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By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s'S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.' There are a few marked discrepancies in the intensity comparison of the two s's, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s' have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955

By Jon J. Connor, Richard J. Ebens

The trace element geochemistry of the cherty clay-rich carbonate residuum cover in much of southern Missouri and adjacent parts of Arkansas was investigated during the earl 1970's as part of a statewide geochemical survey of Missouri.1-8 The study was environmentally oriented and focused on the character of the "natural" geochemical environment of the state. A great deal of effort was made to collect samples that would represent the geochemical variability of the near-surface environment in an unbiased way. In general, this was accomplished by use of randomization procedures in both collection and analysis. Most of the sampling sites were selected randomly to prevent personal bias from entering into sample selection. In the laboratory, samples were analyzed in a randomized sequence to circumvent the effects of any systematic bias that may have entered into the laboratory procedures. Several residuum samples contained 1000 parts per million (ppm) or more of lead, zinc, and barium. All these samples were collected in Washington County in or near the barite district. The frequency distributions shown in [Fig. 1] indicate just how unusual the residuum in Washington County is with regard to these three metals and copper. The shaded parts of the histograms represent the samples from Washington County. The histograms are based on analyses of 141 samples from 38 localities scattered over the subcrop of the Cambrian and Ordovician formations of southern Missouri and northern Arkansas. Eight localities were selected randomly from over each of four bedrock units-Bonneterre dolomite; Potosi and Erninence dolomites; Roubidoux formation; and the Jefferson City, Powell, and Cotter dolomites. Six localities were selected randomly from over the Gasconade dolomite. The geochemical "background" for these elements in residuum is defined by samples from outside of Washington County (unshaded part of the histogram); lognormal distribution curves have been fitted to the corresponding parts of each histogram. Clearly, these lognormal models (curves) describe well the background distributions of zinc, barium, and copper. The background histogram of lead concentrations is notably skewed to the right compared to the model. Lognormal distribution curves were also fitted to the data on lead, copper, and zinc in the residuum of Washington County. No model was fitted for barium in Washington County because of the distinct bimodality in the data. All samples containing more than 1000 ppm were collected in the barite mining district and obviously reflect the elevated levels of barium in the district. The frequency distributions for Washington County are clearly anomalous with respect to the background data, those for lead, zinc, and barium being exceptionally so. The models for anomalous lead, zinc, and copper seem to fit reasonably well, although the scatters in the lead and zinc anomalies are considerably larger than the scatters in the corresponding background data. The copper anomaly, although probably real, is greatly subdued compared to that of lead and zinc. Also, it has a scatter similar to that of the copper background, rather than being enhanced like the scatters of the lead and zinc anomalies. On the basis of techniques described by Miesch,4 the chemical abundance of copper, lead, and zinc in residuum in

Jan 1, 1980

By W. F. White, W. R. Beloff, B. C. Dorwart, G. W. Jaworski

INTRODUCTION The rigid inclusion stressmeter is a relatively low-cost instrument developed by Hawkes and Bailey (1973) and was originally intended to monitor stress changes in mine pillars subjected to uniaxial stress changes. In this regard, this instrument has found considerable use by the mining industry. More recently, there have been attempts to use the stressmeter for determination of more general changes of the in situ rock stress. This paper reports on a study to characterize the performance of the rigid inclusion stressmeter for this application and presents results on the effect of anisotropic stress changes. These stress changes must be accounted for to properly analyze general changes of the in situ rock stress. BACKGROUND INFORMATION The rigid inclusion stressmeter is an instrument designed to measure variations of the in situ stress around a borehole. The stressmeter studied in this work, is manufactured by Irad Gage, Div. Creare Products, Inc. Lebanon, New Hampshire. It consists of a stiff hollow steel gage body that is preloaded across a borehole diameter. The preloading is activated by sliding a wedge between an upper platen and the gage body. Changes in the in situ stress result in slight deformations of the gage body. These deformations affect the stress in a highly tensioned wire that

Jan 1, 1982

By J. M. Gaines, C. H. Herty

It is a matter of frequent record in the literature that manganese will desulfurize molten iron under proper conditions. Particularly has much been written with regard to this action in the mixer, and numerous reports have been published describing experiments in which advantage was taken of this phenomenon in order to obtain a purer iron for the open hearth. The question of sulfur elimination in the ladle has, however, received comparatively little attention. The reaction by which sulfur is removed is considered to be: FeS + Mn = MnS + Fe. The manganese sulfide, being but sparingly soluble in the iron, and of a lower density, will rise from the body of the metal and collect as a slag on the surface. It is therefore an action taking place solely in the metal, and independent of interaction between slag and metal. As will be shown later the presence of slag on the metal tends to offset the effect of manganese elimination. It is this fact which distinguishes desulfuriza-tion in the ladle from desulfurization in the mixer, for it has been shown1 that the amount of sulfur eliminated in the mixer is closely tied up with the composition of the slag. Experimental Procedure In order to ascertain the extent of and the factors controlling this elimination in the ladle, several casts were sampled carefully at the blast furnace and again when the ladles were being emptied, either at the mixer, open hearth, or foundry. If the sulfur content varied from ladle to ladle at the blast furnace the average sulfur content of each ladle was obtained by integrating the curve "sulfur vs. time " for the cast under

Jan 1, 1927

By W. E. Rice

THE ceramic industry has to do with forming or molding articles of clay, and imparting to them their characteristic properties of permanence, strength and color by subjecting them to heat treatment in kilns. This heat treatment is commonly known as "firing" or "burning." The art of firing clay ware antedates the industrial use of coal; hence wood was the fuel first used, and the earliest kilns were built to burn wood. The majority of the clay ware produced today is fired in periodic kilns that are essentially enlarged structures similar to the earliest enclosed kilns; a kiln consists of a large chamber 16 to 32 ft. dia. (or rectangular) in which the ware is charged and fired either in direct contact with flame or hot gases from the fuel, or in saggers which shield the ware from direct contact with the gases. The fuel is burned in a number of small furnaces built in the thick .wall that encloses the chamber; these furnaces are from 16 to 36 in. wide and from 3 to 5 ft. long; some of them have horizontal or sloping grates, but many have no, grates; the last are called "dead-bottom" furnaces. The temperature necessary to mature the charge in the kiln varies for different clays; for some it is as low as 1800°, and for others as high as 2700° F. Wood was an ideal fuel for the low temperatures that were used in early kilns; it burns freely and produces along, clean flame, which promotes uniform distribution of the heat in the kiln; it does not coke and so restrict the passage of air through the fuel bed; the ash does not melt in the fuel bed to form clinker; and the ash that is carried into the chamber and deposited on the charge does not contain iron and sulfur to discolor the clay. The extent of the ceramic industry now precludes the general use of wood in kilns, so that today this industry is one of the large users -of bituminous coal, burning more than eight million tons annually in kilns. Manufacturing plants usually are at or near the source of clay, with deposits of coal suitable for kilns occurring near the clay. The cost of coal is the largest single item of expense in the manufacture of clay ware, and, because all coals are not equally suitable for the process, the careful selection of coal is important. In this selection the desidera-

Jan 1, 1932

By C. W. Reith

The development of production in West Texas during the year 1933 was largely confined to the expansion of proven areas, especially Ward County, Iatan and North Winkler. Wildcat activity was at a comparatively low ebb and resulted only in discoveries of probable minor importance in Ector County. The interest shown in deep wildcatting to test beds of pre-Permian age was a new development, which should soon throw light on the possibilities of deeper production from the present producing fields. The important pre-Permian tests of the year were: 1. Stanolind Oil and Gas Co., Todd No. 1, a unitized test, in north central Crockett County on a probable continuation of the Big Lake trend. The well encountered several showings of oil and penetrated an Ordovician section very similar to the productive zones at Big Lake, but was abandoned when sulfur water was encountered at 8041 feet. 2. Gulf Production Co., McElroy No. 103, in the McElroy Field, Upton County. The well was drilling at 8553 ft. at the close of the year in beds of probable pre-Permian age. The test is an important one because it should prove or disprove deep production in the Church-Fields-McElroy pools and also throw geologic light on the deep possibilities of other fields in the western part of the Permian Basin. 3. Humble Oil and Refining Co., White and Baker No. 1, in Pecos County, about 11 miles west of the Yates field. The well is on a nonproductive Permian high and should indicate the deep possibilities of the Yates field. At the end of the year, drilling had progressed to 7200 ft., where beds of pre-Permian age are believed to have been penetrated. The major fields in West Texas, in which present-day proration had its inception, were produced under increased restrictions. A date of importance in the proration history of the area was $ept. 8, 1933, when the Railroad Commission issued an order placing all producing wells under proration. The severe reductions in total outlet made during 1933 were well compensated for by a more than threefold increase in the price of crude oil. Acid treatment was one of the general engineering developments of interest. The work had not progressed sufficie~ltly at the close of 1933

Jan 1, 1934

By J. Blodget Britton

IN the Journal of the Franklin Institute for May, 1870, there is published a description of a Colorimeter, together with a modification of the method proposed by Professor Eggertz, for determining combined carbon in iron and steel. An instrument of the kind there described, but of a little higher range, though in other respects not differing materially from the one originally made and used in the Iron-Masters' Laboratory, I now submit to your inspection ; and I propose, also, to make some determinations with it for the purpose of showing how quickly they may be made, and enabling you to form some judgment of what reliance can be placed in the results. Professor Eggertz proposed only a single standard, and the solution to be tested should be diluted to exactly correspond in color with that of the standard, and the per cent. of carbon calculated after carefully noting and making allowance for the measures of water used in diluting. In practice, difficulty was found in bringing the color of the normal solution down to the exact shade of the standard ; also other difficulties were met with in conducting the process, causing delay and interfering with the accuracy of the results. To materially overcome these, and after numerous attempts, an instrument such as is now before you suggested itself to me; and also I concluded to use a larger quantity of metal than directed by Eggertz, and, in addition, to filter the solution from its insoluble matter before making the comparison ; and, more recently, to use an acid of just such strength as would completely dissolve the metal without the application of heat. Experimenting with these changes from the original method I obtained reasonably good results. The instrument, you will observe, consists of a series of tubes, sixteen in number, two and a half inches long, and about half an inch in diameter, standing upright, and securely fastened in a light, portable, walnut-wood frame, but separated one from the other so as to allow just sufficient space between to place for comparison the tube containing the solution to be tested. The tubes are filled with

Jan 1, 1873

By Norman Brown, Victor V. Damiano

ThE present paper proposes a mechanism of dislocation multiplication at internal inclusions or cavities and presents experimental evidence of such sources in zinc. Using an etching technique recently described by Damiano, Tint, and Herman1 to study the three-dimensional aspects of dislocations in bulk zinc crystals, an investigation was made of helically shaped and closed-loop etch patterns found to be associated with inclusions. Crystals containing 0.1 pet Cd and grown from the melt were deformed slightly by bending and then aged at room temperature to precipitate cadmium at the dislocations. The crystals were cleaved along the (0001) plane and then etched with Gilman's2 etch. Crystals were continuously viewed on the (0001) plane while the etching was in progress and numerous helical and closed-loops etch patterns were continuously recorded as shown in the sequences printed directly from the cine film in Fig. l(a) and (6). These etch patterns are not to be confused with the etch patterns previously reported by Damiano and Herman3 which revealed dissolution spirals on the (0001) plane of high-purity zinc crystals. In the present case, precipitates arranged in the form of closed loops or helicies are progressively uncovered by etching after suitable aging of cadmium doped zinc crystals. Viewed with dark-field illumination as shown in Fig. 2, portions of a helical figure and subboundaries were revealed simultaneously. Continuous viewing while the etching was in progress revealed in Fig. 1(b) that the short line segments observed on single photomicrographs were in fact continuous and described a helix which had its terminus at an inclusion. The observations suggested that a dislocation once nucleated at the interface between the inclusion and matrix may act in such a way as to produce ad-

Jan 1, 1964

By Henry N. Toler

Activity in the search for oil and gas in Mississippi was greater than it had been for several years. Interest manifested and exploration work in wildcat areas were at an all-time peak. Drilling activity in the state's two proven fields continued to decline; there being only four wells drilled in the Jackson field during the year. At the end of 1937 it seems very likely that 1938 will be a big year in the search for oil in Mississippi. Deilling Activity Jackson Gas Field.—The four wells drilled in the Jackson field during 1937 resulted in three producers and one dry hole. Nine producing gas wells were abandoned during the year because of salt-water encroachment. The total production for 1937 was 14,248,000,000 cu. ft., which was a billion and a quarter increase over 1936, the highest year prior to 1937. The grand total produced from the field is 72,341,000,000 cu. ft. of gas and over 15,000 bbl. of oil. The three wells that had produced oil the past few years were also abandoned during the year because of the small quantity of oil and the large volume of salt water.

Jan 1, 1938

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By Theron Wasson

No major oil-field discoveries were made County; the second in Marion township, in Michigan during the year 1940. Produc- Osceola County. Both are producing from tion for the year was maintained by the Stray sand at about 1350 ft. These discoveries made in 1938 and, as a result, is fields are on structures founci by core test-below the total for 1939. Several extensions ing through the glacial drift. The Six Lakes to old fields have been made, which have field, Montcalm County, discovered in helped to maintain production in the face 1934, is Michigan's largest gas-producing of rather rapid decline in the fields of the field. it has 195 wells producing from the southwestern part of the state. Important Michigan Stray sandstone and the Upper extensions were made in Overisel, Porter, Marshall sandstone. This field was devel-Sherman, and Adams fields. Important oil oped on a 40-acre spacing plan, and gas fields of the state are shown on the -map, Fig. I. WiI~dcat Drilling Michigan's production of 19,700,000 bbl. A test in sec. 29, Winterfield township, during 1940 was 3,800,000 bbl. less than Clare County, which is producing oil from the total for 1939, but about one million the Monroe of Devonian age at a depth of greater than 1938. This brings the total 3760 ft., and a well in sec. 31, Lincoln accumulated production for the state to a township, Osceola County, producing from little over 145,000,000 bbl. the Monroe at 3625 it., should be classed as wildcats that are sure to lead to further Active Oil Fields development in I94L The leading producer for the year was the At the end of the year the Gulf Refining Temple field, Clare County, where 29 new Company's deep test on the Kawkawlin wells were drilled. The Walker field, Kent structure in Monitor township, Bay County, was second, but drilled 183 new County, was preparing to drill deeper after wells in order to gain that position. In the having had a gas blowout from a depth of extension of the Overisel field in Allegan 7775 ft. This test is the most important one County, 115 new producers were drilled. drilling at the end of the year in Michigan, The Adams field, Arenac County, was for should it develop commercial produc- revived by several wells with initial production from deeper beds it will lead to deeper tions of over 1000 bbl. per day from the drilling on many well-known structures Dundee of Devonian age. that have been producing from shallower sands. Active Gas Fields Two important gas fields were discovered Exploration by Taggart Brothers during the year. The A small amount of reflection seismograph first was in Riverside township, Missaukee work was done in Clare, Osceola, and Glad-Win Counties during the year. Exploration Manuscript received at the office of the Institute March 28 1941 by shallow drilling for structural informa- tion on beds below the glacial drift con- 347

Jan 1, 1941

By Theron Wasson

No major oil-field discoveries were made County; the second in Marion township, in Michigan during the year 1940. Produc- Osceola County. Both are producing from tion for the year was maintained by the Stray sand at about 1350 ft. These discoveries made in 1938 and, as a result, is fields are on structures founci by core test-below the total for 1939. Several extensions ing through the glacial drift. The Six Lakes to old fields have been made, which have field, Montcalm County, discovered in helped to maintain production in the face 1934, is Michigan's largest gas-producing of rather rapid decline in the fields of the field. it has 195 wells producing from the southwestern part of the state. Important Michigan Stray sandstone and the Upper extensions were made in Overisel, Porter, Marshall sandstone. This field was devel-Sherman, and Adams fields. Important oil oped on a 40-acre spacing plan, and gas fields of the state are shown on the -map, Fig. I. WiI~dcat Drilling Michigan's production of 19,700,000 bbl. A test in sec. 29, Winterfield township, during 1940 was 3,800,000 bbl. less than Clare County, which is producing oil from the total for 1939, but about one million the Monroe of Devonian age at a depth of greater than 1938. This brings the total 3760 ft., and a well in sec. 31, Lincoln accumulated production for the state to a township, Osceola County, producing from little over 145,000,000 bbl. the Monroe at 3625 it., should be classed as wildcats that are sure to lead to further Active Oil Fields development in I94L The leading producer for the year was the At the end of the year the Gulf Refining Temple field, Clare County, where 29 new Company's deep test on the Kawkawlin wells were drilled. The Walker field, Kent structure in Monitor township, Bay County, was second, but drilled 183 new County, was preparing to drill deeper after wells in order to gain that position. In the having had a gas blowout from a depth of extension of the Overisel field in Allegan 7775 ft. This test is the most important one County, 115 new producers were drilled. drilling at the end of the year in Michigan, The Adams field, Arenac County, was for should it develop commercial produc- revived by several wells with initial production from deeper beds it will lead to deeper tions of over 1000 bbl. per day from the drilling on many well-known structures Dundee of Devonian age. that have been producing from shallower sands. Active Gas Fields Two important gas fields were discovered Exploration by Taggart Brothers during the year. The A small amount of reflection seismograph first was in Riverside township, Missaukee work was done in Clare, Osceola, and Glad-Win Counties during the year. Exploration Manuscript received at the office of the Institute March 28 1941 by shallow drilling for structural informa- tion on beds below the glacial drift con- 347

Jan 1, 1941

By G. S. Hume

As predicted a year ago, owing to the discovery in 1936 of crude oil on the west flank of the south end of Tuner Valley in the eastern foothills of Alberta, 50 miles southwest of Calgary, and the drilling activity that resulted, the production of crude oil in Canada during 1937 showed a very substantial increase over the previous year. The production from other parts of Canada is relatively small and shows slight variations only from year to year. The production of crude oil in Canada and the production in Alberta, the main producing Province, is shown in Tables 1 and 2.

Jan 1, 1938

By William Vietti

WEST TEXAS and New Mexico has been overshadowed by the develop-ment in East Texas to such an extent that the area has been placed on a settled production basis by most of the operators. Considerable develop-ment work on both proven and unproven acreage remains to be carried on, but the incentive, a ready and profitable market, has been lacking. The main characteristics of the fields in this area are so well known that they are not described again in this paper, which thus resolves itself into a statistical review of the more important production features of the area. Proration has been in effect during the year and has been rigorously applied with the full cooperation of all producers. Proration in West Texas and New Mexico is based in the more pro-ductive fields on a potential and acreage distrbution of the allowance to the individual wells or acreage units. Potentials are determined generally by a short production test of from 1 to 4 hr.; and the hourly rate is multiplied by 24 to obtain the 24-hr. production or rated potential of the separate wells. The potential values thus set up have been questioned by many production men who are not willing to concede that the instantaneous (hourly) capacity of a well to produce is its potential capacity for a day with all other wells in the pool producing at their capacity. However, the potential of a well determined as above remains its chief rating as a measure of the permeability in place and as an indication of the possible reserve feeding that well. , The acreage factor has made it unnecessary to overdevelop properties in order to obtain an allowance proportionate to neighbors who are willing to drill an excessive number of wells on a piece of acreage in the hopes of a quick drainage and a corresponding profit. Proration has resulted in an orderly development of many of the pools in this area on the base as out-lined above, resulting in more reasonable spacing of wells and the more even withdrawal of oil and the ensuing expectation of high recoveries.

Jan 1, 1933

By Theron Wasson

The Central Michigan area held first place in the state during the year. Midland and Isabella, the leading counties in 1932, produced most of the oil in 1933. The Porter field southeast of Mt. Pleasant and along the same structural trend saw the greatest drilling activity. In Porter during the year 117 new wells were drilled. Under proration these wells produced 3,583,617 bbl., or nearly one-half the total for the state, which has been estimated at 7,947,695 bbl. The Porter field is already outlined on all sides except the northwest. It probably reached its peak in 1933. Unless a new field of some magnitude is developed in 1934, Michigan will see a continuous decline. The Greendale extension to the old Mt. Pleasant field furnished the new flush for 1932. In 1933

Jan 1, 1934

By R. A. Garling

INTRODUCTION Since the infancy of in situ uranium mining, a growing number of hydrometallurgical processes have been incorporated into pilot and commercial scale flowsheets. Although initial design efforts were geared toward maximizing uranium recovery and minimizing plant and wellfield flow circuit maintenance, recent emphasis has shifted to improved means of water conservation and aquifer restoration. As mining units approached depletion, evaporation ponds reached minimum freeboard, and state and federal agencies demanded proof of groundwater restoration, processes including mixed bed and conventional ion exchange, reverse osmosis and electrodialysis were adopted by the industry. These units served the additional function of reducing process bleed flows during mining in states where the deep disposal well permitting ice remains unbroken. This report concerns the use of electrodialysis as an alternative to the more conventional processes used in in situ mining. In addition to a brief history and description of the process, a comparison to reverse osmosis and operational data derived from testing an Ionics, Inc. 1.31 x 10-3 m /s (30,000 gallon/day) unit at the Teton-Nedco Leuenberger Research and Development pilot will be presented. HISTORY Commercially practicable electrodialysis was contingent upon the development of synthetic ion exchange membranes in 1940's. In 1952, Ionics Inc. demonstrated that the process was amenable to the treatment of salt and brackish water and, in 1954, made their first commercial sale. The following decade saw several major electrodialysis unit sales which were generally targeted for use on private or municipal potable water treatment. Major increases in membrane desalting unit capacities, facilitated by technological advances in the reserve osmosis industry, were noted during the 1970's. The development of polarity reversing electrodialysis equipment which reduced feed pretreatment requirements, increased water recovery rates, and simplified unit operation, kept Ionics Inc. competetive in the water treatment industry. Engineering advances which incorporated automated equipment, non-corrosive construction materials, and improved ion exchange membranes allowed the electrodialysis process to compete in industrial waste treatment among other commercial markets. PROCESS AND APPARATUS DESCRIPTION The electrodialysis process utilizes direct electrical current passed across a stack of alternating cation and anion selective membranes in order to achieve an electrochemical separation of ionized materials in an aqueous solution. The membrane stack has the appearance of a plate and frame filter press and auxilliary equipment includes solution pumps, electrically actuated valves, filters, piping and a direct current power source. The ion separation membranes are thin sheets of synthetic cation or anion selective resins. Attaching sulfonate or quaternary ammonium groups to the cross linked copolymer structure determines the ion selectivity of the membrane. The membranes are separated from each other in the stack by non-conductive spacers that house flow channels which route the flow tortuously and parallel to the membranes. Direct electrical current passing perpendicularly to the membranes and solution passages attracts cations toward the cathode and anions toward the anode (Figure 1). As the ions from the feed stream pass through the ion selective membranes, they become concentrated in the adjacent brine channel and are retained there by the combined attractive force of the electrode and the repelling force of the next membrane toward the electrode. Limiting factors on the degree of demineralization possible include chemical solubilities in the brine flow and the current density that will produce an unacceptable degree of polarization (Figure 1). Feed or brine solution treatment with complexing agents or acids has been successfully applied to prevent membrane scaling. Polarization can occur when sufficient current density is applied to dissociate water in the ion depleted region of the diluting compartments near the membrane surfaces. Significant polarization is evidenced by large electrical resistances across cell pairs and notable pH differences between diluting and concentrating streams. Limiting current densities have been increased in U.S. manufactured equipment by utilizing tortuous flow paths of relatively high linear velocities thereby promoting continous solution mixing. Energy consumption is due to separating electrolytes and solutions, oxidation and reduction reactions occurring in electrode compartments, overcoming electrical resistance, conversion from AC to DC power, solution pumping and auxiliary equipment actuation. A major improvement to the basic electrodialysis process was applied in 1970 which resulted in frequent, automatic cleaning and descaling of membrane surfaces. The process, polarity reversal, incorporates alternating the cathode and anode on a periodic basis while exchanging product and brine flow channels via electrically actuated values. The reversal reduces the potential of stack plugging with CaCO3 (calcite), CaSO4 (gypsum), and colloidal materials and, in most waters, eliminates feed pre-treatment requirements. For approximately two minutes during and following the reversal, off spec. water is flushed to waste or reintroduced to the feed supply. The usual feed treatment on polarity reversing electro-

Jan 1, 1982

By Cornelius J. Dwyer

It is possible to hold a very optimistic view of the future of the U.S. coal industry, and there are those in the coal industry who generally choose to do so. For example, a major coal company stated recently in its annual report, "Coal's prospects appear brighter today than at any period in the past." In order to continue in this state of euphoria, it is only necessary to remind oneself of the following "facts":

Jan 7, 1967

By T. Egleston

During the last winter we have been actively engaged in the School of Mines in search for boracic acid. This has been owing to the fact that Mr. M. W. Iles, assistant in the qualitative laboratory, has discovered a test for that substance which makes its discovery exceedingly simple instead of being, as previously, very difficult. It consists in powdering the mineral, calcining it, then moistening it with sulphuric acid, and heating on a platinum wire until the sulphuric acid is expelled. It is then moistened with glycerin and made to take fire. If boracic acid is present it infallibly gives a green flame. It is not at all surprising, under such circumstances, the test being so easy, that boracic acid has been found by the students in a great many cases where its presence was not previously suspected, and in some where its detection was previously too difficult to warrant looking for it. We were not prepared, however, for its discovery in Lake Superior iron ores, and were disposed at first to think that a mistake had been made. After, however, it had been frequently reported in these ores it was considered worth while

By Dewitt T. Ring

Reliable and detailed data covering the enormous number of wells drilled and the long historical production of the state, many of which were never recorded until recent years, render it impossible to gather statistical material suitable for the Institute's standardized form. The total production of crude oil in Ohio for the year was 3,654,503 bbl., which is less than the total production in the United States for the peak day of August 1937. For a period of eight years, from 1895 to 1902 inclusive, Ohio produced more oil than any other state. During the year, 1271 tests were drilled in the state, or 114 more than in 1936. Of these, 317 were oil wells, with an initial production of 7088 bbl., an average of 22.3 bbl. per well; 503 were gas wells, with an initial open flow of approximately 222,441 M cu. ft., or 443 M cu. ft. per gas well drilled; 451 were dry holes, that is, 35 per cent of the total completions. A number of factors account for the steady decline of oil production in Ohio. In the state, at the close of thc year, there were fewer than 28,122 producing oil wells. In 1936, there were 30,150 operated oil wells with an average yearly production per well of 126 bbl. The production for 1937 averaged 130 bbl. per well. During the year, 2028 oil wells were abandoned. In other words, old wells are being abandoned more than six times faster than new ones are being drilled. Since the inception of the oil and gas industry in Ohio, between 150,000 and 160,000 wells have been drilled in the state; new potential territory, offering desirable locations for either oil or gas, is becoming increasingly more difficult to find; the dry-hole percentage will continue to increase. Prices Another factor directly affecting the crude situation during the year was the matter of price and proration of Pennsylvania grade oil. The posted price for Pennsylvania grade in Ohio on June 7 was $2.37 per barrel; at the close of the year, it was $1.70 per barrel, or a reduction of 28 per cent in price. In addition to this price cut, a 50 per cent pro-

Jan 1, 1938

By C. D. Johnson

Exploration work in 1932 in the Rocky Mountain region, which includes the states of Montana, Wyoming, Utah, Colorado and New Mexico, resulted in the discovery of one new oil field, Cut Bank in Glacier County, Montana; one new gas field, Craig in Moffat County, Colorado; and the definite outlining of a second gas field, Piceance Creek in Rio Blanco County, Colorado, in which there had been drilled but one small gas well prior to 1932. During the year, 95 producing oil or gas wells were completed, giving new initial production amounting to 188,000,000 cu. ft. of gas and 176,420 bbl. of oil per day for the region. By far the largest part of this new production of both oil and gas was developed in southeastern New Mexico, mainly the Hobbs field. However, the Dry Creek field of Carbon County, Montana, contributed over 5000 bbl. of; new oil production. Sixty-two wells were abandoned during the year but of this number only 10 promising structures were nonproductive. The remaining 52 wells had little to recommend their drilling from a structural or strati-graphical standpoint. Eighty-eight wells were suspended in the region' during 1932 before the tests had reached their individual objective horizons. Many of these suspensions were due to financial difficulties and it is possible that several of the operations may be resumed at a later date. At the close of the year, 54 wells were actively drilling, 54 were shut down and there were 20 rigs and locations in the five Rocky Mountain states. The accompanying table gives details of drilling and production.

Jan 1, 1933