\

Jan 1, 1932

By Russell B. Cornell, William B. Plank

AT the close of the academic year 1940-'41 the largest number of students ever recorded received their first or bachelor degree in the mineral technology schools of the United States. The total of men thus prepared to enter their professional careers in the mineral industries was 1601, a number nearly 12 per cent larger than two years ago and nearly 75 per cent larger than four years ago. Notwithstanding this increase in the number of graduates and as had been predicted in the preliminary report in February, there was a slight decrease in the total student population of the schools in both the United States and Canada. During the college year 1940-'41, 9133 students were enrolled in the 54 schools of the United States and 764 in six of the seven schools of Canada.

Jan 1, 1941

By Harry H. Power

INDUSTRY has the right to expect the petroleum engineering schools to supply more than the minimum technical qualifications necessary to obtain or discharge the responsibilities of a particular job. The basic training, social and economic orientation, should go far beyond these minimum requirements. Petroleum engineering students should also be well grounded in the history of the oil business so that they may understand the industry's progress since the advent of the Drake well. Furthermore, according to P. H. Bohart, the schools "have a definite duty to help the students form a workable philosophy of life, which includes an appreciation of the service of science to mankind, and a belief in the obligation of the individual who enters a profession to exalt himself by continuing his studies and growth so that he may never cease making contributions to the advancement of science and industry."

Jan 1, 1948

By Zay Jeffries

Rearmament superimposed on buying sprees by the public, caused a general shortage of metals in 1911. and the rare metals were no exception; they also shared with the more common metals the uncertainty of future demand. In general, the apparent undersupply of metals is a favorable condition for the realization of sleeping possibilities of the rare metals, especially if the supply can he made sufficient to take care of the possible new demand. Many changes in metal usage in 1941 were forced because of shortages. When such changes are in the direction of the economic trend there is a speeding up in the tempo of the inevitable change, but when the forced changes are against the economic trend they are likely to be shortlived. In any event, the latter is not a solid foundation on which to build a future business.

Jan 1, 1942

By Sherwin F. Kelly

THE principal interest in the meeting sings arranged by the Geophysical Committee this year centered around the many papers dealing with the practical applications of geophysical methods to solving geological problems in many other parts of the world. The program Wednesday morning dealt with work in South Africa, Poland, and South America. Rudolph Krahmann's first paper gave a perspective of the geophysical investigations upon mineral deposits in South Africa. A striking point in his story was the tremendous increase in magnetic work during the last two or three years. This is largely accounted for by the intensive exploration for the extension of the Witwatersrand gold mining area. The author mentioned many surveys in which other methods were used for the search for ores of copper, lead, and zinc, and in the study of water-bearing and oil-bearing structures.

Jan 1, 1935

By Walter F. Bradley

CLOSE to 300 members and guests were registered at the Regional Meeting of the Institute in San Francisco. Oct. 3-6, and many other mining men were present at some of the sessions, but failed to register. Headquarters were at the Palace Hotel. Technical papers for the Metals Session were sponsored by the San Francisco Section, whereas the program for the Industrial Minerals Session was arranged by the Southern California Section. Walter W. Bradley, Chairman of the San Francisco Section, opened the General and Metals Session, introducing President Buehler, who gave a hearty welcome to those present. Clyde M. Eye, of the. Benguet Consolidated Mining Co., presented the first paper, entitled "The Economic and Strategic Value of Philippine Metals to the United States." In closing, he urged. that this country retain and control the Philippines because their large

Jan 1, 1935

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division, and revised in 1939. Generally in Table 1 the unit for prescntation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and /or commercial value. As to each spacc in the tabulation, it is citller (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are detcrminable but not detcrminable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries arc not subject to precise determination. In such rases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1939

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (I) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1938

By Theron Wasson

No major oil-field discoveries were made County; the second in Marion township, in Michigan during the year 1940. Produc- Osceola County. Both are producing from tion for the year was maintained by the Stray sand at about 1350 ft. These discoveries made in 1938 and, as a result, is fields are on structures founci by core test-below the total for 1939. Several extensions ing through the glacial drift. The Six Lakes to old fields have been made, which have field, Montcalm County, discovered in helped to maintain production in the face 1934, is Michigan's largest gas-producing of rather rapid decline in the fields of the field. it has 195 wells producing from the southwestern part of the state. Important Michigan Stray sandstone and the Upper extensions were made in Overisel, Porter, Marshall sandstone. This field was devel-Sherman, and Adams fields. Important oil oped on a 40-acre spacing plan, and gas fields of the state are shown on the -map, Fig. I. WiI~dcat Drilling Michigan's production of 19,700,000 bbl. A test in sec. 29, Winterfield township, during 1940 was 3,800,000 bbl. less than Clare County, which is producing oil from the total for 1939, but about one million the Monroe of Devonian age at a depth of greater than 1938. This brings the total 3760 ft., and a well in sec. 31, Lincoln accumulated production for the state to a township, Osceola County, producing from little over 145,000,000 bbl. the Monroe at 3625 it., should be classed as wildcats that are sure to lead to further Active Oil Fields development in I94L The leading producer for the year was the At the end of the year the Gulf Refining Temple field, Clare County, where 29 new Company's deep test on the Kawkawlin wells were drilled. The Walker field, Kent structure in Monitor township, Bay County, was second, but drilled 183 new County, was preparing to drill deeper after wells in order to gain that position. In the having had a gas blowout from a depth of extension of the Overisel field in Allegan 7775 ft. This test is the most important one County, 115 new producers were drilled. drilling at the end of the year in Michigan, The Adams field, Arenac County, was for should it develop commercial produc- revived by several wells with initial production from deeper beds it will lead to deeper tions of over 1000 bbl. per day from the drilling on many well-known structures Dundee of Devonian age. that have been producing from shallower sands. Active Gas Fields Two important gas fields were discovered Exploration by Taggart Brothers during the year. The A small amount of reflection seismograph first was in Riverside township, Missaukee work was done in Clare, Osceola, and Glad-Win Counties during the year. Exploration Manuscript received at the office of the Institute March 28 1941 by shallow drilling for structural informa- tion on beds below the glacial drift con- 347

Jan 1, 1941

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By R. W. Raymond

to same extent, the assumptions tinderlying Dr. Ilu?ley's con alusions. These amrrmptions are: that 'the loss of metal per million tons of trafffc, depends, first upon the circrtnistances under which the rail is worn; secondly, upon the proportions of its various constituents, ancl that the anlorlnt of loss is afEect~d by eacb constitnent in a cer tain ratio, so that if the circunlstances were the same for all tlie mils, the wear per nliilion tons might he upproxi91ately expre~sed by an equation of the form I + Cc + Pp + SR + Mm = R, io wtlioh I is an unknown valne, dependi~.rg on the quantity of iron (and other ingre dients not determined) in the rail, and assumed to be constant for all the rails ; c, p, s, and m are the experimentally determined quan tities of carhon, phosphorus, sulphur, and manganese, as tabulater1 in YIates VT and VII of Dr. Dudley's paper; and R is the experirnen tdlly dcterlnincd wear per million tons; while C, P, S, and M are onknown wfficients. In other words, it is assunled that the differ ence in wear is proportional to a difference in c, p, s, or m, and that the effects of a change in the amonnt of either are independent of the amount of the rest-—within the experinlental limit5 of the problem. It is also assr~med that sulphar, copper, and other ingredients, not determined, are qually present in all the rails, or at least {lo not affect the wear, since I is taken as constant. Dr. Dudley tacitly assumes the coefficient6 C, P, S, and M to be positive; and assigns certain valries to them, by means of which he redom t.he equation to the form I + Pa: = R, x being equal to cc + Es +Mm i Pp, or tjje uanjbe,. of so-called phosphorus units in the rail. But we do not have R directly given under constant circumstances. The varying weights (per engine, car, or train) and the varying epds, we must neglect for lack of data, and assume that in these rwpects the rails examined have been treated srlbstantially alike. But there remain the varying conditions as to track, which mnst he elirninsted. Dr. Dudley gives six clrlsses, four of which contain 8 rails each, and two 16 rails each. Beginning with the 6~st (tangent grade), take the mean of the figures expressing wear for that clam; and continaing tliis process through the other five, we obtain six expressions in quantity of loss 'by wear, which we assome tc, represent, in their differences, the varying conditions of the trarli, with respect to grade and direction. We now take the mean of these moans (giving double weight to the gmiip containing 16 ohwrvafieras). This general rnean is the 10 of metal per million tons of trafio for a rail of avorage constitution under mean ciroumstances.

Jan 1, 1881

By F. H. Wilson, E. W. Palmer

G. L. Bailey (British Non-Ferrous Metals Research Association, London, England)—I was glad to see this further work on the structure and properties of the Cu-Ni-Fe alloys of low nickel content in which we have been so interested in the United Kingdom since before the war." The authors' data on the variation in solubility of iron in both 5 and 10 pct Ni alloys with temperature is based on more detailed observations than we have made but is generally in line with our own work. The difficulty in these matters is in the identification of the structures obtained. The precipitation of the second phase which we presume to be the a' solid solution, richer in nickel and iron, from the a solution with which it is in equilibrium occurs in such a fine state of division that its resolution by ordinary micro-graphic methods is impossible in the early stages. We have published some electron micrographs which illustrate the effects observed more clearly but we agree with the authors when they say that dark staining characteristics when the alloys are subjected to sea-water corrosion are more sensitive in detecting the presence of the a' phase than is the microscope. After taking this point into consideration, however, I confess to some difficulty in understanding Fig. 4. I can only assume that the precipitates visible at such a low magnification as 150 diam in these relatively coarse forms are produced from iron-rich areas of the initial solid solution due to inadequate homogenization. If this is so I find it difficult to accept the authors' contention that such local variations in iron concentration as are capable of giving the heavy precipitates shown in Fig. 4 do not in fact materially affect the solvus surfaces of their equilibrium diagrams. I share the authors' enthusiasm about the resistance to corrosion of these alloys by seawater but I am not fully in agreement with them on the vexing question of the best iron content for these alloys. In Fig. 3 of ref. 8, we give many results showing that the resistance of these alloys to impingement attack in the Jet Test increases as the iron content rises to 2 pct. With higher iron contents pitting at shielded areas is likely to occur. Admittedly the addition of 0.75 pct Fe produces a large improvement in corrosion resistance compared with a pure 90/10 Cu-Ni alloy, but the further improvement on raising the iron to 2 pct is substantial. We recommend from 1.5 to 2 pct Fe as the desirable range from the point of view of corrosion resistance. While it is true that British practice generally uses a hard tube, the corrosion resistance of the 10 pct Ni alloys has in our work been little affected by the structural condition. Although the annealed alloys blacken in seawater, this effect seems to be superficial and not to be accompanied by any real decrease in

Jan 1, 1953

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly dzerent stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report l,8x,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1937

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By L. S. Richardson, N. J. Grant

REACTIONS of oxygen and nitrogen at low pressures with titanium have recently been studied by a number of investigators.1-3 Gulbransen and Andrew' noted that the reaction with nitrogen followed the parabolic rate law whereas the reaction with oxygen deviated slightly from this law in the temperature range 300° to 800°C. In the work reported here, commercial titanium (75 A) was used as the test material. Cylinders 2.5 in. long and 0.25 in. in diameter were machined from heavier bar stock. The test pieces were given a metallographic finish, immersed for 30 min in cold concentrated HC1, washed in water, then acetone, and dried with lint-free cloth. Reaction rates were determined in a modified Sieverts type apparatus by measuring the decrease in gas pressure of the reacting gas contained in a constant volume. The amount of gas added could be measured in a calibrated gas burette to an accuracy of 0.01 mm. During the course of a run the temperature never varied by more than 10°C and then only for brief moments. After placing the specimen in the furnace, the system was first evacuated for 12 hr at room temperature, and then flushed with purified argon five times, adsorbed gases being discharged during this period from the glass system with a high frequency spark coil. The flushing and discharging were repeated at 400°C. This rather involved procedure was found necessary after a number of trial runs indicated extraneous effects traceable to the system. Reaction periods up to 2 hr were used, at initial gas pressures of 0.2 to 0.5 atm. Experimental Results Fig. 1 shows the decrease in oxygen pressure for tests at 0.5 atm at various temperatures as a function of the square root of the time. Deviations from linearity are minor and the parabolic rate law is obeyed. Fig. 2 shows the same plot for the nitrogen reaction. A definite deviation from linearity is noted; however, it is probable that the higher initial rates are caused by the presence of small amounts of oxygen contamination, the initial faster rate changing to the slower rate after about 5 to 10 min. Calculations of the rate constants were made on the basis of the latter portion of the curves. The parabolic rate law constants calculated from these curves are shown for oxygen and nitrogen in Fig. 3. In spite of some scatter the average curves are quite definite. Changes in gas pressure of the order of 20 pct did not result in a measurable change in the rate law constants. The activation energy for the oxygen reaction was calculated to be 47,400 cal per mol (above 700°C), which is not in agreement with the value quoted by Gulbransen and Andrew' for lower temperatures, their value being 26,000 cal below 600°C. The activation energy for the nitrogen reaction was calculated to be 45,400 cal per mol above about

Jan 1, 1955

By C. E. Birchenall, M. H. Davis

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. 'The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew' suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman's' observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with

Jan 1, 1952

By B. L. Averbach, M. Cohen, G. P. Conard

IT has been frequently observed that, when metal crystals are bent and annealed or when they are bent at elevated temperatures, the asterism of the Laue spots is split discontinuously into tiny intensity maxima. This finding indicates that segmented crystallites or subgrains are produced, which are relatively undistorted within themselves but which differ slightly in orientation from their neighbors. The following viewpoints have been put forward concerning the nature of this segmentation process: 1—Crussard' has described the phenomenon as "re-crystallization in situ." According to this mechanism, the deformed lattice recrystallizes on heating into an aggregate of comparatively strain-free subgrains separated from one another by low-angle boundaries and having nearly the same orientation as the original crystal. This process differs from the classical type of recrystallization in that the latter involves the formation of grains having quite different orientations from that of the mother crystal. 2—A similar but more detailed picture has been advanced by Cahn' who adopted the term "polygonization." In this interpretation, the plastic bending of lattice planes results in an excess of dislocations of one sign, but at suitable temperatures these dislocations migrate along slip planes and collect in localized regions to form an array of low-angle boundaries. Concurrently, the lattice segments between the boundaries lose their curvature and elastic strain. 3—The "cell formation" concept of Wood and co-workers: unlike the two hypotheses cited, postulates that the segmentation of the lattice is basically a mode of deformation and is not an annealing phenomenon. Cell formation appears to compete more effectively with respect to the normal slip process as the deformation temperature is increased and as the strain rate is decreased. The present work was performed on 3.2 mm diameter 99.99' pct Zn single crystals, grown from the melt in a gradient furnace. The major impurity was 0.003 pct Fe. The crystal orientations ranged from those with basal plane parallel to the rod axis to those with the basal plane almost perpendicular to the rod axis. The specimens were bent on templates to effective radii varying from 14.2 to 1.3 cm at the temperatures from —196" to 100°C. In each case, the axis of bending was parallel to the basal plane. Subsequent annealing was carried out at temperatures from —196" to 400°C. Back-reflection Laue pictures were taken on the convex surface of the bent specimens, before and after annealing. This procedure was found to yield better resolution of the detail in the diffraction spots than did the previously used Laue transmission technique. Some X-ray pictures of rods bent at —196" and —78°C were taken at these respective temperatures without intermediate warming to room temperature. In addition, bent crystals were acid cut" parallel to the basal plane, and double-crystal spectrometer rocking-curves were obtained from the etched (0001) face before and after increment an-

Jan 1, 1954