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By Walter Renton Ingalls

Metallurgical literature has no record of any ore beneficiated for cadmium alone, and the cadmium of commerce is derived from zinc ore, with which cadmium is generally associated. Zinc ores free from cadmium—e.g., the ores of the Franklin and Stirling mines, New Jersey, and of Broken Hill in Rhodesia—are rare. Blende concentrates of 50 to 60 per cent grade have contained (in production of important tonnage) as much as I per cent Cd, which is unusually high. The concentrates from the Tri-State district average from 0.3 to 0.4 per cent Cd, which is high. The concentrates from mines west of the Rocky Mountains seldom are higher than 0.2 per cent. In the periodic system of the elements, cadmium is in the same group with zinc. Its properties and compounds are similar. Its metallurgy is also similar. Cadmium has a melting point of 320°C. and a boiling point of 778"C., while the melting point of zinc is 415'C. and the boiling point gos°C. These conditions, together with the lower reduction temperature of cadmium oxide, indicate means for. separating cadmium from zinc. Cadmium in spelter is viewed, if not as an impurity, at least as an alloying element that may be objectionable, its special effect being hardening. However, for some purposes, a little cadmium in spelter is desired, and 0.4 per cent may be permissible, even in spelter for rolling. Cadmium in spelter for brassmaking is completely volatilized at the temperature of that process, and in bygone days an immense quantity of cadmium must have been lost in the fumes from these furnaces. Pyrometalltjrgy—Early Cadmium compounds, sulphide and oxide, being more volatile than the corresponding compounds of zinc, loss of cadmium begins to occur from the first furnace operation. In normal roasting, even with Tri-State ore, this loss may not be very high. Raw ore, assaying 0.4 per cent Cd, may be expected to give a roasted product of the same assay, which would imply a cadmium loss of about 15 per cent. Roasted ore, assaying 0.4 per cent Cd when distilled at ordinary furnace temperature, yielded spelter containing about half of that in the ore charged. The first draw of spelter under these conditions may assay 0.8 per cent Cd (accounting for 22 per cent of the cadmium recovery) and after the several draws of spelter have been equalized the cadmium content may average 0.35 per cent. If, therefore, 2000 lb. of blende averaging 0.35 to 0.4 per cent Cd is roasted and distilled, there may be obtained 1000 lb. of spelter, assaying 0.35 per cent Cd or 3.5 lb. content, which entering into Prime Western spelter will be sold at the spelter price. It will be observed from the outline hereinbefore (summarizing conditions prior to the introduction of sintering) that the main loss of cadmium occurred in the distillation process and by failure to condense, which could be ameliorated by attaching a prolong to the condenser, thus collecting

Jan 1, 1944

By A. A. Gustafson

IN diamond or churn drilling for the prospecting of ore bodies, two products can be used for quantitative analyses; i.e., the core and the cuttings, or sludge. Some operators prefer an assay of core; others insist that the sludge be sent for analysis. Both must recover the sludge for check samples or for assays if there is no core recovery for any particular section of the diamond-drill hole. The Freeport Sulphur Co. found that numerous cumbersome sludge boxes or barrels were inconvenient and delayed drilling. The sludge settled slowly in the ordinary shallow, rectangular diamond-drill boxes and its total removal from the container was difficult, time-consuming and unsatisfactory; and sampling of deposits of which the metal contents are easily concentrated, as in ores containing cinnabar, gold and silver, is subject to error if the boxes are not thoroughly cleaned. Mr. Charles Ballard, dredge superintendent at Freeport's operation at Grande Ecaille, Louisiana, developed a portable cone while he was in charge of prospecting a mercury property near Tonopah, Nevada, in 1040. Ballard later improved the design while the settler was being used at a manganese property in New Mexico. The operation is based on the "free settling" of comminuted particles in a quiescent liquid. The ordinary sludge box discharges over a lip 8 to 12 in. wide and consequently the water has sufficient velocity so that the discharge water is never clear. The cone settler used by Freeport Sulphur Co. discharges over the entire circumference, which gives a discharge lip of 9 ft. in the size of cone used at the cinnabar and manganese prospects. Consequently, the velocity of the discharge water is slow enough so that all fine material settles and the discharge water is clear. When the drilling of a sample interval is complete, the sludge can be drawn off by the time the driller is ready to cut another sample. Thus, only one cone is needed per drill. The cone has been used by Freeport successfully in churn-drilling a manganese deposit, in diamond-drilling a mercury deposit, and in diamond-drilling a deposit of ore containing tin, copper, gold and silver. The cone is greatly superior to the old methods of collecting sludge and is now used on all Freeport drilling campaigns in the western states, both for surface and underground drilling. Fig. I shows the important details of a cone designed for average operating conditions, 30 in. in diameter and 36 in. high. Abnormal conditions may require some revisions in design. Fig. 2 shows a working drawing. A hose or pipe larger than the one used to convey water from the pump to the swivel head of the string of rods is connected to the stuffing box at the collar of a diamond-drill hole. The usual T-connection is used. It is not necessary to use a stuffing box if the top of the cone can be placed lower than the collar of the hole. Then the return water and cuttings can be made to flow by gravity. This hose or pipe discharges the cuttings of the drill bit and the return

Jan 1, 1943

By C. S. Smith, K. K. Ikeuye

In an earlier paper1 one of the authors called attention to the significance of the relative free energies of grain boundaries and interphase boundaries in alloys in determining the shape and distribution of micro-constituents. The ratio of the interphase and inter-crystalline boundary energies (that is, —?12, where ?12 is the energy of the interface between a crystal of phase 1 and a crystal of phase 2, and ?11 is the energy of the boundary between two crystals of phase 1) will be denoted by F. It is this ratio that determines, by the simple triangle of forces relation, the dihedral angle, ?, of phase 2 where it adjoins a boundary between two grains of phase 1. On a metallographic sample various angles are actually obtained because of the random orientation of the plane of observation, but the statistically most frequent angle is the true one. These basic principles were discussed in detail in the earlier paper. The experiments described below show the effect of both composition and temperature on ? and T for some alloys containing a liquid phase, and provide data on the rate of approach to the equilibrium angles in both solid and liquid phases. All the alloys were melted in a graphite crucible and cast into ingots 3/4 by 11/8 in. cross-section. Some of the aluminum alloys consisted of two immiscible liquids from which uniform castings could not be obtained. The amount of liquid phase varied locally to a considerable extent and the analyses were meaningless. Nevertheless, the composition of the liquid would not differ from that in an alloy of the intended gross composition, and the synthetic composition of the alloys was therefore used in considering the surface energy results. The ingots were given initial deformation by cold-rolling to 50 pct reduction, annealed, and given a second 50 pct reduction prior to cutting into small samples for heat treatment at the times and temperatures subsequently reported. The resulting micro-samples were carefully prepared metallographically and examined at magnifications of 650, 1280, or 2500. The objectives used were 21X, 0.40 NA (dry); 41X, 0.65 NA (dry); and 80X, 1.40 NA (oil emulsion). The appropriate angles were measured by rotation of the stage of a Bausch and Lomb metallograph to align the appropriate boundaries successively with a cross-hair in a micrometer eyepiece. About 250 angles were measured on each phase. Though the angles were read to 1°, the accuracy is probably not above 3°, because of uncertainty in setting the cross-hair tangent to the sometimes curved boundary. The corners of very small particles, particularly in early stages of adjustment after cold-rolling, were difficult to measure and the results were slightly dependent on the magnification used (compare Fig 1-C and 1-D). With particles of larger size and more nearly equilibrium shape, magnification made no difference (vide Fig 1-F and 1-G). The measured angles were grouped in 10° intervals (5° if ? was less than 20°) and plotted in bar

Jan 1, 1950

• A new curriculum for combined liberal arts-engineering education has been announced by 6 middle western colleges. The plan involves three years of ;study at one of the 5 liberal arts colleges and two years and a summer of 'engineering work at Case; graduates receive both the A.B. and B.S. degrees. * A new kind of mining is being pioneered by a pest Virginia coal operator which enables four men to produce 800 tons of coal a day. The machine that makes this possible is a giant auger, 5 ft in diam and 100 ft long. Together with the carriage in which it is moved about, it weighs 60 tons. A mobile, but separate power plant of 1000 hp drives it. ' * The Sorel smelter, which will reduce Allard Lake titanium ores, will utilize five 6-electrode rectangular electric furnaces. Furnace hearth size will be about 18x50 ft, and the furnace will smelt about 300 tons of ore per day, producing 100 tons of iron and 130 tons of 70 pct Ti02 slag. The furnaces will be fed continuously by gravity from charge bins, and tap at intervals of 4 hr or more. Slag will be transferred to a high speed casting machine, using cast iron molds, then crushed for shipment to pigment producers. The iron will be treated to reduce its sulphur content to 0.03 to 0.05 pct, and then cast into small pigs or ingots for shipment to steel mills. • Flying of North Africa's first airborne mangetometer survey was completed this month, covering approximately 20,000 sq km in north central Tunisia for Gulf Exploration Co.'s program there. Mapping was completed in less than 30 days. •Yore than 9000 employees of 11 electric companies are enrolled in a 6-hr program that successfully informs workers on the principles of the American economic system. The course is given by the Middle West Service Co. which claims that before and after employee opinion polls show that the course instilled a better understanding of free enterprise and consequently a favorable response to it. •According to a report issued by the American Geological Institute there will be 2865 graduates in geology, including advanced degrees from U.S. colleges in 1950. This supply of geologists compares with requirements for 1278 at the professional and subprofessional levels. The report contains a detailed statistical study of the supply and demand situation for geologists in the 1949-50 period. •The dark cloud of over-production in the bituminous coal industry has a silver lining, according to Natural Resources Notes. Closing marginal mines, mostly strip and truck mines, will result in lower average costs and higher quality of the coal still produced. The producers that will then constitute the industry will be properly equipped and adequately financed to carry forward an intensive campaign to holdd and increase the markets for bituminous coal. •A light, compact, highly reliable blasting machine which does not rely for its effectiveness on the operator's skill is being tested by the Army Engineers. Operating under all climatic conditions from -65 to 125F, the 50-cap machine consists of a springwound do generator and is waterproof.

Jan 8, 1950

By Walter Bonsack

THE CHAIRMAN.-This is the third and last session of the Institute of Metals Division's Symposium on Secondary Metals, and certainly the best of those that I have attended in the last few years. I would say that the increase in interest in secondary metals is quite noticeable by the steadily increasing attendance at these meetings. We have heard about the necessity of utilizing salvaged materials, but we still speak about them as low-grade, or down-graded materials. We still have the wrong perspective. We must willingly admit that these materials are valuable; we cannot go on using the choicest primary metals as morsels for our economic diet in a war of such unbelievable dimensions. This brings up the question-why are we so selective. The answer certainly is not that we know nothing else will do, but rather that we do not know what else will do. To be honest, we should admit our lack of knowledge concerning our complex alloys. Compared to the organic chemists, we metallurgists are very conservative, and the sooner we realize this and start to overcome it the better, because if we do not eliminate this difference, many customers of the metals business will go over to the plastics. If we take for example the development of aluminum alloys, you will see what I mean. From the binary aluminum alloys of 1920, we have progressed to ternary and quarternary alloys in the 1930's. We are only now beginning to use more complex alloys as we are forced to learn more about the effect of various elements on existing alloys. The effects of these elements should be studied now. They can be studied by two methods of approach. The usual method is to start from the base alloy and add various elements one by one in increasing amounts and study the resultant changes in properties. This is a tedious, long way. The other method which the smelters frequently use is to take the off-grade heats and study their characteristics. While the producer of primary alloys often has difficulties in alloying certain elements with the alloy under investigation, the smelter often finds them well alloyed in his raw materials and has no difficulties at all. Elements such as lead are difficult to alloy with aluminum and they tend to segregate severely. However, the amount which will remain alloyed in the metal is usually found in some "secondary" aluminum alloys. If one considers such concentration as the saturation, then by dilution with the same type of alloy, but free of such element, one can produce numerous intermediary alloys for investigation. In this fashion one is fairly certain to get uniformly spaced concentrations of the element under investigation. Similar cases probably exist with other metals. Nevertheless, the amount of work necessary to study all possible combinations is still tremendous. Necessity forces us now to utilize alloys which contain more elements than we are accustomed to. It is, therefore, necessary to study carefully the more complicated alloys. In secondary aluminum we are working and using the alloys which contain as many as 6 to 10 elements and we have learned over a period of several decades to balance

Jan 1, 1943

By Charles Trotter

AN instrument has recently been developed for determining the inclination and azimuthal direction of boreholes. This instrument is known as the Tro-Pari Instrument and is the invention of C. Trotter and G. Pajari of Sudbury, Ontario. DESCRIPTION The instrument is characterized by a unit mounted in gimbals and provided with a clockwork mechanism to clamp a compass to indicate azimuthal direction and simultaneously to clamp the unit in its plumb position to indicate inclination (Fig I). By means of a timing ring suitably calibrated in 5-min divisions, the unit may be set to lock after a lapse of time sufficient to allow the placing of the instrument at the desired point in the drill hole where readings are to be taken. The maximum time lapse obtainable with the instrument designed for use in EX or AX size holes is 1 hr 30 min which is considered to be ample time to lower to the greatest depths that may be drilled with this size of equipment. Larger sizes could be developed for larger diameter holes such as BX and NX sizes or the larger oil-well sizes and a correspondingly greater time lapse could be provided for. Up to the present time only the EX-AX size has been built. OPERATION Assuming a borehole is to be surveyed at 1000-ft depth and assuming it will take 30 min to lower the instrument to this depth, the timing ring is rotated through seven divisions which represent a time lapse of 35 min (5-min leeway) and is then returned to its zero position. This operation imparts energy to a spring which drives the clockwork mechanism. Simultaneously the compass needle is freed to swing to its magnetic north-south position and the encased mechanism is freed to hang plumb within a semicircular portion of the frame which is graduated in degrees after the fashion of a protractor. This semicircular protractor portion has a V-shaped notch at each degree division of its inner periphery. The instrument, now in its free position, is inserted in a bronze container made to suit the size of hole to be surveyed (Fig 2). Soft rubber washers are provided within the container to prevent undue shock. The container is connected to the drill rods with three 5-ft lengths of brass or aluminum alloy rods separating it from the steel rods in order to prevent distortion of the magnetic field. The assembly is then lowered to the desired point where readings are to be taken and is allowed to remain at rest until a period of time has elapsed slightly in excess of the time for which the timing ring was set. In the example cited above, when the 35 min has elapsed the compass needle is locked in its north-south position and the protractor locking pin is extruded and locks in the V notch opposite its plumb position. The device may now be removed from the borehole and it will remain in this locked position in spite of jarring or shak-

Jan 1, 1947

By W. R. Opie, O. W. Mole

By confining the electrolytic reduction of TiCl4 to the interior of a porous basket-cathode the electrolyte between the anode and the cathode can be kept free of reduced chlorides of titanium eliminating undesirable reactions of reduced titanium chlorides with brickwork or oxygen in the cell atmosphere. Semiwalls are not needed. Operating conditions are given and discussed. Titanium yields based on TiCl4 introduced are 93 pct. Cell voltage and amperage characteristics are adaptable to multiple cathode-series cell urmngements. EXPERIMENTS conducted in the National Lead Co., Titanium Division, Research Laboratories showed that titanium metal could be deposited in an electrolytic cell in which titanium tetrachloride was introduced through a tubular cathode.' The reduced chlorides as formed were confined to the vicinity of the cathode. They were reduced to form a cocoon-shaped growth of sponge titanium metal at the end of the cathodic tube below the surface of a sodium chloride-strontium chloride electrolyte. No diaphragm was needed.' Although high-purity, coarse crystalline metal was produced in the cocoon growth, the yields of metal removed from the cell, based on the amount of titanium introduced as TiCl4, were usually only 40 to 60 pct. The growth of the cocoon deposits was away from the cathodic tube for introduction of TiC14 toward the anode following the flu lines. The reduced chlorides of titanium diffused through the deposit and were reduced to titanium electrolytically within the deposit or on the outer surfaces. Deposition within the pores of the cocoon was detrimental to further deposition because it plugged the passages used by the reduced chlorides to diffuse away from the point of titanium introduction. As plugging due to deposition in the pores proceeded, the reduced chlorides in the center of the cocoon would force their way out by forming a channel and would escape from the vicinity of the cathode without being reduced to metal. Some work had been done previously1, 2 which indicated that if the end of the cathodic tube for introducing TiC14 was surrounded by a screen connected to the tube so that it too was cathodic, growth could be made to occur within the screen. Direction of growth was observed to be from the screen toward the point of TiCl4 introduction. Through a series of design modifications a cathode evolved which consisted of an introduction tube surrounded by a perforated metal basket as shown in Fig. 1. Modifications of this design are described in Refs. 3, 4, and 5. This basic cathode designa" was incorporated in electrolytic cells containing graphite anodes and constructed of high-silica brick refractory for containing the electrolyte (see Fig. 2). The inner crucible was surrounded by insulating brick and the entire unit contained in a welded steel shell. Suitable cooling chambers with inert gas atmospheres were devised so that the cathode could be removed from the cell without exposing the deposit to air while hot. Various alkali and alkaline earth chlorides were used as electrolytes.

Jan 1, 1961

By Charles Trotter

An instrument has recently been developed for determining the inclination and azimuthal direction of boreholes. This instrument is known as the Tro-Pari Instrument and is the invention of C. Trotter and G. Pajari of Sudbury, Ontario. Description The instrument is characterized by a unit mounted in gimbals and provided with a clockwork mechanism to clamp a compass to indicate azimuthal direction and simultaneously to clamp the unit in its plumb position to indicate inclination (Fig I). By means of a timing ring suitably calibrated in 5-min divisions, the unit may be set to lock after a lapse of time sufficient to allow the placing of the instrument at the desired point in the drill hole where readings are to be taken. The maximum time Lapse obtainable with the instrument designed for use in EX or AX size holes is I hr 30 min which is considered to be ample time to lower to the greatest depths that may be drilled with this size of equipment. Larger sizes could be developed for larger diameter holes such as BX and NX sizes or the larger oil-well sizes and a correspondingly greater time lapse could be provided for. Up to the present time only the EX-AX size has been built. Operation Assuming a borehole is to be surveyed at 1000-ft depth and assuming it will take 30 min to lower the instrument to this depth, the timing ring is rotated through seven divisions which represent a time lapse of 35 min (5-min leeway) and is then returned to its zero position. This operation imparts energy to a spring which drives the clockwork mechanism. Simultaneously the compass needle is freed to swing to its magnetic north-south position and the encased mechanism is freed to hang plumb within a semicircular portion of the frame which is graduated in degrees after the fashion of a protractor. This semicircular protractor portion has a V-shaped notch at each degree division of its inner periphery. The instrument, now in its free position, is inserted in a bronze container made to suit the size of hole to be surveyed (Fig 2). Soft rubber washers are provided within the container to prevent undue shock. The container is connected to the drill rods with three 5-ft lengths of brass or aluminum alloy rods separating it from the steel rods in order to prevent distortion of the magnetic field. The assembly is then lowered to the desired point where readings are to be taken and is allowed to remain at rest until a period of time has elapsed slightly in excess of the time for which the timing ring was set. In the example cited above, when the 35 min has elapsed the compass needle is locked in its north-south position and the protractor locking pin is extruded and locks in the V notch opposite its plumb position. The device may now be removed from the borehole and it will remain in this locked position in spite of jarring or shak-

Jan 1, 1949

By J. H. Slater

There is nothing particularly new about the use of sinter in a blast-furnace burden. For many years flue dust has been sintered at the various blast-furnace plants to put it in a form that could be recharged to the furnace with some assurance that it would stay in the second time. This paper is not a compilation of scientific data but only an attempt to give our experience with sinter. There are some unexplained discrepancies in the tests given here, such as the flue dust produced and iron tonnages, but the results given are the results that were obtained. Sinter is not the cure-all for blast-furnace problems. A good coke is still the most important factor in good furnace operation. However, good sinter is a big help. As flue dust is produced under varying operating conditions and fluctuates greatly in carbon content, it is difficult to produce from flue dust alone a uniform sinter, which will give satisfactory blast-furnace results. Sinter made from flue dust alone will change in character with every carbon variation. Almost invariably flue dust contains carbon in excess of the amount necessary to make good sinter, and this excess must be burned out. This, of course, necessitates reduction of the speed of the sintering machine and thus a decrease in tonnage. An alternative is to dilute with a carbon-free material to use up the excess carbon. High-carbon material when sintered results in a very dense, undesirable product, since the excess heat melts the charge into a hard, nonporous mass, and tends to form refractory silicates. At the Republic Steel plant in Cleveland, there had existed since 1924 a continuous-type sintering machine having 224 sq. in. of grate-bar area, capable of producing 9 to 11 tons of sinter per hour from flue dust. Under a former management, it was the practice to sinter only the flue dust from the blast furnaces, no attempt being made to recover the gas-washer sludge. As the dust was limited, the plant operated only part time. In other words, there was a sintering plant representing considerable investment, with good facilities for screening and preparation of raw materials, and flue dust available for only part-time operation. The sinter produced was costly and not a very desirable product. The first step was to install equipment for the recovery of the gas-washer sludge. This was done in the form of two large thickeners and a filter, which have proved very satisfactory. It was then decided to screen out the minus 3/8-in. fines from the Mesabi ores, mix them with flue dust and coke breeze when necessary, and operate the plant at full capacity. The tonnage increased to 18 tons per hour and the product was much improved. Sintering costs fell and the product was a preferred blast-furnace material, which on an iron unit cost compared very favorably with good Mesabi ores. On the average, 40 per cent flue dust and 60 per cent fine ore was being used. The oversize from the ore screening also became a preferred product for the

Jan 1, 1941

By C. E. Sims

In some experimental work conducted several years ago, it was noted that sulphur seemed to have a distinct influence on grain size of carbon steels. 111 order to check this observation, a series of S..A.E. 1040 steels was made with the normal composition held as nearly constant as possible. The steels were made with three sulphur levels, which were 0.012, 0.024 and 0.038 per cent sulphur, respectively. For each of the sulphur levels, steels were made with only silicon deoxidization and with aluminum additions of 0.1015, 0.025, 0.050 and 0.10 per cent. The melting medium was an acid-lined high-frequency induction furnace. These steels were forged and rolled and differentiall!. quenched from temperaturcs in the range of 1500O to 1800°F. After this, the A.S.T.M. grain size was determined and plotted as in Fig. I. It will be noted, first of all, that the aluminum-free steels had filler grain size with higher sulphur when heated to 1500, but that this condition was reversed at 1700°. When aluminum was added to produce fine grain size, the steels in the lowest sulphur level were fine-grained only to 1600°. and then only with an addition of one pound of aluminum per ton. The medium sulphur steels werc fine-grained to 1600' with a wider range of aluminum addition. The steels in the highest sulphur level were fine-grained at 1600° over a still wider range of aluminum additions and fine- grained at 1700° with an addition of one pound per ton. Fig. 2 shows curves of the grain-coarsening temperature for these steels and illustrates how sulphur and aluminum combine to give greater inhibition to grain growth than aluminum alone. Only the highest sulphur steels have a grain-coarsening temperaturc above 1700°.. At 1650°, the low sulphur steel is fine-grained only at its peak, while the highest sulphur steel is fine-grained over a wide range. In these tests, one pound of aluminum per ton gave the best results; this is equivalent to about 1 1/2 lb. per ton for commercial condition. IllcQuaid-Ehn tests made on these steels showed the same trend but to a lesser degree. The tests were repeated on a series of S.A.E:. 1015 steels with sulphur levels of 0.02 and 0.03j per cent. Aluminum additions were made in the range from 0.025 to 0.15 per cent. These steels were forged and rolled, normalized at 2000°F. to put them all in the same starting condition, then reheated to various temperatures from 1600" to 1800" and cooled at rates that would allow ferrite precipitation in the austenitic grain boundaries. The results of these tests arc shown in Fig. 3. It will be noted that. up to the temperature of 1650°, there is very little difference in the grain size obtained from the two levels of sulphur. .At temperatures of 1700° and 1750°, however, the lower sulphur steel was fine-grained only with an aluminum addition of 1 1/2 lb, per ton;

Jan 1, 1945

By Dwight K. Smith

A new pozzolanic composition has been developed for cementing oil wells where moderate to high temperatures prevail. This material is an entirely different concept to other oil well cementing materials, such as portland cements, cements containing additives, or liquid resins. Its characteristics are such that it is not, at present, recommended for use at temperatures less than 140º F. It can he either accelerated or retarded across a wide range of well conditions. This new cement is composed of a pozzolanic material, hydrated lime, and a chemical activator to give it early initial strength. This material can be used in wells from 6,000 to 18,000 or more feet where temperature conditions are similar to those along the Gulf Coast. This cement, when set, has no soluble portion subject to leaching or any compounds that should be attacked by sulfate waters or brines. For this reason, it should be permanent when placed adjacent to formations carrying any type of fluid. The compressive strengths in 24 hours are more than adequate for wells where temperatures are 140°F and higher. These values ore in excess of many other types of cementing composition presently in use in the field. This pozzolanic composition does not retrogress in strength at high temperatures as do some other types of cementing materials. The slurry weights of this material will vary slightly according to the specific gravity and water requirements of the pozzolnn itself. The materials covered herein will mix from 13.5 to 14.3 lb/gal, and will have a waiting-on-cement time comparable to other materials used under the same conditions. Economically speaking, this composition is less expensive than either portland cements or retarded cements presently being used under deep well conditions. INTRODUCTION Pozzolans are siliceous material which, though not cementitious in themselves, contain constituents which at ordinary temperatures will combine with lime in the presence of water to form compounds which have a low solubility and possess cementing properties. The use of pozzolanic materials dates back many hundreds of years and both the ancient Greeks and Romans were aware that certain volcanic deposits, if finely ground and mixed with lime and sand, yielded a mortar which possessed special properties. Generally, the early strengths of such materials were rather weak and were considered insufficient for modern commercial usages. Pozzolanic materials have been used extensively with portland cement in mass concrete to obtain special properties. In recent years, large quantities of certain pozzolanic materials have been used successfully admixed into portland cements for oil well cementing. Pozzolans, being reactive silicates, will combine with the free lime that is an inherent component of set portland cements and thereby. becomes cementitious themselves. POZZOLANS FOR OIL WELL CEMENTING There are many types of pozzolans, some of which are more reactive than others. The quality of the pozzoIan depends on the degree of reactivity, chemical composition, fineness, and other less well understood factors. Some of the more widely accepted pozzolans are those classified as fly ashes, while others are certain materials of volcanic origin. pozzolans which require large vol-

Jan 1, 1957

By C. A. Siebert, D. J. Girardi

PRACTICALLY every metallurgical process in-volves, at some stage or another, the contact of a metal with a gas. Because of this, gas-metal re-actions are of great practical importance and have been subjected to numerous investigations. It has long been recognized that the presence of cuprous oxide in liquid copper has an important effect on its casting characteristics and .physical properties. This has led to the desirability of determining the quantitative relationships between cuprous oxide in the liquid copper and the usual gases present during processing. Such data are not only of practical importance but also of a theoretical interest in that they provide a means of applying the principles of physical chemistry to problems in applied metallurgy. The object of this investigation was to determine the quantitative relationship at equilibrium between the gases carbon monoxide and carbon dioxide and the cuprous oxide content of liquid copper. The reaction and its equilibrium constant may be expressed as follows: 2 Cu (liq) + CO2 (g) = Cu2O + CO (g) acu2o X aco/a2 cu X aco2 Here the underlined symbol Cu2O designates cuprous oxide dissolved in liquid copper and (a), the activity of the various constituents. The activities of carbon monoxide and carbon dioxide are assumed to be directly proportional to their re- spective partial pressures and the activities of cuprous oxide and copper are taken to be proportional to their respective mol fractions. The equilibrium constant may then be expressed as follows: K2 = Ncu2o X Pco [Ncu]2 X Pco2 where N = mol fraction The solubility of carbon monoxide and carbon dioxide in liquid copper is a rather controversial subject.'-' A review of the literature is given by 0. W. Ellis.' It appears that carbon monoxide and carbon dioxide are both only very slightly, if at all, soluble in liquid copper. Volskii and Slobodskoi5 determined the equilibrium between carbon monoxide, carbon dioxide, and liquid copper at 1100°C. Their results show a higher cuprous oxide content for a given CO/CO2 ratio than found in the present work. The system hydrogen, water vapor, and liquid copper was investigated by Allen and Hewitt8 over the temperature range of 1090" to 1350°C. Equilibrium values for the system carbon monoxide, carbon dioxide, and liquid copper calculated from these data agree reasonably well with the present work. Materials and Procedure The copper used was oxygen free, designated as OF and analyzed as 99.98 pct copper with no appreciable amount of any one impurity based upon spectrographic determinations. The carbon dioxide was cylinder gas averaging about 99.95 pct CO2 with air as the major impurity. The carbon monoxide was produced by passing carbon dioxide over heated charcoal. Alundum combustion boats were used as containers for the liquid copper. No appreciable reaction took place between the copper and the alumina. This was evident from the fact that the copper sample after a run did not ordinarily adhere to the bottom of the boat and that the

Jan 1, 1951

By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By Arthur Knapp

No oil territory in the world has been so rich in large producing wells, in a comparatively small area, as the Baku field. Particularly is this true of the Bibi Eibat field, which formerly produced millions of "poods," of " gusher," or as it is called in Russia, " fountain " oil. The Bibi Eibat and Balachany fields have been exhausted of gas and ruined by water, but the Surachany and Benegadi fields are still fountain territories and many outlying districts that have only been prospected produce rich fountains. The method of controlling fountains, or gushers, is the result of growth, along with the Russian system of drilling, where large diameters and riveted casing have been in vogue. The screw casing is seldom used except to exclude water. Formerly the method of finishing wells and the condition of the casing at the top of the well would not permit the use of gates, manifolds, and connections as is standard elsewhere. The life of the flowing wells is very short, particularly those 10 in. (25 cm.) or more in diameter, which produce large quantities of sand and often flow for but a few days and are then a complete loss. More than 1,000,000 poods in 24 hr. have been claimed in several instances, but in no case was the flow for more than a few days. The oil sands of this district are free uncemented sands and vary in thickness from paper thin to a maximum of 10 ft. (3 m.). The sands are interlaid with strata of soft clay. In spite of this, the practice has been to drill into such sands and produce from the open hole without screen or liners. Sometimes the casing is set below the oil sand but in this case holes from 2 ½ to 3 in. in diameter are drilled opposite the oil sand, which would not have the effect of a screen.

Jan 1, 1920

By Earl F. Hanson

Fires in heavily timbered mines are disastrous, involving danger to both life and property. Some mines have been completely ruined or so heavily damaged that reopening them would not pay. Though few mines are entirely free from danger of fire, the risk is minimized by proper care and good design of plant. The Tintic Standard mine is at Dividend, Utah, in the famous Tintic mining district, about 60 miles south of Salt Lake City. The development of the mine was begun in 1907 by the late Mr. E. J. Raddatz and his associates. From the beginning, the work was hampered by high rock temperatures and the presence of high concentrations of rock gases such as carbon dioxide and nitrogen. Development work was carried on with great perseverance for nine years, and resulted in the discovery of ore in 1916. The total production of the Tintic Standard mine to Jan. 1, 1936, amounted to 1,664,388 tons of ore, having a gross value of $61,996,719. General Layout of the Mine The No. 2 shaft, which is the main working shaft of the Tintic Standard, is within the main orebody and is connected with the five other shafts. Their respective positions with respect to the No. 2 shaft are as follows: North Lily, 2770 ft. northwest with drift connections on the 700 and 900-ft. levels; No. 3 shaft, 670 ft. east connected through the 700-ft. level; Eureka Standard, 4550 ft. south, connected on the 900-ft. level; No. 1 shaft, 1470 ft. southwest, with connecting drifts on the 900 and 1250-ft. levels; Eureka Lilly, 2000 ft. southwest, with connecting drift and raise through the 1250-ft. level. The Tintic Standard orebody consists essentially of one continuous oreshoot extending from the 600-ft. level to the 1450-ft. level, with a cross-sectional area of approximately 70,000 sq. ft. at both top and bottom, reaching a maximum area of 215,000 sq. ft. between the 1100

Jan 1, 1937

By Harry L. Brown, James M. Dickinson, Philip E. Armstrong

The elastic stiffness coefficients of niobium have been rneaslrred from -150°C to over 650 C and ave in accord with the anomalous temperature dependence previously observed for Young's modulus. This unusual behavior has been shown to be the result of changes in the relative values of the shear elastic coefficients. The bulk modulus remained essentially constant over the temperature range studied, while changes in the shear coefficients produced a more nearly isotropic behavior as the temperature increased. A number of investigators have reported data on the temperature dependence of Young's modulus of polycrystalline niobium. The values cited for the room-temperature modulus ranged from 0.71 to 1.17 x 10" dynes-cm-' (10.3 to 17.0 x lo6 psi) and in each case the modulus was observed to decrease with increasing temperature. In our recent study,8 both polycrystalline and single-crystal samples of essentially strain-free high-purity niobium showed a Young's modulus whose temperature dependence as well as magnitude was strongly dependent on specimen orientation. This was shown to be the result of changes in the relative magnitude of the two shear moduli, C and C'. Young's modulus of polycrystalline samples with strong [110] textures and Young's modulus of single crystals whose orientations were away from the [loo] actually increased as much as 12 pct between room temperature and 1000°C. While studies on the residual effects of previous fabrication, thermal treatments, and impurity contents will probably resolve the problem of the widely differing Young's modulus values observed in polycrystalline niobium, a more complete description of the elastic properties requires an evaluation of the single-crystal elastic constants. A knowledge of these constants can provide a clearer picture of the nature of the temperature dependence, as well as establish a basis for predicting the modulus behavior of polycrystalline niobium, both in the randomly oriented condition and with various fabrication textures. The effects of residual strains on the elastic behavior then can be separated from orientation effects. EXPERIMENTAL METHOD Thin rod-resonance techniques were used to obtain both the Young's modulus and shear modulus of single-crystal specimens. The determination of these moduli as functions of the crystallographic orientation of the specimen axis provided sufficient information to permit calculation of the single-crystal elastic constants. The necessity for torsional as well as longitudinal measurements led to the design and assembly of a vertical-tube vacuum furnace incorporating probes for the simultaneous determination of both longitudinal

Jan 1, 1967

By J. C. Fisher, J. H. Hollomon, David Turnbull

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949