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By Galen Clevenger

TELLURIUM has had the rare and unpleasant distinction of having fewer uses than any of the other common elements; indeed, it has had no regular or important uses. It is not only a useless and disagreeable element, but to the metallurgist it has been a nightmare. The interference of tellurium with the recovery of gold and silver from certain ores, as well as the difficulties it occasions in the electrolytic refining of copper, lead, and silver, are too well known to require enumeration here. In fact, the potential producers of the element have been quite willing to throw the crude products from which it might be recovered into the sewer. First isolated from a gold ore in 1782, although remaining a practically unknown element to the general public, it has long been a guiding star to the Western prospector in his quest for the "golden fleece." On the burning sands of the desert, in the frigid North, and in the mountain fastnesses of the more temperate regions of this and other continents, he has endured all manner of hardships in his search for tellurides; for where he found indications of tellurium, there he expected also to find rich deposits of gold and silver. This peculiar superstition, that tellurium, associates itself in nature with the precious metals, is not with-out reason, for witness the fabulously rich gold tellu-ride deposits of Cripple Creek and Western Australia. Selenium, the sister element of tellurium, which it resembles in many of its properties, was first isolated in 1817. It is found in small amounts in certain native sulfur deposits, and in many copper and silver ores from all parts of the world. Until a few years ago, selenium, like tellurium, was practically useless. The, unusual property of having its electrical conductivity influenced by light has long been known. Selenium cells, which for many years have been a scientific curios-ity, in the future may come to be of more commercial importance, but this use could scarcely absorb any large amount of the element.

Jan 1, 1923

By J. O. Whiteley

IT is difficult to give a refining outline that may be followed for any and all combinations of the platinum metals; different combinations require different methods of attack. This paper does not pretend to go into all of the reactions of the metals of the platinum group, but will outline the commercial refining of platinum scrap. TYPICAL PLATINUM SCRAP As a concrete case, let us take 100 oz. of miscellaneous scrap, made up of jewelry scrap, dental scrap and laboratory ware. This lot will contain some platinum, palladium, iridium, ruthenium, rhodium, gold, silver and copper. The first problem is to get all of the metals in solution. If the scrap is principally platinum, palladium and gold, a treatment with aqua regia is the course to pursue; but if the scrap contains alloys high in iridium or ruthenium, aqua regia will act too slowly. In the case in hand, we are going to presume that we have scrap high in iridium and ruthenium, and proceed accordingly.

Jan 1, 1928

By R. F. Ashton, D. S. Thompson

In reporting results of precipitation hardening experiments, it is customary to include such conditions as solution heat-treatment temperature, specimen size, and quench medium as well as the aging time and temperature. One portion of thermal history that is often overlooked is the effect of the heating rate employed to achieve the aging temperature. It is the intent of this note to demonstrate the importance of the rate of heating to aging temperatures. This work was carried out on the aluminum alloy 7075 aged at 162oC, a temperature commonly used to obtain stress corrosion resistant tempers. A 2 in. thick plate of 7075 was quenched into 24°C water after solution heat-treatment for 2 hr at 470°C. Approximately 13 in. around the periphery of the plate was discarded to minimize quench rate variations, and the remainder was divided into 0.5 by 1.8 by 2.0 in. blocks which were held at room temperature, 24oC, for 4 days. This aging, or incubation period, at room temperature allowed a copious supply of GP-zones to form. Blocks were then heated at various rates to 162oC using the practices shown in Table I. Both single- and two-step aging practices were employed for each heating rate. The single step consisted of heating directly to temperature at the indicated rate while the two-stage practice included an interruption of heating for 7 hr at 107°C. In the case of the two-stage 100°C per min heating rate experiment, the specimens were returned to room temperature after 7 hr at 107°C where they were held for 16 hr be-fore finally heating at this rate to 162°C. This devia-tion in practice is not considered to be significant. Blocks were removed after various times at 162oC, and aging curves were determined from duplicate R. F. ASHTON and D. S. THOMPSON,Member AIME, are Senior Scientists, Metallurgical Research Division, Reynolds Metals Company, Richmond. Va. Manuscript submitted December 2. 1968. IMD Table I. Aging Practices Two-step Single-Step Heating Rate* Aging Aging Heating Method oC per Min A B Programmed Air Oven 0.23 * 0.01 C D Programmed Air Oven 0.93 ? 0.03 E F Air Oven at Temp -10 G H Oil Bath at Temp ˜100 *Heating rate was measured with a thermocouple at the center of a specimen. An average value between the starting temperature and 3°C below the aging temperature is reported for practices E-H. PRACTICES 70 — A B C E and G 50 - 2 4 6 810 20 40 60 HRS.AT 162°C Fig. 1—The influence of processing variables on 7075 aging curves. Fig. 2—7075 aged according to practice H (single-step aged, fast heating rate) for 3 hr. Magnification 100,000 times.

Jan 1, 1970

By C. P. Kempter, H. L. Brown

Recently Chang determined heat content values of tantalum monocarbide and tungsten monocarbide from 325" to985°Kand 326" to 912"K, respectively, and, using other published data, made certain solid-state calculations for these two compounds. Chang expressed his Cp values in units of cal per "g-atom alloy" OK. We consider this poor usage since l) tantalum monocarbide and tungsten monocarbide are not alloys, and 2) an atom of an alloy does not exist. However, one may convert his values to units of cal per mole OK by merely doubling them. For TaC he calculated a Nernst-Lindemann parameter of 9.07 x lo-' "g-atom per cal". We have refined the calculation of this parameter and have arrived at a much lower value. Rather than approximating the true coefficient of volume expansion, a,, as three times the true coefficient of linear expansion, a, we calculated u, from the TaCo.99, lattice expansion data of Fries and Wahman.38 At 25°C a, = 14.3 x 10s per OC. The molar volume was calculated to be 13.32 cu cm per mole at 25°C. From the lattice compression data of Champion and Drickamer~' for "TaC,.,," we determined the room-temperature compressibility to be 3.5 x 10-l3 sq cm per dyne by plotting l/Vo (aV/ap) vs applied pressure. (Since the lowest pressure at which Champion and Drickamer reported a relative volume was 20 kbars, one may calculate an approximate compressibility only. Chang calculated a compressibility of 3.175 x 10-l3 sq cm per dyne from the same data.) We also used twice Chang's value of Cp = 4.38 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated a Nernst-Lindemann parameter of 5.8 x 10-l4 mole per erg or 2.4 x lo- ' mole per cal, and a Cdil value of 2.3 x 10' ergs per mole OK. In the case of tungsten monocarbide no isothermal compressibility has been reported; however, one may calculate an approximate Nernst-Lindemann parameter by using the adiabatic compressibility reported by Brown, Armstrong, and Kempter." Using the WC lattice expansion data of Mauer and Bolz~l we calculated a, to be 12., x l0-' per OC. The molar volume was calculated to be 12.5 cu cm per mole. We used twice Chang's value of Cp = 4.18 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated an approximate Nernst-Lindemann parameter of 2 x lo-' mole per cal, which is much

Jan 1, 1969

By D. C. Buffum, L. D. Jaffee

QUANTITATIVE measurements of the temper brittleness of steel are made by comparing the difference between embrittled and unembrittled specimens in the temperature of transition from ductile to brittle fracture. Since hardness affects the transition temperature, a study of the combined effects of hardness and temper brittleness appeared desirable. In this investigation a commercial SAE 3140 steel, which has been reported on previously in temper brittleness studies,* was used. Blanks from this steel were austenitized for 1 hr at 900°C and water quenched. The blanks were then divided into six groups and further heat treated as follows: Group 1—tempered at 675°C for 4 hr and water quenched; Groups 2, 3, 4, and 5—tempered at 675", 650°, 625', and 600 °C respectively for 1 hr and water quenched; and Group 6—tempered at 500°C for y2 hr and water quenched. Each of these groups was divided into two parts; one part was tested without further heat treatment, and the other was embrittled for 48 hr at 500°C and water quenched. Tempering treatments between 500" and 600°C were avoided because of the rapid embrittlement occurring in that range for this steel. The heat-treated blanks were machined into standard V-notched Charpy bars. Each group was tested over a range of temperatures on a 217 ft-lb Charpy machine. The energies necessary to fracture the bars and the percentage fibrous fracture of each bar were recorded. The transition temperatures were obtained from a plot of the percentage fibrous fracture as a function of testing temperature. They were taken as the lowest point on these curves at which the fracture was 100 pct fibrous. The transition temperatures for both embrittled and unembrittled specimens are presented in Fig. 1 as function of the hardness. It will be noticed in this figure that the point for the unembrittled condition at 21 Rockwell C is out of line. These specimens were tempered for 4 hr at 675 °C and this point indicated that under isothermal conditions at this temperature, as is well known, embrittlement may develop fast enough to more than offset the effects of softening. From this data, it was concluded that the difference between transition temperatures for the embrittled and unembrittled conditions at any given hardness, within the range of Rockwell C 24 % to 32lh, is constant. It is also concluded that, within the hardness range studied, the transition temperatures for embrittled and unembrittled specimens rise in a parallel fashion with an increase in hardness. The authors wish to acknowledge the assistance of Frank Carr in this work.

Jan 1, 1952

By W. C. Ellis, E. S. Greiner

METALLIC titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arkel2 and Fast3 prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kroll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper: was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725°C5 it may be classed as a light metal since the specific gravity is 4.5 g per cc-1. The crystal structure is close-packed hexagonal from room temperature t0 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat8 electric resistance9 and thermoelectric force10 at temperatures near 890°C. It is reported11 that annealed titanium has a tensile strength 0f 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between - 200 and 1000°C have been determined. MATERIALS For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was lade from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at 1000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was lade from a rod of titanium, 0.19 in. in dial, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table I. Oxygen and nitrogen which were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1948

Engineers and masters of enterprise are waking fast to the realization that there is something more in the relations of employer and employee than mechanical output, which can be measured mathematically, and that the human side of service must receive greater consideration for the future. So much has been said and written on this subject that it has passed into a truism. Should not the same element, long neglected, be considered as of even greater importance than questions of "administration and membership, in the plans of engineering societies? Should mutual service and interest end with mere technical output by members and the rendering of care and management by officers? The world is recognizing, as never before, obligations for service to fellowmen clue from all, high or low, in rank or wealth. Our technical societies, organized for professional protection and advancement, are, insensibly to themselves, almost without conscious intent, widening their field of service to members and dealing heartily with questions broader than technique. Those who are doing such service find unconsciously more and more satisfaction in work so rendered. The growth of knowledge that comes to subaltern engineers or veterans by converse and contact with their fellows, working along and versed in the same subjects, brings interest and friendship. In this way are built some of the warmest friendships of life, coming as incidental and pleasurable result of meetings undertaken for other purposes. Should not the friendly purpose, the desire for service one to another, and es-

Jan 1, 1919

By C. F. Floe, M. Cohen, M. B. Bever, V. G. Paranjpe

NITROGEN is becoming recognized as one of the important elements in ferrous physical metallurgy. Several investigations indicate that nitrogen plays a significant part in such phenomena as strain aging and temper brittleness. Nitrogen is known to be a powerful austenite stabilizer and may be a useful alloying element in stainless steels. The hard-enability of steels has been found to be increased by nitrogen. The nitriding and carbonitriding pro- cesses are examples of successful industrial application of nitrogen in ferrous materials. For a complete understanding of the various roles played by nitrogen in ferrous metallurgy a knowledge of the phase relations in the binary iron-nitrogen system is essential. The literature contains a variety of iron-nitrogen phase diagrams. Those suggested by Fry, Sawyer,² Epstein and his coworkers,³,4 Lehrer,5 Eisenhut and Kaupp, and Hägg7,8 differ significantly from one another. Moreover, the most recent of these investigations dates back about twenty years. A re-determination of the entire diagram, therefore, appeared desirable. In addition to the published phase diagrams, investigations have been carried out on portions of the iron-nitrogen system. Bramley and Haywood determined the composition and temperature of the iron-iron nitride eutectoid. The maximum solubility of nitrogen in a iron was investigated by Portevin and Seferian10 and by Diikstra. 11 Several investigators have determined the crystal structure of the various iron-nitrogen phases. In fact, Eisenhut and Kaupp6 and Hägg7 based their entire phase diagrams on the results of such studies. Epstein' and Emmett12 reported lattice-parameter measurements on the E (hexagonal close-packed) phase. Osawa and Iwaisumi13 also studied the change in lattice parameters of the a, ? and E phases with nitrogen content. Brill" and Hägg7 showed that the y' phase has an ordered structure, and Hendricks and Kostingsl5 suggested a structural relation between the E and phases. In a recent investigation Jackl6 arefully studied the super-lattice reflections from the y' and phases. Experimental Procedure A large variety of experimental methods has been used by previous investigators in studying the iron-nitrogen system. These methods include thermal analysis, microscopic examination, X ray diffraction, magnetic measurements, dilatometric analysis and anelastic experiments. Thermal analysis is of low accuracy in determining changes in the solid state. This accuracy is further decreased for iron-nitrogen alloys since composition changes will occur during heating or cooling unless extreme care is taken to use a proper atmosphere. Metallographic methods are of small value . because homogeneous iron-nitrogen alloys of sufficient size can be produced only with great difficulty. The dilatometric method is open to the same objections as thermal analysis in that changes in composition may occur during heating and cooling. Lattice parameter measurements by X ray diffraction can be used satisfactorily for determining phase boundaries if cooling is fast enough to prevent structural changes. In view of the limitations of the various other techniques two methods only were adopted in this investigation, (1) X ray diffraction measurements, and (2) a controlled nitrogenizing method. The second method is an innovation for investigating the iron-nitrogen system, and will be described at length. Materials: All iron-nitrogen alloys were prepared from carbonyl iron powder of the analysis shown in table I. The average particle size was about 20

Jan 1, 1951

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period Mar. 10 to Apr. 10, 1915: Oscar Lachmund, Greenwood, B. C. Harvey B. Small, Mangaugue, Colombia. S. W. Ough, Pachuca, Mexico. M. F. Sayre, Schenectady, N. Y. B. W. Vallat, Detroit, Mich. James W. Hambleton, Parral, Mexico. Charles Mentzel, New York, N. I . Philip L. Gill, Woodmere, L. I., N. 1. M. K. Rodgers, San Francisco, Cal. John T. Fuller is President of the F. Shepherd Mining Co., operating at Rush Mountain, Ark.

Jan 5, 1915

By P. G. Carpenter, R. G. Nisle, F. W. Bubb

It is the purpose of this paper to describe an electrical computer which has been constructed to solve the equations for vapor-liquid equilibrium in multi-component systems. The instrument consists of seven component-computing units each with proper indicating means and power supplies. Each unit is a resistance network with a voltage matching servomechanism, and each provides an output voltage proportional to the mol-fractions for vapor and liquid phases. These voltages are summed and matched with a reference voltage to provide the solutions. Any reasonable number of such units may be put together to make a computer. The theory and operation of the computer is discussed. A number of applications and examples of computer results are given. The computer yields the over-all vapor or liquid fraction to a probable error of 0.002. An interpolation method is described which reduces the probable error to 0.0002. INTRODUCTION The process known as Flash Vaporization may be described as follows: A mixture of known composition of relatively volatile components is allowed to come to thermodynamic equilibrium at some given temperature and pressure by any path whatsoever. In general, a vapor and a liquid phase will be present at equilbrium. The problem is to determine the fractions of the mixture in the vapor and liquid phases, and to determine the mol fractions of the various components in each phase. The relations that exist between these various quantities at equilibrium are well known and will be given later. These equations are difficult to solve, yielding only to trial-and-error methods. The virtues of the analog computer are its speed and the automatic character of its calculations. The device is operated by turning a crank which varies the value of v, the total vapor fraction. This actuates a number of servomechanisms which perform automatically all computations. This computer facilitates the solution of such problems as (to mention a few] : Analysis of separator operation, studies of changes in composition of reservoir fluids with pressure decline, and analysis of natural gasoline plant operation. Examples of some of these problems are given in detail later. STATEMENT OF THE PROBLEM The essential equations are xm = 1+(km-l)v . . (1) Kmzm ym =------------------------. . (2) 1 + (Km-l)v ; n n S S xm= --------------------=1 1 + (Km-l)v m = 1 m=1 ......(3) n n S = S Km Zm =1 S ym 1 + (Km-1)v m=1 m = l ......(4) where ym = Vm/V = Mol fraction of m-th component in vapor phase. xm = Lm/L = Mol fraction of m-th component in liquid phase. Zm = Fm/F = Mol fraction of m-th component in mixture. KM = ym/xm = Equilibrium constant for m-th component at the given temperature and pressure. v = V/F = Mol fraction of vapor in the mixture. F = Total mols of a mixture of n components. V - Total mols of vapor in the mixture. L = Total mols of liquid in the mixture. Fm = Total mols of m-th component. Lm = Mols of m-th component in liquid phase. Vm = Mols of m-th component in vapor phase. Assuming the total mols of the mixture F and its composition (all the Fm) to be known — either from a quantitative analysis or from the amounts put together to make the mixture — the zm = Fm/F may be regarded as known quantities. From the given temperature and pressure of the mixture the K., are known (principally from experimental data). The primary problem is then: having given all the zm and Km to calculate v and all the fractions xm and ym. Having calculated these ratios, it is a simple matter to calculate V. L. Vm, Lm from their defining equations. SOLUTION OF THE PROBLEM Basic Computer Unit The computer consists of n units, each of which provides voltages xEo and YE, proportional to x and y as in

Jan 1, 1950

By Elton A. Youngberg

The Holden mine operated by the Chelan Division of the Howe Sound Co. is on the east slope of the Cascade Range in north central Washington on the south slope of Railroad Creek valley at an elevation of 3500 ft. The mine may be reached by a 40 mile boat trip from the town of Chelan which is at the southern tip of Lake Chelan, to Lucerne at the mouth of Railroad Creek and an 11. mile bus ride up Railroad Creek to Holden. A11 freight and concentrate is moved over this route to Chelan Falls on the Columbia River which is on the railroad four miles below the town of Chelan. The mine is now producing 2000 tons of gold, copper, and zinc ore per day which is treated in the Holden mill. Gold-copper and zinc concentrates are made, the first of which is shipped to Tacoma, Wash., and the latter to Kellogg, Idaho, for smelting. Ore is broken by long-hole blasting using the Noranda system which has been modified to meet local conditions. Until recently, blastholes have been drilled by diamond drills. Now a partial substitution of percussion drill holes, drilled with tungsten carbide insert bits, is being made. Geology The ore body occurs as a replacement deposit in a highly metamorphosed series of sedimentary rocks, mainly gneiss and schists, in a shear zone several hundred feet in width and of undetermined length. Commercial ore has been found in mineable widths of 25 to 100 ft for approximately 2500 ft along its strike. The commercial minerals are chalcopyrite, sphalerite, and gold. During the period of mineralization considerable silicifica-tion took place giving the ore an abrasive drilling characteristic. Following the period of mineralization, numerous dikes were introduced into the ore body. The earlier ones were of granite composition having a width of a few inches up to 80 ft. These were followed by much younger, fine grained basic dikes which usually do not exceed 2 ft in width. Development of Percussion Blasthole Drilling Equipment Test work with the 1½-in. tungsten carbide bit was carried on in development headings for several months early in 1947. The short life of the bits, because of gauge loss caused by the abrasive nature of the rock, prevented its adoption for this use. However fast drilling speed and ability to drill a long uniform hole suggested its use for drilling blastholes in competition with diamond drills as diamond costs were steadily increasing and exper-ienced drillers were difficult to obtain. The 1½-in. bit was the largest available at the time initial test work was started with sectional steel. The 1½-in. hole limited the diameter of the steel thread and coupling which could be used. Type F couplings were first used but because of the small thread section excessive breakage of the steel was experienced. Type H couplings were tried next. In order to use this coupling which is 15/8 in. in outside diameter, it was reduced to 1 3/8 in. giving 1/8 in. clearance between the coupling and the hole. Rod breakage at the thread was substantially reduced but some coupling breakage was experienced, however the overall performance was considered satisfactory (see Fig 1 for illustration of coupling and thread). Early test work with the 1½ in. bit indicated machines of piston diameters larger than 255 in. would cause inserts to loosen or break. It was found however that the additional weight of the sectional steel cushioned the blow enough to prevent bit failures when 3-in. Leyners were used. Rods used with the 1½-in. bits were 7/8 in. q. o. for sectional steel and 1 in. q. o. for all chuck pieces. In May 1948, 2-in. tungsten carbide bits became available and test work was immediately started. The 2-in. hole approximated the AX (1 15/16 in.) diamond drill hole which was being used exclusively for blastholes and permitted their substitution for diamond drill holes in a ring without alteration of pattern, burden, or explosives. The 2-in. bit also gave room in the hole for larger couplings and permitted the use of heavier rods and 3½-in. machines, increasing the

Jan 1, 1950

By M. P. Nackowski

Geological engineering expanded its role and significance during 1966 in the areas of construction, raw materials exploration and inventory, water supply and pollution, mechanical properties of earth material and regional environmental planning. Efforts varied immensely in scope and magnitude, in simplicity, difficulty and importance. Observations, measurements, and analysis encompassed both simple and sophisticated procedures. CONSTRUCTION Activities in construction ranged from preliminary to detailed evaluations of sites, development of preventative measures and designing corrective measures following construction failures. Most investigations concerned dam sites, highway locations and slope stability, building sites, tunnels and underground storage facilities.

Jan 2, 1967

By D. D. Button, L. D. Jaffee

INTEREST in the use of graphite as a high-temperature engineering structural material has recently increased markedly. However, actual use of this material has been limited, in part because information about its high-temperature mechanical properties has been lacking. The information needed includes not only reliable values for the properties, but also how to control these properties. Malmstrom, Keen, and Greenl have reported on the tensile and creep properties of some graphites above 2700° F (1500°C). They observed measurable creep under tensile loading at 4000 OF (2200 °C) and higher, with elongations of about 7 pct at 4500°F. Their typical elongation-vs-time curve showed the normal three stages of creep found for many metals at elevated temperatures. The specimens used were heated by passing an electric current through them. This method of heating caused a significant difference between the surface and axis temperatures, and may have affected the results. More recent work by kattus, in which the specfinens were also heated by their own resistance, showed very little plastic deformation for either slow or fast tensile testing or for creep testing. Work at this Laboratory, already reported,3 showed that for temperatures above 4500 "F and under conditions of slow tensile loading some commercial graphites exhibited elongations up to 20 pct. The work reported here is the continuation of a study of the tensile creep behavior of some commercially available synthetic graphites at temperatures up to 5300°F, and is preliminary to a more systematic investigation of the variables governing the high-temperature mechanical properties of graphite. MATERIALS TESTED The tests were conducted on six blocks from four lots of synthetic graphite bearing four different commercial-grade designations. These blocks were selected because their tensile stress—strain properties had been determined in previous work.3 Table I pre- sents the available information, supplied by the producers, on the processing of these materials. Also included in this Table are the densities and the tensile strengths at room temperature and 4500°F determined by the authors. EXPERIMENTAL TECHNIQUE The furnace used to heat the specimens for testing is shown in Fig. 1. The heating element was a graphite tube, 3-in. OD by 2 1/2 in. ID by 24 in. length. A spiral was cut into the 6-in. center portion of this tube to provide a high-resistance sec-

Jan 1, 1961

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3'= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker's experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

PRESIDENT PHILIP N. MOORE, ST. Louis, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS NEW YORK, N. Y. L. D. RICKETTS NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. TREASURER GEORGE C. STONE NEW YORK, N. Y.

Jan 1, 1917

By Edwin Higgins

INTRODUCTION IT is the purpose of this paper to set forth the relation and functions of the various organizations and institutions engaged in the promotion of safety iii the iron mines of the Lake Superior region; also to indicate the value of this work. Ten to 15 years ago there was practically no organized safety work; the accident rate was high, excessively so in some districts, and dangerous practices and conditions existed in many of the mines. During recent years, however, a gradual change for the better has been made. The chief causes of this change have been (a) public opinion, which has set the stamp of disapproval on the disregard for human life; (b) certain State laws which have made the operators responsible in dollars and cents for injuries to workmen; and (c) the humanitarian attitude of many of the operators, who have always decried the great loss of life in the mines. Today the Lake Superior region as a whole stands second to no other metal-mining district in the United States in its efforts to promote the welfare and safety of the miner. Dangerous practices in and about the mines are fast disappearing. The operators are ready and eager to adopt any expedient, rule, or device that holds forth a reasonable promise of reducing the hazards of the miner. Today the value of a mine captain or shift boss is reckoned, not alone on his ability to "get the ore," but also on his capacity for reducing accidents. While the progress made has been remarkable, there still remains much to be done, for the accident records of the Lake Superior iron mines, while lower than those of the chief metal-mining regions of the United States, still compare unfavorably with those of the metal mines of practically all foreign countries.

Jan 10, 1914

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.', ' Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,' are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952