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By E. R. Gilbert

Klopp et al. have reported data on tensile and creep properties of are-melted and electron-beam-melted tungsten. We would like to point out some similarities between their creep results and ours on are-melted and powder-metallurgy tungstenand offer some alternate interpretations of the data which lead to different rate-controlling mechanisms. Klopp et al. observed extensive transient creep in the 2250" to 3500°F temperature range where the acthetivation energy is 106,400 ± 3300 cal mole-1. They suggest cross slip as the possible rate-controlling mechanism since "cross slip may occur only by the movement of screw dislocations, and not edge dislocations, thus allowing only partial recovery of the strain hardening and resulting in a continuously decreasing creep rate, characteristic of transient creep.'' Our tests on are-melted tungsten and powder-metallurgy tungsten displayed an extensive transient creep stage in the same temperature range but they also displayed a steady-state creep stage. The stress levels and strain rates of the two investigations, 1.4 to 7 kg mm-2 and 10-7 to 10-4 sec-1 for that of Klopp et al. and 4.5 to 10 kg mm-2 and 10-8 to 10-4 sec-1 for those of Gilbert et al., are overlapping. The activation energy for creep of our powder-metallurgy tungsten is 105,000 cal mole-1. This close agreement with the value found by Klopp et al. suggests that the same mechanism may be common to both types of materials. It may be possible to gain some additional insight into the rate-controlling mechanism by applying the analysis made by conrad22 in terms of the activation volume. The value for the activation volume depends upon the dislocation mechanism and may be used to help differentiate between various dislocation mechanisms. The activation volume for cross slip is 10 to 100 b3. Values determined from our data were 130 to 220 b3 which are in better agreement with the range of 102 to 104 b3 for nonconservative motion of jogs. Values determined from data of Klopp et al. are 240 to 1040 b3. We suggest that the rate-controlling mechanism for creep in this temperature range may be nonconservative motion of jogs assisted by enhanced diffusion along grain boundaries or dislocations. This model requires an activation energy lower than that for self-diffusion as is observed. If this is the controlling mechanism, a higher activation energy which is closer to that for self-diffusion might be expected for tests conducted on specimens with reduced grain boundary area, i.e., larger grain size. In support of this premise we have conducted tests on speci- mens having one to three grains per cross section for which a higher activation energy of 130,000 cal mole-1 was observed. Also, in agreement with results of Klopp et al., a faster creep rate resulted from the increased grain size and probable decreased dislocation density. Further argument against the cross slip mechanism is based on the constant activation energy we obsserved over the range of 5.0 to 10 kg mm-2,21 whereas the activation energy for cross slip displays a significant stress dependence.23 In addition to this, the powe on the stress term for the strain-rate dependence appears too high for cross slip. The values for tungsten fall in the range of 4.5 to 7 (Klopp et al. and Ref. 21) whereas values of approximately 2 are observed in creep by cross slip for hep metals.24 At temperatures from 3300° to 4000°F, Klopp et al. observed an activation energy of 141,000 ± 4000 cal mole-' which is less than that for self-diffusion, 153,000 cal mole-1, 25 and less than that reported for high-temperature creep of powder-metallurgy tungsten by Green:' 160,000 cal mole-1. Klopp et al. suggested that recovery of strain hardening by dislocation climb is the rate-controlling mechanism in this temperature region. Actually an activation energy larger than that for self-diffusion is predicted by this model if the temperature dependence of the elastic modulus27 is taken into consideration. Klopp et al. attributed this lack of correlation to the compositional differences between powder-metallurgy tungsten used by Green and their own arc- and EB-melted tungsten. It is our position that the value of 141,000 ± 4000 cal mole-' represents a transitional value between the higher and lower activation energies and does not represent a discrete mechanism of deformation. If the tests had been extended to higher temperatures the higher value of activation energy would have been observed as has been demonstrated by both our analy sis'' of isothermal test data by GE-NMPO28 and differential temperature tests28 on are-melted tungsten. The activation energies determined (170,000 and 160,000 cal mole-1) were greater than that for self-diffusion and are in better agreement with the value found by Green. The model of dislocation climb is associated with ; activation volume of 1 b3 according to Conrad.22 The activation volume calculated for the creep data of fou independent investigators in the temperature range where the activation energy for creep is near that for self-diffusion (Klopp et al. and Refs. 26, 28, and 30) is 110 to 2800 b3 and is in the range suggested for nonconservative motion of jogs. In the case of tungsten this mechanism may be preferred over that of dislocation climb. Sincere appreciation is expressed to Messrs. J. E. Flinn and F. L. Yaggee for the helpful discussions and suggestions in the preparation of this communication.

Jan 1, 1967

By Elmer R. Kaiser

Industry Adopts Research: Seventy-Ave years ago Thomas A. Edison began in a modest way and with limited funds to gather about him men of various talents to form the first industrial research laboratory. His laboratory at Menlo Park, N. J., became famous for many discoveries and inventions, but possibly the most important of all may yet be the industrial research laboratory itself. Today, private industry operates 2500 research laboratories in which 135,000 persons' are directly and indirectly creating new processes and products and improving old ones, as well as developing new information to help keep the fountain of knowledge from running dry. In this change-making function, the scientific personnel comprises 41 pct; the technical personnel 26 pct; and the balance, 33 pct, nontechnical. The term "industrial research" has become so broad as to include almost everything beginning with the search for and discovery of the laws governing the properties of matter and energy to the development and testing of processes, methods, and equipment. These classes of investigation commonly merge so that no sharp boundary can be traced between them. The National Research Council therefore defines industrial research as "the endeavor to learn how to apply scientific facts to the service of mankind."' Currently, expenditures for research by industry are variously estimated at between $450,000,000 to $700,000,000 a year,' or about twice the expenditure for 1940. The President's Scientific Research Board" estimated that the national research and development for 1947 (excluding atomic energy) was as follows: A few companies spend as much as 5 pct of their gross receipts for research, but 1% to 2 pct is considered a good proportion by many." Shortages: Commendable as is the record of growth and accomplishment of science in industry, it is only a beginning. America and the rest of the world have merely sampled the fruits of industrial research; most industries have yet to make research the key to their future. A top research consultant, T. A. Boyd, of General Motors, states ". . . perhaps 90 per cent of all companies still have no research laboratories."Y or example, of more than 17,000 manufacturing concerns whose gross sales exceed $500,000 a year, less than 2500 have research laboratories. A still smaller proportion of the 184,230 manufacturing establishments in 161 industriese have or could afford their own research facilities. Yet, the small and mediurn-sized com,panies with less than 250 employees each, produce one half of the dollar volume of manufactured products.' How are these companies to participate in and share the benefits of research? Boyd gives two reasons for the inadequate number of laboratories in industry: Many people still do not appreciate the importance of research, nor understand its tremendous potentiali-

Jan 1, 1951

By Elmer R. Kaiser

Industry Adopts Research: Seventy-Ave years ago Thomas A. Edison began in a modest way and with limited funds to gather about him men of various talents to form the first industrial research laboratory. His laboratory at Menlo Park, N. J., became famous for many discoveries and inventions, but possibly the most important of all may yet be the industrial research laboratory itself. Today, private industry operates 2500 research laboratories in which 135,000 persons' are directly and indirectly creating new processes and products and improving old ones, as well as developing new information to help keep the fountain of knowledge from running dry. In this change-making function, the scientific personnel comprises 41 pct; the technical personnel 26 pct; and the balance, 33 pct, nontechnical. The term "industrial research" has become so broad as to include almost everything beginning with the search for and discovery of the laws governing the properties of matter and energy to the development and testing of processes, methods, and equipment. These classes of investigation commonly merge so that no sharp boundary can be traced between them. The National Research Council therefore defines industrial research as "the endeavor to learn how to apply scientific facts to the service of mankind."' Currently, expenditures for research by industry are variously estimated at between $450,000,000 to $700,000,000 a year,' or about twice the expenditure for 1940. The President's Scientific Research Board" estimated that the national research and development for 1947 (excluding atomic energy) was as follows: A few companies spend as much as 5 pct of their gross receipts for research, but 1% to 2 pct is considered a good proportion by many." Shortages: Commendable as is the record of growth and accomplishment of science in industry, it is only a beginning. America and the rest of the world have merely sampled the fruits of industrial research; most industries have yet to make research the key to their future. A top research consultant, T. A. Boyd, of General Motors, states ". . . perhaps 90 per cent of all companies still have no research laboratories."Y or example, of more than 17,000 manufacturing concerns whose gross sales exceed $500,000 a year, less than 2500 have research laboratories. A still smaller proportion of the 184,230 manufacturing establishments in 161 industriese have or could afford their own research facilities. Yet, the small and mediurn-sized com,panies with less than 250 employees each, produce one half of the dollar volume of manufactured products.' How are these companies to participate in and share the benefits of research? Boyd gives two reasons for the inadequate number of laboratories in industry: Many people still do not appreciate the importance of research, nor understand its tremendous potentiali-

Jan 1, 1951

By R. M. Asimow, J. J. Svitak

Tile crilical resoll,r,d shear stress, CRSS, for slip of slow1y cooled Ag-All single crystals was measured at 201K. Tlze importance of short-range order and Suzuki sogregalion was inrestigated by deter~rlining llze ciic.cl of quenching on the CRSS. Thr obserz.ed rfrtenching effects were generally small and indicate that short-range ordcr and Slczuki srgregation do no1 account for n significant portion of the solid-solution strengthening in this system. However, all alloys slzozcwi yield drops ulhich rilere heat- lreat nrenl-sensiline THERE have been a number of mechanisms proposed to explain alloy strengthening in the Ag-Au system. The effectiveness of some of the proposed mechanisms, especially those that depend on Suzuki segregation1" or on short-range order,2-6 SRO? should be strongly dependent on heat treatment. Since internal friction investigations in this system indicate that there is stress-induced order,' we must also consider the possibility of local atomic rearrangement or short-range ordering in the stress field of a dislocation. There is not complete agreement whether these mechanisms should be most effective in raising the flow stress, in causing yield drops. or some combination of these two effects. This work was undertaken to determine the effects in the Ag-Au system of mechanisms that depend on segregation or order by using known but drastically different cooling rates following a high-temperature treatment. By comparing the critical resolved shear stress, CRSS, for slip measured after a very slow cool and again after a fast cool (quench) of the same crystal, it is possible to determine the effect of cooling rate on CRSS* and on yield drops. The single-crystal CRSS was determined at several compositions because there has been no data published across the phase field since the publication of room-temperature flow stress by Sachs and Weerts.' EXPERIMENTAL PROCEDURE Starting with materials of 99.999 pct purity, single-crystal specimens of random orientation 1.25 mm square by 4 cm long were prepared with 0, 10, 14, 25, 30. 50, 70. 75. 80, 90. and 100 at. pct Au. Crystals were grown in an inert atmosphere using a modified Bridgman technique with a growth rate of 1.5 cm per hr in a gradient of 3°C per cm. To obtain a maximum practical degree of SRO, the crystals were cooled at a rate of 275'C per hr to about 310°C and then cooled at 6°C per hr to approximately 200°C. Specimens were tested in tension immersed in an alcohol bath at -72°C (201°K) at a strain rate > = 0.003 mm"1 to determine the CRSS (7). The activation volume of several crystals was determined from the flow stress increment (72 - T1) for a tenfold increase in strain rate. The total shear strain varied from 0.05 to 2.3 pct but was generally less than 0.4 pct. After testing, each crystal was then held at 500°C for 10 min, quenched into brine at -35°C and. after storage at -71°C for 1 day, retested in tension using a procedure identical to that of the first test. The quenching apparatus, see Fig. 1, was designed to enable accurate temperature control and rapid quenching while preventing specimen contamination and accidental deformation. Test data from a specimen with a fine thermocouple spot-welded to it indicated a cooling rate of 104C per sec. The relatively low heat-treatment temperature was chosen to minimize quenching defects caused by a large vacancy

Jan 1, 1970

By Reginald E. Hore

Since the discovery of silver at Cobalt, Ontario, in August, 1903, more than 100,000,000 oz. of silver have been produced by the mines in the Nipissing district, and there is reason to believe that at least as much more will be produced in the nex five years. The estimated value of the aggregate output o ore to the end of 1910 is $48,327,280. The ore yielded 93,977,833, oz. of silver and was mined at a net profit of abou $16,000,000. For 1910 the production was 30,558,825 oz., valued at $15,436,894, and yielding a profit of about $9,000.000. The details of the production of the Cobalt district for the years 1904 to 1909, inclusive, as reported by the Ontario Bureau of Mines, are given in Table I. The shipments from Cobalt are in the form of smelting-ore, concentrates from milling-ore, and bullion. The smelting-ore is largely high grade, averaging about 3,000 oz. per ton A smaller return is from what is called low-grade ore and which

Jan 1, 1912

By Y. H. Liu, G. W. Powell

Thin foils made from the gold-rich region of- short (0.15 mm)Au-Ag diffusion couples annealed at 880°C for 1 hr were examined in ax electron microscope and the structures were compared with that of pure gold subjected to identical heat treatments. The couples underwent Plastic deformation (bending) during the diffusional anneal. The foils prepared from the diffusion zone have a higher dislocation density and incidence of subboundaries than pure gold. The plastic bending of the couple can be interpreted in terms of the climb of edge dislocations, which are pavallel to the bend axis, along the direction of diffusion. THE interaction of lattice defects during interdiffu-sion between two metals has been considered by several investigators. In particular, da Silva and Mehl,1 Barnes,' and Bardeen and Herring3 have proposed models based on interactions between point and line defects to account for the Kirkendall effect (marker movement). Each of these models is based on dislocation climb, which can either add or remove lattice planes, induced by an under- or supersaturation of vacancies. A theoretical treatment of the nucleation and growth of voids by the condensation of vacancies has been presented by Seitz.4 Stresses can arise in a binary diffusion couple as a result of the vacancy flux and the gradient in the lattice parameter. rinkmman' has investigated the effects of diffusion-induced stresses on void formation; the results of his analysis suggest that voids can form and grow under the influence of these stresses in the absence of an excess vacancy concentration. The relationships between vacancy supersaturation and diffusion-induced stresses and void formation have been elucidated also by Balluffi and seigle6 who concluded that the stress generated by a vacancy supersaturation aids the growth of voids. Experimental evidence which indirectly shows that stresses are produced by chemical diffusion has been obtained by several researchers.2,7-9 This evidence consists in part of the observation by light microscopy of the formation of subgrains, a process characteristic of the high-temperature deformation of some metals during creep.'0 More striking, however, is the plastic bending of short (0.2 mm) Cu-Ni couples observed by Barnes2 and of boron-doped silicon crystals reported by Queisser.9 Diffusion-induced dislocations in iron and silicon have been investigated by Ainslie et a1.11and Schwutte and Queisser,12 respectively, the former using transmission electron microscopy and the latter an X-ray transmission technique. Matthews and Crawford13 observed the formation of boundaries by the climb of interfacial misfit dislocations in thin, vapor-deposited Au-Pd couples diffused in situ in an electron microscope. In order to obtain additional information on the phenomena associated with defect interaction and diffusion-induced stresses in binary couples, an electron transmission study of foils prepared from the diffusion zone of short Au-Ag couples was undertaken. The initial objective was to investigate the processes occurring at various points of the diffusion zone. Subsequent research demonstrated that foils could be prepared only from the gold-rich region of the diffusion zone using the technique described herein. EXPERIMENTAL PROCEDURE Preparation and Annealing of the Diffusion Couples. The couples were made from annealed, high-purity (99.999 pct). polycrvstalline gold and silver sheets (0.075 mm thick). Shall (0.075 by 5 by 17 mm) elec-tropolished coupons of gold and silver were pressure-bonded by heating the two metals in a graphite device to 770°C and holding at this temperature for approximately 30 min. The quality of the bond was ascertained by metallographic examination at 150 times. Each couple subsequently was annealed at 880°C for 1hr; under these conditions, the extreme portions of the

Jan 1, 1968

By T. S. Lundy, J. Askill

J. Askill and T. S. Lundy (Oak Ridge National Laboratory)—Moore has proposed a simple correlation between the activation energy for solute diffusion in fee metals and the atomic volume of the diffusing species using both tracer and chemical-diffusion data. The first point we wish to make is that it is wrong to attempt such correlations without separating the two types of data. Activation energies obtained using tracer techniques cannot, in general, be directly compared with those obtained from chemical-diffusion experiments. A knowledge of the variations of chemical potentials with composition is necessary and chemical-diffusion data must be corrected for such variations, even for dilute alloys, before a comparison is possible. Secondly, for nickel, iron, aluminum, and lead, Moore neglected a number of recently published works, e.g., Al26 and Mn54 in aluminum,46 cr51 in nickel,47 and Fe55 in iron.48 These and others should have been used. If one considers only the tracer diffusion data, there is left no simple correlation of the type proposed by Moore. For example, in the case of solute diffusion in aluminum the only reliable tracer data listed by Moore are for zinc and aluminum. The nickel, cobalt, and iron data of Agarwala49 are representative of near-surface diffusion-not bulk diffusion. In conclusion we suggest that for tracer diffusion data in these fee metals there is no justification for proposing any simple correlation of activation energy with atomic volume using the limited data that are presently available. R. H. Moore (author's reply)—The writer has proposed a simple correlation which is useful in estimating the internal consistency of diffusion data. The accuracy of the correlation is, of course, a function of the number of data available. Lundy and Askill take issue with the writer's decision to include data for the systems: nickel, iron, aluminum, and lead, taking the view that the data are insufficient to establish the correlation. The writer agrees that the data are insufficient and has cau- tioned the reader that the correlation is tentative in these instances. Inclusion of these systems is justified by the interesting trends the correlation reveals. For example, the distinction between interstitial and substitutional diffusion may be clearly established, Figs. 4 and 6, and the behavior of transition elements and nontransition elements is indicated to parallel the behavior illustrated by the silver and copper systems. Lundy and Askill have singled out the aluminum system for special criticism. The writer chose to discuss the data for diffusion of iron, nickel, and cobalt in aluminum in the terms used by the original authors9 and has included the comments of Balluffi.l0 The writer did not intend the reader to conclude that data for these elements should correlate with data for the nontransition elements as Lundy and Askill have evidently assumed. Iron, nickel, and cobalt form intermetallic compounds with aluminum, so the activity coefficients of these elements may be expected to deviate markedly from unity. This may account for the low frequency factors observed by Hirano.9 The nontransition elements, on the other hand, yield relatively simple phase diagrams with no evidence for intermetallic compound formation as in the case of iron, nickel, and cobalt. In dilute solution, Henry's law should be closely obeyed, the activity coefficients should not deviate markedly from unity, and the effect on the activation energy should not be large. The accuracy of the correlation applied to these systems will improve as the data is extended. It does not seem unreasonable to conclude that its extension should be encouraged.

Jan 1, 1965

By M. J. Saarivirta

A high-purity copper-zirconium alloy system was imesti-gated. The zirconium content of the alloys studied varied from 0.003 to 0.23 pet. The solid solubility of zirconium in copper and some physical and mechanical properties of the alloys have been determined. By proper heat treatment, Cu-Zr alloy can develop a high electrical conductivity and resistance to softening at temperatures up to 500°C (930°F). This combination of desirable properties makes this alloy superior, to other com-merzcrrl copper base alloys for- use in the electrical conductor field. DEMAND for high conductivity copper alloys that retain their mechanical properties at elevated temperatures is growing rapidly. At present, copper-base alloys such as copper-silver and copper-chromium are used where these characteristics are required. As an example, commutators in electric motors are often made of these alloys. However, the life at elevated temperature of commutators made of copper-silver alloys is much shorter than the life of the same part made of copper-chromium and copper-zirconium alloys. Copper-silver alloys are subject to creep and subsequent failure when the service temperature exceeds several hundred degrees centigrade. Use of copper-chromium alloys has been known for the past several years, but little information is available in the literature concerning the properties of alloys in the copper-zirconium alloy system. Some work had been directed toward determining the solubility of zirconium in copper as well as determining properties of the Cu-Zr alloys. These investigations have revealed the superior high-temperature and electrical conductivity properties of copper-zirconium alloys over copper-chromium alloys. The United States Metals Refining Co., Carteret, N. J. has recently produced OFHC R copper-zirconium alloys for experimentation and evaluation. Because OFHC R copper contains no appreciable oxygen, no harmful oxides are formed and the full benefit of Zr as an alloying addition is obtained. This paper describes the results of this work. It contains room-temperature and some high-temperature data which have been obtained after various processing techniaues. Actual elevated temperature properties are being determined and will be reported in a separate paper. Preliminary results obtained at elevated temperatures suggest that the Cu-Zr alloy is superior to other high conductivity copper-base alloys. WORK PROCEDURE The high-purity oxygen free (OFHC R) copper-zirconium alloys with zirconium content ranging from 0.003 to 0.23 pct were cast into 4-by 4-in. wirebars by both continuous casting and conventional casting methods. Zr was added in the form of a master alloy containing 30 pct Zr and 70 pct Cu. Castings were analyzed for zirconium and nine bars containing various amounts of zirconium were selected for this study. The results of analyses and the sample numbers are given in Table I. Typical analyses of OFHC R copper are also shown. The following properties were studied: A) Solid solubility of zirconium in copper. B) Effect of zirconium on properties of copper. C) Effect of combined working and heat treating on properties of Cu-Zr alloys. The solid solubility of zirconium in copper was determined by metallographic techniques. Specimens for this phase of the investigation were hot rolled at 900oC (1650oF) to 0.250-in. rod. The rolled rods were cut into 2/3-in. long specimens and solution annealed at 950 °C (1740°F), 980°C (1795 °F). and 1020 °C (1870 °F) for 6 hr and quenched in water. In order to find the solid solubility limits at lower temperatures, the homogenized specimens were reheated at various temperatures for 1 hr and quenched. The physical and mechanical properties were determined on 0.250 in. rod, 0.132- and 0.081-in. wires. The wires were cold drawn from the 0.250-in. rods after they were solution annealed at 980 °C (1795°F) and quenched in cold water. Mechanical and electrical properties were determined on cold drawn and

Jan 1, 1961

By C. A. Hartnagel

The production of petroleum in New York state in 1942 amounted to 5,410,000 bbl. This represents an increase over each of the four preceding years, and, with the exception of 1937, is the largest production since the peak of over six million barrels in 1882, shortly after the discovery of oil in Allegany County. The oil industry in New York is virtually stabilized and there has been little or no exploration for new sources of supply in recent years. The boundaries of the present fields were established more than 30 years ago and since then no additional reserves have been found. Deep drilling for natural gas during the past 10 years both within and without the oil fields has failed to find oil in quantity below the present producing sands of Devonian age. Oil Since 1882, the New York fields have produced approximately 140 million barrels of oil. Of this amount, 65 million was produced up to the year 1919 by ordinary pumping methods; that is, without flooding by water or the use of other secondary-recovery methods. In the year 1919, when a law was passed making the use of water-flooding methods legal, the oil production, of the state amounted to only 851,000 bbl. In the 23 years since 1919, there have been produced in the state 75 million barrels, or 10 million more than in the previous 37 years, which included the period of flush production. Price.—On March 26, the price of crude oil was raised from $2.75 to $3.00 per barrel, hut this increase had little or no effect on the number of wells drilled. In the Allegany field, which accounts for three fourths of the state's oil production, 1259 wells were completed in 1942, 7 less than in 1941. The smaller number of wells drilled was not only due to the shortage of labor but also was caused by the fact that in water-flooding territory a definite program for drilling wells is followed, and the flush period of an oil well is not usually reached in time to profit by any given price increase. Daily Production.—All of the oil wells in New York state, some 21,000 in number, are small producers. The average daily oil production is 7/10 bbl. per well. Under good flooding conditions, a maximum production of 5 to 8 bbl, a day is reached about one year after the flood begins to act on the well. In 5 years the daily production usually is less than one barrel. Although most of the oil in New York is produced by flooding, an estimated 2500 old wells produce without flooding. Some of these produce as little as 1/20 bbl. a day and are pumped only at intervals. The small producing Wells are mostly on lands leased to the larger oil companies and later will be included in a flooding program. At present, they are pumped only because the owners of the land insist on the royalty. Government Aid Needed.—Because of its good lubricating qualities, New York oil is one of those for which there is an insistent and growing demand, but even at its present price of $3.00 per barrel, many of the operators are producing at a loss.

Jan 1, 1943

By C. A. Hartnagel

The production of petroleum in New York state in 1942 amounted to 5,410,000 bbl. This represents an increase over each of the four preceding years, and, with the exception of 1937, is the largest production since the peak of over six million barrels in 1882, shortly after the discovery of oil in Allegany County. The oil industry in New York is virtually stabilized and there has been little or no exploration for new sources of supply in recent years. The boundaries of the present fields were established more than 30 years ago and since then no additional reserves have been found. Deep drilling for natural gas during the past 10 years both within and without the oil fields has failed to find oil in quantity below the present producing sands of Devonian age. Oil Since 1882, the New York fields have produced approximately 140 million barrels of oil. Of this amount, 65 million was produced up to the year 1919 by ordinary pumping methods; that is, without flooding by water or the use of other secondary-recovery methods. In the year 1919, when a law was passed making the use of water-flooding methods legal, the oil production, of the state amounted to only 851,000 bbl. In the 23 years since 1919, there have been produced in the state 75 million barrels, or 10 million more than in the previous 37 years, which included the period of flush production. Price.—On March 26, the price of crude oil was raised from $2.75 to $3.00 per barrel, hut this increase had little or no effect on the number of wells drilled. In the Allegany field, which accounts for three fourths of the state's oil production, 1259 wells were completed in 1942, 7 less than in 1941. The smaller number of wells drilled was not only due to the shortage of labor but also was caused by the fact that in water-flooding territory a definite program for drilling wells is followed, and the flush period of an oil well is not usually reached in time to profit by any given price increase. Daily Production.—All of the oil wells in New York state, some 21,000 in number, are small producers. The average daily oil production is 7/10 bbl. per well. Under good flooding conditions, a maximum production of 5 to 8 bbl, a day is reached about one year after the flood begins to act on the well. In 5 years the daily production usually is less than one barrel. Although most of the oil in New York is produced by flooding, an estimated 2500 old wells produce without flooding. Some of these produce as little as 1/20 bbl. a day and are pumped only at intervals. The small producing Wells are mostly on lands leased to the larger oil companies and later will be included in a flooding program. At present, they are pumped only because the owners of the land insist on the royalty. Government Aid Needed.—Because of its good lubricating qualities, New York oil is one of those for which there is an insistent and growing demand, but even at its present price of $3.00 per barrel, many of the operators are producing at a loss.

Jan 1, 1943

By AIME AIME

THE meeting of the Petroleum Division at Houston, Oct. 10-12-headquarters, Rice Hotel-was preeminently a technological success. Two hundred and twenty-five attended the Thursday morning session and approximately 200 attended the sessions on Thursday and Friday afternoons and Saturday morning. Harry Power, Chairman of the Division, in his opening remarks, credited Paul Weaver and M. Albertson, respectively chairman and vice-chairman of the local committee, with working long and prodigiously in organizing the program. The theme of the initial session was indicated by Mr. Albertson in a statement relative to the estimation of developed petroleum reserves. He said that the problem of securing more accurate estimates of developed petroleum reserves existed prior to curtailment of production. With curtailment, however, the problem became an acute one. Mr. Albertson gave some of the more important reasons for this situation. Since the decline-curve method became inapplicable, the volumetric method has become the chief one used. It depends on the factors of productive formation volume, porosity, saturation, and recovery. He briefly discussed the factors necessary for application of the volumetric method. P. P. Gregory discussed the estimation of petroleum reserves in prorated lime¬stone fields (see his paper in the October

Jan 1, 1935

By Ralph W. Smith

DEVELOPMENT of the lime industry- in Ste. Genevieve County began in a crude way in 1840. According to information furnished by the Missouri Bureau of Geology, in the early days small vertical kilns built of stone were used, and wood was the fuel. Modern development began in 1904 when one company introduced steel shells lined with firebrick. Within a few years two more companies erected similar plants, and in 1925 a fourth company began operations. Thus there are today four lime companies at Ste. Genevieve, all operating at high capacity and with a gradually increasing production. GEOLOGY The limestone of Ste. Genevieve County, which has the chemical composition and purity required for lime burning, is the upper 80 or 90 ft. of Spergen formation. The Missouri Bureau of Geology, in its geological map of Ste. Genevieve County, gives the Spergen formation a total thickness of 160 ft., but only the upper portion is pure enough for lime burning, with an average raw-stone analysis of 98.7 per cent CaC03; 0.35 Si02; 0.3 R203; 0.35 MgCO3; 0.3 S03. The Spergen, one member of the Meramac group, Iowa series, of the Mississippian system, underlies an area approximately 12 miles long north and south, by 5 miles wide east and west (Fig. 1) in Ste. Genevieve County. The entire eastern two-thirds of Ste. Genevieve County is sedimentary, the formations dipping gently toward the east on an average grade of about 4 per cent, or 2 ½ º. Thus the outcrops of the various sedimentaries run approximately north and south. A line running west from Ste. Genevieve crosses the outcrops of the sedimentaries, ranging from the top of the Mississippian to the Ozarkian geological system in a space of 12 miles. Thus with the gentle dip of 2 ½ º the 160-ft. thickness of the Spergen formation stretches out in its outcrop so that it is approximately one mile

Jan 1, 1938

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

Oct. 8-13, 1917 The St. Louis Meeting of the Institute will be held Oct. 8-13, 1.917. Various committees are being organized to perfect the arrangements for the meeting. A number of excellent technical papers have already been secured end an attractive series of excursions has been outlined. The following is the outline plan for the meeting. More detailed announcements will be made as the plans mature. MONDAY, OCT. 8 Morning: Registration and Technical Session. Afternoon: Boat ride to Herculaneum, Mo., to visit smelter. and Evening: Dinner on boat and social evening.

Jan 4, 1917

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott's extension of Hildebrand's method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965

By L. C. Brown, E. B. Hawbolt

The formation of grain boundary precipitates has been studied in Ag-5.64 wt pcl Al alloys at 688°C. Large-grain specinzerzs were used and the boundary misorientation measured by X-ray diffraction. At low-angle grain boundrrries Primary sideplates form. u)hile abore a 17-deg misorientation lenticular precipitates predominate. Growth of the lenticular precipitates was studied on individual grain boundaries using a statistical technique. The thickening and lengthening rates appeared to be independent of &apos;pain boundary misorientation, indicating that grain boundary diffusion was not significant in this system. The precipitates grew urith constant shape, with both the length and thickness increasing parabolically with time. The parabolic lengthening rates were unexpected since previous theory and experimerztal results had indicated linear growth. By approximating the shape of the precipitate to that of an oblate spheroid grouling with constant shape an equivalent diffusion coefficienl was calculated. The zlalue obtained was in good agreement with nleasurements obtained fron, diffusiorz couples. IF a single-phase alloy is heated or cooled to a temperature such that the phase becomes supersaturated, there is a tendency for a second phase to precipitate from it in order to remove the supersaturation. Precipitation takes place initially on grain boundaries due to preferred heterogeneous nucleation, but subsequently Widmans kitten plates may form in the grain interiors if the grain size and supersaturation are sufficient. The type of grain boundary precipitate formed depends on the nature of the boundary. Aaronson1 and clark2 have shown that grain boundary misorientation can be characterized by the simple parameter R, where and X, Y, and Z represent the minimum rotations about three orthogonal axes required to bring the two lattices forming the grain boundary into coincidence. The maximum value for R is 60 deg. In using this parameter the orientation of the grain boundary itself is, of course, neglected. However it was found in both Fe-si3 and A1-Ag2 that the precipitate shape depended only on the parameter R. Clark found that the vast majority of precipitates formed were allo-triomorphs— lens-shaped precipitates that grew along the grain boundaries. At low-angle boundaries, however, (R < 15 deg) Widmanstatten sideplates nucleated at the grain boundaries and grew into the adjacent grains. It has been reported that the rate of growth of grain boundary precipitates is controlled by diffusion within the supersaturated phase.&apos; The theories which have been developed for growth rates have assumed the diffusion coefficient constant over the composition range of the supersaturated phase. This is a fairly good approximation if the composition range involved is not large. Thickening rates have been calculated using the theory developed by Zener4 and by Frank5 for the growth of planar precipitates. A parabolic growth law

Jan 1, 1968

By B. D. Lichter

The lattice parameters of zirconium and zirconium-oxygen solid solutions (hcp) were determined from measurements of back-reflection X-ray photograms obtained at 29°C using a symmetrical focussing camera. The following linear equations between parameters (c,a) in angstrom units (10-8 cm) and atom ratio (m) of oxygen to zirconium were obtained: c = 5.14764 + 0.2077m a =3.23168 + 0.1099m. The linear equations given are valid over the range 0 to 5 at. Pct 0. The accuracy of individual parameter measurements approaches the limiting accuracy determined by the spectral broadening of the incident characteristic radiation, and exceeds the accuracy of previously reported values. THE present work was undertaken in order to determine the lattice parameters of zirconium-oxygen solid solutions with an accuracy that allows quantitative determination of oxygen in zirconium. The results indicate that this is possible if very careful measurements are made, since the parameter change is only a few hundredths of a percent per at. pct 0.1, 2 In the present investigation the desired accuracy was achieved with large-grained samples using a back-reflection focussing camera and maintaining good temperature control during exposure. In addition a digital computer was used for calculation of the parameters by means of an analytical extrapolation.37 Suitable diffraction photograms were obtained from large-grained samples by using a modification of the technique described by Graf and Monteil.5 This consists of simultaneous rotation and oscillation of the specimen about two mutually perpendicular axes during exposure. Whereas, normally the upper limit of grain size is about 50 µ for useable diffraction photograms, this technique allows extending the upper limit of grain-size to exposure of a single crystal. EXPERIMENTAL Preparation of Alloys for X-ray Diffraction—Zir-conium, designated as hafnium-free, Westinghouse "Grade 1," was swaged from l/2-in.-diam crystal bar to 3/8-in.-diam rods. Substantially all of the hydrogen was removed from the zirconium by annealing at 1200°C in a high dynamic vacuum. The rods were then swaged to 0.2 in. diam without intermediate annealing, and 2 in. lengths were cut for alloying with oxygen. Samples for chemical analysis were taken from portions of the rods between each 2 in. length. Chemical analysis of the dehydroge-nated zirconium is given in Table I. Commercial tank oxygen (99.5 pct 0) was condensed in a liquid nitrogen-cooled trap, and part of the condensate was slowly reevaporated into 5-liter storage flasks. Nitrogen remained as a reactive impurity, and the calculated maximum increase in nitrogen content after a 5 at. pct 0 addition to zirconium was 50 ppm by weight. However, chemical analyses of several of the prepared alloys indicated that the maximum increase in nitrogen content was 10 ppm. The storage flasks, a Sieverts-type gas burette and manometer, and associated traps, pumps, and pressure gauges were connected through a glass high-vacuum manifold to comprise the gas addition system. A fused silica tube, connected to the mani-

Jan 1, 1961

By F. H. Spedding

From thermal, metallographic, X-ray, dilatometric, and electrical resistance data a Phase diagram is proposed for the La-C system. TWO compounds are formed, body-centered-cubic Laz C, having a large range of solid solubility, and body -centered-tetrago-nal Lac2 . The former melts incongruently at 1415°C, and at 25OC it has an electrical resistivity about two and one-half times that of bure lanthanum. The latter melts congruently at 2356°C and at room temperature has an electrical resistivity about equal to that of bure lanthanum. The addition of carbon to La lowers the melting Point of La about 115&apos; C, raises the higher (B-Y) transfomzation about 10" C and appears to have no effect on the lower ( a-0) transformation. The addition of carbon appears to lower the oxygen content in the metal and improve the machinability; however, the tendency to oxidize is increased. Two eutectics are formed in the system. The first occurs at 2.2 pct C and melts at 806" C, while the second occurs between Lac2 and C with a melting point of2271"C. PETTERSSON,~ in 1895, was the first to prepare lanthanum dicarbide by heating the oxide with carbon in an electric furnace. He showed that this yellow, crystalline but brittle carbide had a formula corresponding to LaCz and that it reacted with water with the evolution of hydrogen and hydrocarbons and the formation of the hydrated oxide. Von Stackelberg&apos;s investigation of the crystal structure of the MCz carbides showed that the lanthanum dicarbide is of the tetragonal calcium dicarbide-type structure. He found the lattice parameters were a = 3.92 and c = 6.56.* Bredig,&apos; using X-ray methods, showed that the room-temperature form of lanthanum dicarbide is stable up to 1750 °C and that above this temperature it transformsoto a face-centered-cubic structure, a = 6.0 ± O.lA, probably of the pyrite, FeSzstruc- typ? The reported discovery of two new cerium carbides, suggested that a corresponding face-centered-cubic lanthanum monocarbide and a body-centered-cubic lanthanum sesquicarbide might exist. This paper describes work on the lanthanum-carbon system which is part of a study of the rare earth metals and their alloys now in progress in this laboratory. EXPERIMENTAL PROCEDURE Source of Materials—The lanthanum metal was prepared at the Ames Laboratory by metal1o;hermic reduction of the fluoride with calcium metal. The results of spectrographic and chemical analysis indicated the presence of 0.01 pct Y, Al, Cu, Fe, and Si; 0.02 pct Ca and Mg; 230 ppm C; and 115 ppm N. The carbon used was of two types: 1) "National Special Graphite Spectroscopic Electrodes," and

Jan 1, 1960

By E. A. Gulbransen, W. S. Wysong, K. Andrew

INTRODUCTION THE reaction of carbon in solid solution in a metal with the surface oxide film on many metals may be inferred from thermodynamic calculations for high vacua and high temperature conditions. Holm1 has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. Considerable work has been described in the literature on the decarburization reaction. Several general references may be noted.2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides 0n strips of various types of chrome-nickel alloys. Some of the early experiments on the behavior of 13 pct chrome-iron in vacua of the order of 5 X 106 mm and at a temperature of 600°C have been reported.5 These experiments showed a slow reaction with the residual oxygen or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600°C pure enough to reduce Cr203 formed on the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome iron and Nichrome V has been investigated in the thin film range by Gulbransen, Phelps and Hickman,6 and shown to be Cr203. It was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pct nickel and 20 pct chromium was heated to 850°C in a high vacuum, the specimen&apos; lost weight. The rate of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. TYPE REACTIONS Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature, of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type. They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: [I. Metal • (gas) ;--* metal + gas - degassing of the metal 2. xM(s) + y ½ 02(g) tom- M.0„ (s) – oxidation]

Jan 1, 1948