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By Harold Markus, Gerhard Derge

THE first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from I.I2[t] volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. EXPERIMENTAL DATA Cations.-The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.2 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 0 7-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Oswald J. Heinrich

(Read at the Philadelphia Meeting, February, 1878.) DURING the last twenty years much has been done to investigate and define the Mesozoic formation of the United States along the Atlantic States, as well as in the Territories. The investigations of Professors Hitchcock, Emmons, Hayden, H. D. Rogers, and those now in progress in connection with the geological surveys of Penn-

Jan 1, 1878

By Philip D. Wilson

SPEED is essentiaI in this war program and it is hard to keep up with developments. When the title of this paper was chosen, the contemplated magnesium production for which plants were then under construction was some 200,000 tons of metal per year or sixty times the 3350-ton production in prewar 1939. A few- days later an analysis of the President's 185,000-plane pro-gram, incendiary bomb schedules, and the additional requirements of the Army. Navy and Maritime Commission made it apparent that a much greater amount of magnesium must be provided in 1943. The new figures are huge but the censor will not per-mit their disclosure.

Jan 1, 1942

By C. R. Kuzell

GEOGRAPHICAILY the industry of reducing and refining of copper continued to migrate from the .United States during 1931. While this country is losing the predominant position of its copper industry, our engineers still enjoy their pre-eminent position as leaders in the design and operation of the new plants being brought into production in the four quarters of the globe. Progress in the art, as indicated by the construction of the recently completed works, has not been revolutionary. Standard methods have been followed, augmented by novel features in flow-sheets demanded by the results of progress in the art of ore-dressing, and by reason of problems incidental to the peculiarities of the new ores being treated. Design and construction progress has likewise been orderly and without radical departure from less recent practice; new features in primary and secondary equipment being logical developments to provide for special conditions to keep abreast of improve¬ments in accessory apparatus. The new plants are being rapidly brought in without hazardous novelties and for the purpose of yielding the principal ingredient, copper, in as large a volume as it will he possible to market; the old United States procedure. In the meantime the domestic plants are shut down or operating at a very low capacity, threatened with untimely demise unless the metallurgist can extract and develop other valuable products from the ores. International agreements .and tariff protection may be a temporary reviving stimulant, but for many mines the days of profit will be numbered unless the ores can be made to yield as values the ingredients now being discarded. Invisible progress in this direction has been made during the past year, and it is to he hoped that time will prove that the outstanding progress of 1931 was in the development of processes for the ultimate recovery of by-products from copper ores, perhaps even relegating the value of the copper yield to secondary importance.

Jan 1, 1932

By M. J. Saarivirta

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

Jan 1, 1961

By Dennis A. Clark, Brent Larsson

Tunnelling today is a lot more than drilling and blasting. The developments in drilling and blasting technique have made it pos¬sible to save costs both by increasing the advance per round and optimizing the demands on the final contour. Increasing the hole depth by using longer feeds and bigger dril¬ling rigs make the drilling time shorter compared to the set up time. It is important that the deeper holes are followed up by using a suitable cut. The most common cut in Sweden today is a parallel hole cut with one or more large holes; with a diameter corresponding to the hole depth and wanted advance per round. It is often specified that smooth blasting is to be carried out with a specific drill hole spacing. It is extremely rare, however, for specifications to be issued concerning the alignment of the raw of holes closest to the contour holes. It is very easy to ruin the effect of smooth blasting altogether by firing the rest of the round carelessly with an excessively high charge distribution. The drilling and blasting of the contour holes and the line of holes closest to the contour holes is therefore an extremely important part of any underground work. Accuracy and care in connection with the drilling of contour holes is also extremely important since it is possible to reduce the amount of overbreak, the result being more rapid mucking out, smoother and more durable surfaces and also less consumption of concrete for lining purposes.

Jan 1, 1983

By W. E. Keck

THE potential iron ores of Michigan can be classified from the stand-point of the predominant impurities into siliceous, sulphurous and phos-phorous ores. Research on the flotation of each of these classes of ore was carried out in the following Planner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly, pure state. There are two varieties of the mineral-specular hematite and massive hematite. The latter is the principal variety, but the former is an Impor-tant mineral of iron in some of the potential ores. Because of this condi-tion, flotation research was performed with both varieties. This research consisted essentially of: (1) a survey of the literature on hematite flota-tion, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the; development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a pro-prietary frother and oleic acid or other soluble oils 2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1937

By Franklin G. Pardee

IN 1920 the Minnesota Tax Commission estimated a reserve of 1,341,674,538 long tons of iron ore in Minnesota, the Michigan State Tax Commission report showed 199,092,855 long tons in reserve in that state, and the Wisconsin Geological Survey set the Wisconsin reserves at 21,500,000 long tons. The total reserve that year for the Lake Superior District amounted to 1,562,267,393 long tons. Ten years later the reserves of iron ore in these same districts were Minnesota 1,235,227,510, Michigan 168,349,823, and Wisconsin 23,000,000, or a total of 1,426,577,333 long tons. The decrease in ore reserves in this ten-year period was 135,690,060 long tons, but the shipments were 520,746,975 long tons. In other words, the ten-year depletion in reserves was only 8.68 per cent. If similar conditions carry into the future this calculation would indicate a life for the ore reserves of the Lake Superior region of over 100 years.

Jan 1, 1933

By J. F. Wolff, Anson A. Betts

The following correspondence relating to a paper bearing the above title, presented by J. F. Wolff, at the New York meeting in February, 1917, and published in the Transactions, Volume LVI, page 142, has passed between the author of the paper, and Mr. Anson G. Betts, and is interesting, although it was received much too late for incorporation in its proper place in Volume LVI. Anson G. Betts, Asheville, N. C.—1. I should like to ask Mr. Wolff if he finds from analysis of the iron formation and of the iron ore, and from the relative amounts of each in each unit area of the formation, unleached and after leaching, that the iron remains entirely insoluble and the total quantity still remains present; or whether he finds that some of the iron is removed, or possibly even added by deposition from the water passing through the formation. 2. The water that passed into the iron formation had to go somewhere; was it absorbed by underlying formations through hydration, or, after passing through the ore formation, did it come to the surface in springs at a lower elevation, or how did it escape from the ground? 3. I should like to ask Mr. Wolff whether he finds that the iron formation in the sedimentary series does not come next to the quartzites and generally between the quartzites and slates. J. I?. Wolff, Duluth, Minn.—1. In common with others, you appear to have some hesitancy in accepting the fact of the removal, by solution, of the enormous quantity of silica which has been leached out of portions of the Biwabik iron formation, thus forming orebodies of merchantable iron ore. I believe that even Dr. Waldemar Lindgren once hesitated to accept this fact. However, the evidence is so simple and absolutely conclusive that the fact is established beyond all question. At the contact of orebodies with their rock walls, the bands of iron ore in the orebody can be seen in contact with the corresponding bands of original iron oxide in the rock wall, and the chert layers in the rock wall can be seen to give place to fine granular material (fine silica and iron oxide) and pore space. This is especially noticeable where slumping at the rock walls has not been so great as to displace the layers in the orebody from their contact with their corresponding layers in the rock wall. Although complete analyses of the entire original rocks in the iron series have not been made in any place, to my knowledge, from the best data at hand as to the average analysis of the Biwabik series and the

Jan 1, 1920

Date of Congress: Sept. 20-25, 1915 The Committee on Local Affairs is fortunate in having secured for a period expiring on Oct. 17, an option. on 100 rooms at the Palace, St. Francis. and Fairmont hotels, the three leading hotels in San Francisco, with the distinct understanding that, on account of previous engagements whereby the hotels are reserved to their capacity, the rooms must be vacated on Sept. 25, 1915. The rates applying will be $7 per day for the court rooms occupied by two people, or $10 per clay for outside rooms occupied by two people. The outside rooms will face the main thoroughfares at the Palace and will face the city and bay at the Fairmont, which latter is situated oil a high hill. The St. Francis faces an open square and is flanked by main thoroughfares on two sides. If any members desire their reservation to extend either before the 20th or beyond the 25th, the Committee will use its best endeavors to secure such extension in individual cases, in accordance with the indicated wish. The Hotel Bureau in San Francisco is co-operating actively and closely with the. Committee on Local Affairs of the International Engineering Congress and offers the choicest rooms in any of 350 hotels other than the three mentioned above. This Hotel Bureau controls 50,000 rooms in San Francisco, which are all provided with hot and cold water, stationary basins, baths, house telephones, elevators, and bell boy service.

Jan 9, 1914

By Henry N. McCarl

[The Construction Materials section contains the following Chapters: Aggregates Cement and Cement Raw Materials Crushed Stone Dimension and Cut Stone Lightweight Aggregates Gypsum and Anhydrite Sand and Gravel Insulating Materials-Thermal and Sound Slag Roofing Granules] Mineral aggregates are those natural and manufactured industrial mineral and rock materials that provide bulk and strength in portland cement concrete, bituminous concrete mixes, and plaster or stucco surfaces. They may also provide special characteristics such as thermal and acoustical insulation, weight, surface textures, abrasion resistance, and impermeability to various concrete products and mixes. Most aggregates are relatively inexpensive materials, but despite their low unit value, the tonnages consumed each year in the United States and throughout the" world make mineral aggregates by far the leading industrial mineral and rock materials both in terms of volume (tonnage) produced and value consumed. The major use of mineral aggregates is in concrete. The low cost, high bulk aggregates tend to keep concrete construction costs at levels competitive with other building materials. Other major uses of aggregates include highway and railroad base or ballast materials, graded fill, and various industrial uses such as metallurgical and chemical fluxes and raw materials-these latter uses are often considered nonaggregate uses of mineral aggregate materials. The per-ton value of mineral aggregate materials at the production plant in 1980 and 1981 varied from $2 to $5 for most sand and gravel and crushed stone, $3 to $6 for air-cooled slag, $7 to $20 for expanded slag and expanded clay or shale aggregate, to as much as $165 to $320 for expanded perlite or vermiculite. The expanded lightweight aggregates have been dramatically affected by increasing fuel costs. It is ironic that the specialized aggregates used as insulating materials to conserve energy cost so much more to produce due to the high proportion of energy consumed in their production. The first four parts of "Construction Materials" deal with the utilization of four major mineral aggregate types: Crushed Stone, Lightweight Aggregates, Sand and Gravel, and Slag. While the focus will be on the use of these industrial minerals and rocks, there will also be some coverage of sources, mining and production, especially in those cases where they are not discussed in the Commodity section of this book.

Jan 1, 1983

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By Jun-Yan Chen

Ground control problems in sublevel caving become evident as the rock pressure increases with depth. Recently, a finite element analysis of the stability problem of the sublevel caving method was completed by the author. This paper summarizes the results of stress analysis in sublevel extraction drifts under different field stress conditions by using linear elastic and nonlinear elastic-plastic finite element modeling techniques. A critical stress concentration will occur in the uppermost sublevel drifts beneath the caved area or blasted ore area. During the blasting and drawing cycle, a tensile and shear failure condition could develop in the center extraction drift when it would be mined last. Under a high horizontal stress field condition, almost all tensile stress in the back of the extraction drifts will be eliminated and only slight yield can be seen in the floor of the extraction drifts. Compared to the cases under the stress field where vertical stress is the dominant factor, the total yielding zone will be greatly reduced because of an in- creasing horizontal stress field with depth. However, it is predicted that the center of each ore column side will experience excessive shear stress that probably will result in ore failure. The two major conclusions drawn from this study to improve the overall stability of sublevel caving are: (1) the drift width must be carefully controlled and an appropriate stoping sequence selected; and (2) the sublevel caving method can be used in deep min

Jan 1, 1983

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.

By L. C. Morganroth

Magnesites are of two general classes - massive and crystalline.

Jan 1, 1915

By H. D. Strain

Potash is a generic term used to describe a number of compounds containing the element potassium (K), which is one of the three major plant nutrients. Potash content of these compounds is commonly expressed as percentage potassium oxide (K20), and the market value of the products is usually dependent on contained K20. Most of the potash produced (approximately 95%) is used in agriculture as fertilizer. Potash products today are shipped by producing countries all over the world to meet the need for increased food production. WORLD POTASH RESERVES Apparent world potash reserves are shown in Table 15.2B.1 and total some 96 billion mt of recoverable potassium oxide. The Canadian reserves account for approximately one-half the known world reserves. The reserves shown represent the potassium oxide content of a variety of potash-bearing ores. The major ore is sylvinite (a mechanical mixture of KC1 and NaCl) from which KC1 or sylvite is recovered (63.2% K20 equivalent). Other ores, such as langbeinite (potassium, magnesium sulfate-22.7% K20) and carnallite (potassuim magnesuim chloride-17.0% K20) are also mined in various parts of the world, mainly for the potassium content. Theoretically, potassium is available in almost unlimited qualities from brines and saline waters. To date, the cost of recovery from salt brines has been greater than the costs by mining operations, but new technology could make brines and seawater an increasingly important source. POTASH PRODUCTION Potash production dates back to the 1860s in Germany, which was the only recorded producing country until 1912. By 1912 Germany was producing approximately 1 million tpy of K2O equivalent. Production began in France in 1913 and in the United States in 1915. World potash production and consumption are shown in Table 15.2B.2 for the years 1950-51 through 1967-68. In 1967 and 1968 the major potash-pro¬ducing countries in order of importance were those listed in Table 15.2B.3. By 1972 Canadian production had outstripped U.S. production. WORLD CONSUMPTION World consumption of potash for the years 1950-51 through 1967-68 is shown in Table 15.2B.2. Table 15.2B.4 shows total world consumption of potassium materials in 1967-68 by country. More than 70% of the world's potash is

Jan 1, 1976

By Ross W. Smith, Nikhil Trivedi

The variation of point of zero charge (PZC) of both simple and complex oxide minerals was studied as a function of aging time in water. In most cases the PZC's of the simple oxides moved toward more basic pH values with aging time. Evidence to date suggests that this phenomenon relates to dissolution of disturbed layers on the mineral's surface accompanied by later readsorption of metal hydroxy species back onto these surfaces. The readsorption takes place after the solution becomes supersaturated with respect to some crystalline phase. The variation of PZC's of complex oxides as a function of aging time in water is apparently related to several different mechanisms. In a few cases PZC shifted toward more basic values with time. This shift could be attributed to much the same mechanism as for simple oxides. In most cases, however, PZC of complex oxides shifted toward more acid values with aging time, probably because of loss to solution of soluble cations whose oxides possess basic PZC's.

Jan 1, 1975

By L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948

By A. W. Ashbrook

There are essentially three main classifications for extractants: acidic, basic, and neutral. The acidic and basic are also referred to as cationic and anionic, respectively. Some extractants are shown in Table 11-1. Acidic Extractants Acidic extractants which are of use, because of cost and/or insolubility in water, are alkylphosphoric, sulphonic, aliphatic monocarboxylic acids and naphthalene derivatives.

Jan 1, 1978

By C. Laird, C. E. Feltner

An investigation into the effect of a material's slip character on its high strain fatigue properties has been carried out using copper and Cu-7.5 wt pct A1 as representative wavy and planar slip mode materials, respectively. In copper, the constant term and exponent in the Coffin-Manson equation, ?EpNf1/2 = const, are unaffected by the temperature of testing or the history of the metal. On the other hand, in Cu-7.5 wl pcl Al, while the exponent is invariant, the constant is increased with respect to copper and increased further with decrease in temperature. The life in Cu-7.5 wt pct A1 is double that of copper at room temperature and about four times at 78°K. Fractoflaphic studies indicate that these diffevences in life are associated with the early stages of cracking. In copper, severe surface rumpling provides crack nuclei at pain boundaries independent of' testing temperature or the history of the metal. In Cu-7.5 wt pct Al, the planar slip mode of deformation prevents grain boundary folding; crack nucleation is therefore mainly transgranular and the increase in life with respect to copper is associated with a prolonged linking-up stage of such transgranulay cracks. At the lower temperature the increased difficulty of cross slip inhibits multiplication of trans-granular cracks and retards the linking-up process, giving a further enhaancement in life. It is expected that such behavior will be found general in materials of wavy and planar slip mode, respectively. STAGE II crack propagation in high strain fatigue takes place by a repetitive process of crack tip blunting in the tension part of a fatigue cycle followed by resharpening of the crack in the compression part.1-3 This mechanism has come to be called the "plastic relaxation process".3 At very high strains (lives to failure less than 103 cycles), most of the life of a specimen is spent in crack propagation by the plastic relaxation process.4,5 Since the differences in the cyclic strain hardening behavior of metals and alloys are comparatively small in this strain range,6,7 the amount of blunting at a crack tip depends primarily on the applied strain amplitude. The rate of crack propagation in this life range is therefore nearly constant with respect to material and temperature of testing. In the longer life portion of the high strain fatigue range (l03 to 103 cycles to failure), a considerable fraction of the lives is spent in crack initiation and Stage I growth. Grain boundaries have frequently4,5,8 been found to be the sites for this growth which is also associated with a surface folding process.4'5 Such folding behavior may also be general in any material having a grain structure and capable of plastic deformation. It has therefore been suggested475 that the universality of the Coff in-Manson law,9'10 constant,* where ?Ep is the plastic strain range and Nf the number of cycles to failure, is reflected in the approximate invariance of both the crack initiation and propagation behavior. It happens that, in most investigations of the phenomena associated with failure,4,5,8 materials with a wavy slip mode have been used as vehicles for the studies, or else "normally" planar slip mode materials have been tested under conditions giving rise to wavy glide deformation, e.g., stainless steels cycled at high temperature.'' The purpose of the present investigation was to determine whether or not different cracking phenomena would occur when the slip mode of a material is planar and if the associated life to failure would be different than that of a wavy slip

Jan 1, 1968