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By F. F. Sharpless

ARRIVING at Davis Junction, after leaving Portland, we expected to wait for an hour and a half, but found the superintendent of motive power of the Southern Pacific, Mr. Williams, waiting for us with a car, and were immediately taken aboard this and whisked off to Sacramento. After dinner, we were taken to the railroad shops to see their work in reclaiming scrap steel. We saw them draw off the slag from the electric furnace, and later make a casting. At about 11 o'clock, we took the train for Reno. A delegation of the Nevada Section, with Mr. Kirchen and Mr. Rives at its head, met us at the station. Immediately after breakfast, we started for the property of the Comstock Mines Co., where General Bulkeley Wells was to be our host. We had a de-lightful ride out to the mines and through the old city of Virginia, or through what was left of that old city, reaching General Wells' camp at about 10:30. This contains the newest thing in cyanidation and a remarkably fine iron and concrete mill building. After a trip underground, we were called to luncheon, where about 250 sat down. The afternoon was spent in the mill, and we were taken to Gold Hill, which is a part of Virginia City, for dinner, again as the guests of General Wells, who made a consummate toastmaster. Governor Emmet Boyle was the first speaker; he was followed by President Dwight, and then came President William Sproule of the Southern Pacific. A song, "The Engineer," was followed by Senator Key Pittman, Professor Jones of the State University, Mayor Stuart of Reno, and ex-Senator Charles Hend-erson. The president of the Western Pacific and the president of the Pacific Coast Line were there, also many notable operators of Nevada and California.

Jan 11, 1922

By Meredith Johnson

THE year 1924 saw little change in the production of oil and gas it either Pennsylvania or New York. In the early months of the year the price of Pennsylvania crude oil, $4.00 to $4.50 a barrel, was sufficiently high to cause operators to lay plans for rather extensive drilling opera-tions. But when, in August, the price dropped to $2.85 a barrel, there was no inducement for new work and drilling was curtailed. In spite of the curtailment, however, the combined production of the two states for the year showed a slight increase over 1923, the production being 8;859,000 bbl. in 1923, and 8,901,000 bbl.1 in 1924. The increased production was due entirely to. the continued development of flooding operations in the Bradford field, all other oilfields showing a decline for the year. TABLE 1. Production of Crude Oil in Pennsylvania and New York for the Last Ten Years a Production, Barrels Production, Barrels Year Year Pennsylvania I New York Pennsylvania I New York 1915 7,838,000 888,000 1920- 7,438,000 906,000 1916 7,593,000 874,000 1921 7,418,000 988,000 1917 7,733,000 880,000 1922 7,425,000 1;000,000 1918 7,408,000 809,000 1923 7,609,000 1,250,000 1919 8,137,000 851,000 1924 7,535,0006 1;366,0006 a U. S. Geological Survey figures. b Estimated. Much of the drilling in the southwestern part of Pennsylvania was done in search of gas. Natural gas in Pennsylvania is fast being recognized at its true worth and the increased prices allowed 'the gas companies for their product induced quite a bit of new work. The relative importance of natural gas compared with manufactured gas is shown in Table 2.2

Jan 3, 1925

By O. U. Bradley

The methods of handling the oil output of the Mid-Continent fields are not unlike those practised in other oil fields of the United States, and it is not expected that this paper will present any entirely novel ideas. Some features of the practice of handling this oil may be of interest, however. Wooden Gaging Tanks Practically all of the oil sold to pipe line? and other purchasing agencies throughout the Mid-Continent field is gaged from wooden tanks. Steel gaging tanks are slowly coming into use, and are preferable in many ways—leakage and evaporation are reduced, and the strapping and recalculation of capacities are unnecessary. The wooden tanks are slightly coned to facilitate tightening the hoops. The sizes in common use are 250, 500, 800 and 1600 bbl. The number and the capacity of the gaging tanks upon any producing oil property depend upon its production, and the facilities for disposing of the output. The 1600-bbl. size was the most common in the Cushing field, particularly during the period of flush production. The tanks are distributed over the leased premises in groups of two, three, and four tanks each, and these are filled from flow tanks, or through direct pipe connections with the heads of the wells. Flow tanks are merely temporary reservoirs to facilitate the transfer of oil from the wells to the gaging tanks. They diminish fire risk, and are considered indispensable on small producing properties where water is pumped with the oil, as they permit the refuse and water to 'settle out before the production is run to the gaging tanks. strapping and Calculations After a gaging tank has been strapped (measured) and its contents computed, a deduction of 3 per cent. is made from its computed volume. The strapping of a tank requires four steps: (1) The outer circumferences

Jan 1, 1920

By Fred T. Greene

(San Francisco Meeting, September, 1915) MOST of. the recent discussion of the mineral land law published in the Transactions is in the abstract-an exception being Mr. Goodale's paper, The Apex Law in the Drumlummon Controversy,1 which illustrates in concrete instances many of the practical disadvantages of what Dr. Raymond has. called "The Law of the Apex." The present paper, it is hoped, may serve a similar purpose, emphasizing the necessity for a change in our mining laws, and bringing home to mining engineers some of the defects and dangers of our present code. There are many storm centers of "apex litigation" in the Rocky Mountains; and not the least of them is the Wardner camp, where such litigation has been almost continuous since 1892, and the end is not yet. In their decisions, the courts have accepted the claims of the litigants that the " Wardner vein" is a broad zone varying from 250 to 500 ft. in width at the surface. This is the simplest theory which could have been advanced, and probably decreased, rather than augmented, the number of contests; in fact, every one of the claim owners seemed to feel that the greatest advantage would accrue to him if this theory were adhered to. The dominant structural feature of the Wardner vein is a persistent fault, striking N. 40° W., clipping about 40° to the southwest and called the "Wardner foot wall." Fig. 1 is a composite of two adjacent cross-sections of the vein and is a fair representation of the relative size and shape of the orebodies and their relation to the "Wardner foot wall." The country rock is a comparatively thin-bedded sericitic quartzite which has an average strike of N. 80° W. and clips at high angles to the north and south.

Jan 5, 1915

By Darrel W. Hansen

Morrow Point Dam and Power Plant are principal features of the Bureau of Reclamation's Curecanti Unit of the Colorado River Storage Project. They are under construction on the Gunnison River 20 miles east of Montrose, Colo. Johnson-MK is the prime contractor, and represents a joint venture of Al Johnson Construction Co., Minneapolis, Minn., and Morrison-Knudsen Co., Inc., Boise, Idaho. The power plant will be housed in an underground chamber in the left abutment, approximately 250 ft behind the original canyon wall. The chamber is 206 ft long and 57 ft wide. The distance from the foundation to the spring line of the roof arch varies from 51 ft in the service bay to 120 ft in the control bay. The roof arch has a rise of 16 ft. The longitudinal center line of the chamber is orientated east-west with the draft tubes discharging nearly due north. Access to the power plant chamber was possible through the cable tunnel, access tunnel, two draft tube tunnels, two penstock tunnels, exploratory tunnel, which became the ventilation tunnel, or the grouting and drainage tunnel leading to the dam. (See Fig. 1.) The shortest and fastest access was through the cable and access tunnels, and the contractor drove these two tunnels simultaneously. The cable tunnel and cable gallery excavation exposed a transverse section, at the west end of the chamber, that was 15 ft wide and extended from the crown to 5 ft below spring line. It was here that arch excavation began. The first 34 ft of advance along the arch was driven on three headings, and the muck was removed through the cable tunnel. Meanwhile, the access tunnel was completed, and a raise was driven from its crown to intersect the advancing arch excavation near the longitudinal centerline

Jan 1, 1968

By S. Zador, C. B. Alcock, K. Sudo

Measurements have been made of the standard free enevgies of formation of the sulfates of cobalt, Cupric copper, nickel, and ferric iron in the temperature range of 750° to 950°C. Dynamic gas-solid techniques have been employed in which oxide-sulfate and basic sulfate mixtures were placed in a stream of gas of controlled SO3 potentials. Thermal analysis and thermogvavimetry were used as detection methods, and it was found THE formation of sulfates during the roasting of sulfide ores is now considered to arise in many cases from the interaction of sulfur trioxide in the gas and the metal oxide which is formed on the sulfide as a first step.' As a preliminary to the investigation of the kinetics of sulfate formation during roasting, measurements have been made of equilibria from which the free energies of formation of cobalt, copper, nickel, and iron sulfates can be that the range of temperatures which could be investigated and the choice of method was largely controlled by the kinetics of these gas-solid reactions. The results are compared with previous results obtained from static measurements with which they agree quite well, and calculations have been made employing themal data to interrelate the present results with those for other sulfates. calculated. The method used has been to expose the solid sulfate (or basic sulfate) to a controlled flowing gas mixture of SO,, 02, and SOs and to observe the temperature of decomposition. The onset of decomposition was detected by thermal analysis or thermogravimetry. EXPERIMENTAL METHODS The thermal-analysis method was similar to that employed by Dewing and Richardson.' The sulfate was dehydrated at 250°C in air, and placed in a small alumina crucible which was held by a quartz ring in the hot zone of a horizontal furnace. The reaction tube of this furnace was made of mullite.

Jan 1, 1965

By A. E. Harnsberger

IT is obvious that details such as the physical and chemical properties and methods of heat-treating of the materials mentioned must be omitted in a paper on the subject of materials used in oil-refinery pumps1. Only sufficient identification is given to enable the reader to find additional information from already published data. Also, the subject covers many operating conditions, but only the most important services can be discussed here. To the oil refiner, the pumping equipment is of vital interest. Practically every refinery operation, from the charging of crude oil to a distillation unit to the shipping of refined products, involves some form of pumping machinery. Intermediate refining stages involve a great variety of pumping machinery to carry out successfully the aims of the refinery technologist. Temperatures at which oils are handled vary from -50° F. to 900° F. Pressure may vary from subatmospheric to 2000 lb. per sq. inch. The selection of the proper materials involves a careful consideration of the conditions under which the particular pump must operate. The four, most important considerations are temperature, pressure, corrosion, and abrasion or wear. Consideration of temperature may be divided into three parts: (1) extremely low temperatures of the order of -50° F.; (2) temperatures at atmospheric or slightly above; .(3) temperatures from 200° to 900° F. Pressures fall into two groups: (1) pressures reached by ordinary trade pumps of the order of. 200 lb. per sq. in., (2) extreme pressure conditions involving pressures as high as 2000 lb. Noncorrosive and corrosive oils can be treated differently. Under the latter falls corrosion in the presence of water, which will occur up to 250° F. The second type of corrosion occurs in high-temperature pumping equipment, with temperatures from 450° to 900° F., largely caused by sulfur compounds. There are also other corrosive conditions met with

Jan 1, 1935

By Kandalla Ravindranath, C. C. Patel

Studies of the adsorption of dialkyldithiocarbamates at the surfaces of galena and sphalerite have shown that characteristic contact angles are obtained at galena surfaces in the 7-10 pH range, whereas lower angles are obtained at unactivated sphalerite surfaces even at pH 71 Further, the angles at sphalerite surfaces progressively decrease with increase in pH. However, when sphalerite is activated with cupric sulfate, characteristic contact angles are obtained at pH 7 and beyond. This shows that galena and sphalerite can be selectively floated with dithiocarbamate collectors at pH 7 and beyond. Experimental Materials Ore: The lead-zinc ore for the present study was obtained through the courtesy of the Geological Survey of India from Dariba, Udaipur, Rajasthan, India. The average ore analyzed 15.5% lead, 11.6% zinc, 6.7% iron, 15.6% sulfur and 36.6% acid insolubles. The ore was crushed in a Denver laboratory rod mill and sieved in a Denver automatic sieve shaker to obtain a -200- to +250-mesh (Tyler standard) fraction. This particular size was chosen because it was conducive to good liberation of sulfide minerals, both from one another and from gangue minerals. Collectors: Dimethyl, diethyl, diisopropyl and diisobutyl dithiocarbamates were prepared and purified by the methods described by Klopping and Van der Kerk.2 A freshly prepared 0.03% dithiocarbamate solution in distilled water was used for flotation studies. Frother: A 0.03% solution of pine oil in ethyl alcohol was employed. Activator: 7.3 g of cupric sulfate pentahydrate were dissolved in 1 1 of water and used for the activation of sphalerite. Depressant: 16.0 g of zinc sulfate heptahydrate were dissolved in 1 1 of water and used for the depression of sphalerite.

Jan 1, 1972

By H. E. Lee, P. C. Feddersen

Blast-fuRnace operation at the Bunker Hill smelter deviates somewhat from common practice. Under existing conditions it is economical to operate the furnaces at "forced" capacity. The furnace feed consists chiefly of sinter and averages close to 50 per cent lead. Experience in smelting such material favors a low charge column attended by smaller proportions of coke and a low blast pressure. Under such conditions the gain in furnace tonnage greatly overbalances the somewhat higher slag losses and increased percentage of material fumed Furnace Charge The ingredients for the blast-furnace feed are stored in a group of 24 charge bins (3600 cu. ft. capacity). Each bin has two discharge chutes. Beneath each chute is a steel weighing hopper, suspended from a Fairbanks scale. The several hoppers are kept filled with the exact amount of material required to complete a furnace charge. The weighed material is discharged into a standard-gauge, bottom-dump charge car containing two compartments, each of which holds a complete charge (approximately 1½ tons). It is hauled to the blast furnace by a 44011 electric trolley locomotive. The proportionate parts of the various constituents of a representative blast-furnace charge are shown in Table 1. Table 1.—Representative Blast-furnace Charge at Bunker Hill Smelter Material Pounds Sinter.................................................. 2500 Limerock............................................... 0- 50 Coke................................................. 250-300 Scrap iron.............................................. 0-25 Settler skulls.......................................... 75 Undried zinc-plant residue................................ 0-200 Siliceous ore............................................ 25 Baghouse dust.......................................... 0-50 By-product slag......................................... 100 A variable stock tonnage of zinc-plant residue and return by-products results in fluctuations in the percentages of these materials in the blastfurnace feed. Accompanying such variations are corresponding increases or decreases in the amounts of coke, limerock and scrap iron necessary to obtain good furnace operation and adequate reduction.

Jan 1, 1937

By G. B. Pryde

IN laying out a new mine, provision should be made for the ultimate recovery of as much coal in any given bed as is consistent with safety and economic mining. Though each mining district, if not each individual mine, has problems that make the adoption of any hard and fast rule impossible, certain basic principles are adapted to practically all conditions. One of the most vital is the provision for barrier pillars of ample dimensions to protect all haulage and permanent airways during the life of the property. Where conditions permit, room or butt entries should be driven on the strike or slightly to the raise and rooms turned at right angles to said entries. The width of rooms and room pillars is governed by conditions prevailing in the mines under consideration. A safe rule is: In advancing, extract not more than 25 to 35 per cent. of the entire seam; in exceptionally thick seams, considerably less than 25 per cent. should be taken. Rooms usually vary in length from 250 to 350 ft. (76 to 106 m.) with a barrier pillar of not less than 80 ft. between the last crosscut in rooms, and entry and room crosscuts should be driven on sights; room crosscuts should be driven at right angles to the direction of the rooms. In mines under excessively heavy cover or where roof conditions are bad, rooms should be driven narrow and a barrier pillar left at every fifth to tenth room. This barrier should be of such dimensions that one or more rooms, with pillars of usual dimensions, may be turned through it when the barrier is no longer required. Two of the advantages of such a barrier are the protection of the panel against peaking of roof load during pillar extraction and the easy closing of the entry in case of fire.

Jan 2, 1921

By Milnor Roberts

The Nicola Valley coal-field is small, but it seems likely to become important because of its commanding position in a rich region that is developing rapidly. Bituminous coking-coal in workable quantity has not been found at any other point between the Crow's Nest Pass region, about 400 miles to the east, and Vancouver island, 250 miles westward. The Canadian Pacific railway reached the Nicola valley two years ago ; two other lines, the Canadian Northern and the Great Northern, are building towards the valley. The vast region between the Rocky mountains and the Pacific coast, extending northward for several hundred miles from the international boundary, which has been the scene of extensive mining- and smelting-operations for many years, is filling up with settlers, who are attracted by the wealth of minerals and timber, the rich soil of the valleys, and the fine climate. The Nicola river, flowing westward through the valley of that name in the Yale district, discharges into the Thompson river, which is the eastern branch of the Fraser. The transcontinental line of the Canadian Pacific railway crosses the mouth of the Nicola river at Spence's bridge, 178 miles from Vancouver. From Spence's bridge the Nicola branch line ascends the valley for 40 miles to Merritt, the coal-center, and continues 7 miles farther to the town of Nicola. Thus the haul from the mines at an elevatioiz of 2,000 ft. to salt water is 218 miles down river-grades. The Nicola branch will be continued about 150 miles farther eastward to Penticton, where it will connect with an extension of the line through the rich Kootenay and Boundary districts. The Canadian government has granted a subsidy of $6,000 per mile, to which the provincial government is planning to add $5,000 per mile, to assist in the construction of the Nicola extension. Upon the

Jan 1, 1910

By J. M. Hartman

ONE of the most important subjects to the blast-furnace engineer is a thorough knowledge of the conditions affecting the temperature in the different portions of the furnace. All efforts to decrease the consumption of fuel and improve the working of the furnace must be based upon it, and I may, therefore, be permitted to place before you the results of my observations, and detail the conclusions to which they have led me. Tracing the thermic conditions from below upwards we have at the bottom of a blast furnace making No. 3 iron a temperature of 2900' F., which increases slightly to a point a little below the tuyeres. In the immediate vicinity of the tuyeres the temperature is somewhat lower, owing to the entering blast; but a short distance above the tuyeres, where all the oxygen of the blast has been converted into carbonic acid, the highest temperature in the furnace must be attained. This carbonic acid is, however, almost as soon as formed, converted by the glowing coal into carbonic oxide, a process which absorb, heat, reduces the temperature, and provides the active agent for the reduction of the iron ores. In its ascent the hot carbonic oxide gradually parts with its heat, first melting the descending iron and earthy materials, which drop down to the hearth of the furnace. The limit of this zone of fusion is rather sharply defined, and the temperature above this zone suddenly decreases. In its further ascent the hot gas drives off the carbonic acid from the limestone, which causes a further absorption of heat, and finally the gas escapes at the top, at a ternperature of about 250' F. if the furnace is working well. These changes of temperature I have attempted to represent graphically,

Jan 1, 1880

By J. M. Hartman

ONE of the most important subjects to the blast-furnace engineer is a thorough knowledge of the conditions affecting the temperature in the different portions of the furnace. All efforts to decrease the consumption of fuel and improve the working of the furnace must be based upon it, and I may, therefore, be permitted to place before you the results of my observations, and detail the conclusions to which they have led me. Tracing the thermic conditions from below upwards we have at the bottom of a blast furnace making No. 3 iron a temperature of 2900° F., which increases slightly to a point a little below the tuyeres. In the immediate vicinity of the tuyeres the temperature is somewhat lower, owing to the entering blast ; but a short distance above the tuyeres, where all the oxygen of the blast has been converted into carbonic acid, the highest temperature in the furnace must be attained. This carbonic acid is, however, almost as soon as formed, converted by the glowing coal into carbonic oxide, a process which absorbs heat, reduces the temperature, and provides the active agent for the reduction of the iron ores. In its ascent the hot carbonic oxide gradually parts with its heat, first melting the descending iron and earthy materials, which drop down to the hearth of the furnace. The limit of this zone of fusion is rather sharply defined, and the temperature above this zone suddenly decreases. In its further ascent the hot gas drives off the carbonic acid from the limestone, which causes a further absorption of heat, and finally the gas escapes at the top, at a temperature of about 250° F. if the furnace is working well. These changes of temperature 1 have attempted to represent graphically,

Jan 1, 1880

I. The Property. The Homestake Mining Co. has acquired through consolida tion the ground and equipment of the Father De Smet Con solidated Gold-Mining Co., the Deadwood-Terra Mining Go., the Caledonia Gold-Mining Co. and the Highland Mining Co., at and near Lead, Lawrence county, South Dakota, in the northern portion of the Black Hills. The company owns or controls 250 claims, comprising 2,616 acres and covering about 8,000 ft. along the strike of the lode. At the surface there are several veins, of which three have united in depth, where the main vein ranges from 300 to 500 ft. in width. The 1,100-ft. level is the lowest at present. The rock of both walls is, so far as known at present, carboniferous alate, and the country is penetrated by a system of porphyry dikes, and in some places capped with porphyry. The output of the company up to January, 1903, has been, approximately, $70,000,000. II. The Ore. The oxidized, open-cut ore is nearly all treated in the three mills on the northern part of the property, which are as follows : The Mineral Point (formerly the De Smet), of 100 stamps, the Monroe (formerly Caledonia), of 100 stamps, and the Pocahon tas (formerly the Deadwood-Terra), of 160 stamps. A cyanide plant, to treat the leachable portion of the tailings from these North End mills, has recently been installed and put into oper ation at Gayville, or Blacktail as it is now known. The Homestake lower-level ore, which comprises the greater part of that being milled at Lead, may be described as a horn blende, garnetiferous schist or slate, which has been crushed and infiltrated with free silica and pyrites, the latter being

Jan 1, 1904

By Lo-Ching Chang, Kenneth M. Goldman

INTRODUCTION THE kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was simple. A graphite crucible 1 5/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an induction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature [ ] for 3-5 min., after which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 min. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the temperature of the furnace in 1 to 1 1/ 2 min. Slag

Jan 1, 1948

By Victor G. Hills

CONTRARY to what seems to be the general impression, the island of Cyprus was not named for the metal copper, but the reverse was the case. The origin of the name is entirely lost. The ancient city Kition, the birthplace of Zeno, is supposed to be the same as Kittim mentioned in Gen. x, 4; Jeremiah ii, 10 and Ezekiel xxvii, 6, and Josephus states that this name seems to have been applied to the city and also to the island itself. Cyprus is 50 miles off the coast of Asia Minor. The mountains on the mainland are plainly visible across the sea from where I write six miles from the shore of Morphou bay. It is 200 miles from Joppa the port of Jerusalem, and 250 from Port Said. The shape of the island is like a lizard, the tail pointing directly toward the old city of Antioch near the northeastern corner of the Mediterranean. The island was once heavily timbered. Among the great trees the cedars were said to even excel the famous cedars of Lebanon. The Odyssey refers to it as the "sweet smelling island" and makes other references. But the continual wars of every race and age completely stripped it of its timber, and for centuries it has been woefully barren. There are two ranges of mountains. One borders the north coast and runs out in a slim rocky ridge forming the "tail." The other occupies the southwestern part of the island, the highest point being Mt. Troodes 6600 ft. high, sometimes called Mt. Olympus. Whether or not it be the Mt. Olympus, anyway right around there the ancient gods and godesses frequently "started things." These peaks are in plain sight 10 miles south from where I live.

Jan 1, 1926

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.' The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;' and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.' The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.' who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967