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By H. T. Kennedy

The fact that intrusion of water into oil wells can be prevented by treating the sand adjacent to the well seems to have been only recently recognized. Swan1 mentions the process of solidifying naphthalene in strata. R. Van A. Mills2 recommends the use of materials such as sodium silicate and sodium carbonate, which react with oil-field water to form solid plugging agents. When a well is drilled in a new field the oil sands are found essentially devoid of water (Fig. 1). Unless a completely impermeable break exists over wide areas in the field, no water is found above the lower limit of the oil zone and no oil is found below the upper limit of the water zone. After considerable oil has been taken from the well, however, it is almost universal experience that water intrusion occurs. This intrusion may be of two kinds. The water may follow a path parallel to the bedding planes of the producing formation through loose streaks in the pay sand, as shown in Fig. 2, or the water level of the field may rise and enter the well by coning (Fig. 3). Water entering from the side is called "edge water," and that coming in from the bottom is called "bottom water.'' Effectiveness of any method for shutting off water depends not only on the effective treatment of the sand adjacent to the well but on

Jan 1, 1936

By H. T. Kennedy

The fact that intrusion of water into oil wells can be prevented by treating the sand adjacent to the well seems to have been only recently recognized. Swan1 mentions the process of solidifying naphthalene in strata. R. Van A. Mills2 recommends the use of materials such as sodium silicate and sodium carbonate, which react with oil-field water to form solid plugging agents. When a well is drilled in a new field the oil sands are found essentially devoid of water (Fig. 1). Unless a completely impermeable break exists over wide areas in the field, no water is found above the lower limit of the oil zone and no oil is found below the upper limit of the water zone. After considerable oil has been taken from the well, however, it is almost universal experience that water intrusion occurs. This intrusion may be of two kinds. The water may follow a path parallel to the bedding planes of the producing formation through loose streaks in the pay sand, as shown in Fig. 2, or the water level of the field may rise and enter the well by coning (Fig. 3). Water entering from the side is called "edge water," and that coming in from the bottom is called "bottom water.'' Effectiveness of any method for shutting off water depends not only on the effective treatment of the sand adjacent to the well but on

Jan 1, 1936

Jan 1, 1966

By E. C. Harder

J. T. SINGEWALD, JR., Baltimore, Md.-I might say a word further in regard to the Miguel-Burnier district. I am sorry Mr. Harder is not here. I had hoped to be able to ask him a few questions in regard to some of the features of those deposits. This Miguel-Burnier district is the other district that I referred to that lies in the State of Minas Geraes. The interpretation that Mr. Harder gives to, these deposits is the same as that given by Harder' and Chamberlin in a previous paper, and that is that they consist of lenticular deposits of sedimentary origin in a series of rocks that also include lenses of limestone, but they seem to think that the manganese ores occur at a definite horizon and at a horizon different from the limestone. We found that the manganese ores occur at several horizons, as also do the limestone lenses, and the limestone masses are of the same shape as the manganese orebodies, so that our own feeling was that these manganese ores simply represent concentrations within the zone of oxidation formed as. a result of decomposition and replacement of this limestone. To the east of Miguel-Burnier there is a big bend in the railroad which cuts through, at right angles to the strike, this series of rocks. Here is shown very well both the local character of the limestone lenses and the local character of the manganese lenses in that, though the distance across the bend is only a couple of hundred yards, the limestone and. ,manganese lenses do not match up at all, and it also shows plainly that both occur at more than one horizon.. Consequently there is no reason why the manganese ore could not represent alterations of this limestone. The mine workings do not as yet give very definite information on this point in that they are all comparatively shallow and within what would be the zone of oxidation so that what they will grade into below that depth, we do not know. On the other hand, the character of the ore suggests that it may, represent such -a product in the zone of oxidation in that it tends to be quite earthy; whereas, if the manganese had been there originally as such it would have undergone the same metamorphism that the other rocks have undergone and one would have expected that it would have been converted into a hard manganese ore that would today stand out pretty much as do the iron ores of that same region and not have the soft, earthy texture which is a prevailing characteristic.

Jan 4, 1917

By Wilson Lundy

THE history of the production of sulfur from salt domes in Louisiana and Texas originated with the operations of the Union Sulphur Co. at Sulphur, La., followed by the Freeport Sulphur Co. at Bryanmound, Tex. Including the present development of Grande Ecaille by the Free-port Sulphur Co., which constitutes the tenth dome to be equipped for the production of sulfur in the Gulf Coast, less than 10 per cent of all the known domes have proved to contain sulfur in commercial quantities. The Grande Ecaille salt dome is in the tidal marsh of the Mississippi River delta in Plaquemines Parish, Louisiana. It is 10 miles southwest of the right descending bank of the river approximately 45 miles below the city of New Orleans and is within 4 miles of the shore line of the Gulf of Mexico.

Jan 1, 1934

By R. W. Regehr, R. A. Burmeister

Epitaxial growth of GaAs 1-xPx on germanium substrates was achieved using an open tube vapor transport system. The compositional range of 0.3 < x < 0.4 was examined. The best results were obtained with (311) orientation of the germanium substrate. The physical and chemical properties of the resulting layers were investigated using several techniques. Spectrographic analyses of the layers indicate substantial incorporation of germanium into the GaAs t-X Px layer. Evidence is presented which indicates that this incorporation occurs via a vapor phase transport process rather than by solid phase dijfu-sion. Electrical measurements suggest that the germanium thus incorporated behaves predominantly as a deep donor in the compositional range of 0.33 < x * 0.40 and has a deleterious effect upon the luminescent properties of GaAs1-x Px. The increasing technological importance of GaAs1-xPx for use in light-emitting devices has led to an evaluation of several aspects of existing growth processes. The method most commonly used to prepare GaAs1-xPx for electroluminescent device applications is vapor phase epitaxial growth on GaAs substrates.&apos;-4 In a typical electroluminescent diode structure the active region of the diode is entirely within the epitaxial layer and thus the electrical properties of the substrate are relatively unimportant since it is effectively a simple series resistance (assuming hetero-junction effects to be negligible). The use of germanium rather than GaAs as the substrate material is of interest for several reasons. First, GaAs of reasonable structural quality has been epitaxially grown on germanium4-2 and it is reasonable to expect that GaAs1-xPx could subsequently be deposited on the GaAs layer. Second, germanium substrates are readily available with both lower dislocation densities and larger areas than GaAs. Finally, single crystals of germanium are more economical than GaAs single crystals. The principal objective of the present investigation was to test the feasibility of growing GaAs1-xPx epi-taxially on germanium substrates, and to evaluate the properties of such layers with regard to electroluminescent device requirements. The approach used was to a) demonstrate epitaxial growth of GaAs1-xPx on germanium, and b) characterize the relevant structural, electrical, and optical properties of the GaAs1-xPx layers. The possibility of germanium incorporation into the grown layers was of special interest since there was some indication of this in previous studies of GaAs growth on germanium.5&apos;11,12 Although a study of the electrical properties of germanium in GaAs1-xPx was not an intent of this investigation, several features of the electrical properties of the layers grown in the present study which appear to be due to germanium are described. EXPERIMENTAL PROCEDURE The open-tube vapor transport system used for the epitaxial growth of GaAs1-xPx is illustrated in Fig. 1. This system utilizes the GaC1-GaC13 transport reaction and is similar in most respects to the larger system described elsewhere.&apos; The germanium substrates were n-type, with a resistivity of 40 ohm-cm (Eagle-Picher Co.). These were cut to the orientations of {100), {111), and (3111, and were mechanically polished and chemically etched in CP-4 (5 min at 0°C) prior to growth. In some cases, a GaAs substrate was employed in addition to the germanium. The orientation of the latter was {loo}, and they were also mechanically polished and chemically etched prior to growth. The initial composition of the deposited layer was pure GaAs. After approximately 10 microns of GaAs was deposited on the germanium substrate, the phosphorus content of the layer was gradually increased over a distance of approximately 15 microns to the desired concentration and maintained at this value throughout the remainder of the growth. Typical operating parameters used during growth are given in Table I. Selenium was used as a n-type dopant in several runs to facilitate comparison of the electrical properties of the layers grown on germanium with those of layers grown on GaAs substrates, which are usually doped with selenium. The concentration of H2Se in the gas phase was adjusted to a value which would normally yield a carrier density of 1 to 5 x 101 7 at room temperature in layers grown on GaAs substrates. The terminal surfaces of the epitaxial layers were examined by optical microscopy for structural characteristics. Laue back-reflection photographs (Cu radi-ation) were also made on the terminal surface to verify the epitaxial nature of the deposit. After these steps

Jan 1, 1970

1-Iron and Steel JOHN A MATHEWS, Chairman Ralph H SWEETSER Vice-chairman WILLIAM CAMPBELL, Vice-chairman MAX ROESLER, Secretary Iron Ore CHARLES B MURRAY, Chairman R C ALLEN W O HOTCHKISS MAX ROESLER ERNEST F BURCHARD THOMAS T READ DWIGHT E WOODBRIDGE M M DUNCAN WILLIAM KELLY CARL ZAPFFE C T FAIRBAIRN CHARLES F RAND

Jan 1, 1923

By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961

By Michael Tenenbaum

The importance of semikilled steel as a high tonnage grade has long been recognized. The increasing severity of the applications for which semikilled steel is used makes it desirable to obtain further information regarding the features of open hearth practice and ingot structure that can affect steel performance in subsequent rolling and fabricating operations. Accordingly, an investigation is being carried out studying the structure of various types of semikilled steel ingots. This paper reviews some of the observations made and information gathered in this investigation. By definition, semikilled steel may be considered to include all nonrimming steels in which the natural shrinkage occurring during ingot solidification is offset to an appreciable degree by gas formation. Accordingly, this type of steel includes the entire range intermediate between rimmed and fully killed steel. The resultant ingot structures range from those of steels that have been capped to suppress a weak rimming action to those steels that have been killed in the furnace or ladle to the extent that no mold deoxidizer is required. A survey reported to the 1946 -AIME Open Hearth Conference&apos; reviewed the practices being used at 28 major plants for the deoxidation of semikilled steel. It was found that most plants divide the deoxidizing additions between the ladle and the mold—many of the plants adding only minor amounts of deoxidizer to the bath or none at all. Silicon, aluminum and titanium were the only elements used for ladle and mold deoxidation. Mold deoxidizers were added as capping additions or as uniformly fed additions. Several practices were reported in which the steel was deoxidized in the ladle to the extent that little or no mold deoxidation was needed. No reference was made to grades capped by using special mold designs or special closures over the top of molds. .Accordingly, specific examples of this type of practice will not be considered in this paper. It appeared from this survey of deoxidation practice that semikilled steel can be divided into three types, namely, capped semikilled, in which aluminum is added near the end of pour or after shut-off, intermediate semikilled steels, in which aluminum is fed uniformly throughout the pour, and semikilled steels requiring no mold deoxidation. In an attempt to cover the ingot structures obtained by the range of practices reported in the preceding survey, three series of experimental heats were made using increasing amounts of aluminum, silicon and titanium for ladle deoxidizers. The ladle deoxidizers were added as stick aluminum, 50 pct ferrosilicon and 20 pct ferrotitanium (4 pct carbon), respectively. Two methods of studying ingot structures were used. Ingots were removed from production, burned longitudinally and machined to allow observation of the central pipe and coarse blowholes. During the machining operation much of the finely porous subsurface structure was obliterated. Accordingly, observations were also made

Jan 1, 1949

By Michael Tenenbaum

The importance of semikilled steel as a high tonnage grade has long been recognized. The increasing severity of the applications for which semikilled steel is used makes it desirable to obtain further information regarding the features of open hearth practice and ingot structure that can affect steel performance in subsequent rolling and fabricating operations. Accordingly, an investigation is being carried out studying the structure of various types of semikilled steel ingots. This paper reviews some of the observations made and information gathered in this investigation. By definition, semikilled steel may be considered to include all nonrimming steels in which the natural shrinkage occurring during ingot solidification is offset to an appreciable degree by gas formation. Accordingly, this type of steel includes the entire range intermediate between rimmed and fully killed steel. The resultant ingot structures range from those of steels that have been capped to suppress a weak rimming action to those steels that have been killed in the furnace or ladle to the extent that no mold deoxidizer is required. A survey reported to the 1946 -AIME Open Hearth Conference&apos; reviewed the practices being used at 28 major plants for the deoxidation of semikilled steel. It was found that most plants divide the deoxidizing additions between the ladle and the mold—many of the plants adding only minor amounts of deoxidizer to the bath or none at all. Silicon, aluminum and titanium were the only elements used for ladle and mold deoxidation. Mold deoxidizers were added as capping additions or as uniformly fed additions. Several practices were reported in which the steel was deoxidized in the ladle to the extent that little or no mold deoxidation was needed. No reference was made to grades capped by using special mold designs or special closures over the top of molds. .Accordingly, specific examples of this type of practice will not be considered in this paper. It appeared from this survey of deoxidation practice that semikilled steel can be divided into three types, namely, capped semikilled, in which aluminum is added near the end of pour or after shut-off, intermediate semikilled steels, in which aluminum is fed uniformly throughout the pour, and semikilled steels requiring no mold deoxidation. In an attempt to cover the ingot structures obtained by the range of practices reported in the preceding survey, three series of experimental heats were made using increasing amounts of aluminum, silicon and titanium for ladle deoxidizers. The ladle deoxidizers were added as stick aluminum, 50 pct ferrosilicon and 20 pct ferrotitanium (4 pct carbon), respectively. Two methods of studying ingot structures were used. Ingots were removed from production, burned longitudinally and machined to allow observation of the central pipe and coarse blowholes. During the machining operation much of the finely porous subsurface structure was obliterated. Accordingly, observations were also made

Jan 1, 1949

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,&apos; and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.&apos;.&apos; Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett&apos;s No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

Discussion of the paper of E: D. Gardner, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 91, July, 1914, pp. 1467 to 1471. H. V. WINCHELL, Minneapolis, Minn.-There are two questions I should like to ask: First, does the Department still adhere to the decision made in the East Tintic case? Second, does the Department require placer ground to he of such value that, in the opinion of the Forest Service employees, it will pay to work, before admitting the location to be valid? T. C. HOYT,* Ogden, Utah.-With reference to the first question: the Department does not hold to that decision, as it was reconsidered by the Secretary Of the Interior, and the Department is governed by the decision of the Secretary Of the Interior, on those points always. The Department of Agriculture makes no decision as to what constitutes a sufficient discovery. The mineral examiners simply report their findings and Opinions. These are transmitted to the chief of the field division of the General Land Office, who in turn transmits the reports to the Commissioner Of the General Land Office, who decides whether the report raises an issue requiring a hearing. If a hearing is ordered, expert testimony is given on the question of the discovery, as well as the evidence of practical people who operate in the vicinity of the claim in question. As to the extent of placer values considered sufficient to justify a location, my answer will need a little amplification. I couldn&apos;t answer it directly for the reason that sometimes people resort to placer claim location as a means of acquiring land for Other purposes than placer mining, which makes it absolutely necessary that the government give close attention to the question of whether good faith has been shown, as it is the evidences of good faith that largely determine whether a report adverse to a claim shall be made. That is a difficult point to cover sometimes. For instance, in the region I have recently visited there are some 17 miles of a valley, from ¼ to ¾ mile in width, all covered by placer locations. It is valuable stock-grazing land, and is stocked at the present time. It also contains a stand of timber, and is on the watershed of an important stream-important from the fact that it furnishes the water supply to government storage reservoirs, and to pending reclamation and Carey Act projects. In this case the placer claims will not be disturbed as mere locations. They will simply remain there, and there will be no action with reference to them until the claimant asks for patent or, before patent, begins to denude that watershed and remove that timber. Then the government would direct that the mineral experts go on to the ground, examine it, prospect it, and submit their report, with a view to seeing if

Jan 11, 1914

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world&apos;s mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep-resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geologi-cal Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals. Coal, although it is one of the most important minerals, was omitted because, not more than one or two per cent of the world&apos;s production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

HAVING told you of the practices of the arts involving other metals, I wish to tell you also of the practice of that of tin.* Indeed, since this is an easily melted metal, in common use for the utensils which are made for human needs, it is an art known not only to skilled men but also almost to children, wherefore I could proceed with- out telling of it. However, besides the production of plates and bowls and many other dishes for eating from and keeping things in, this embraces two other arts, both of which you should know about because they are useful and beautifid. One of these is the art .of making the letters with which books are printed, and the other is that of making the sheets from which organ pipes are built. The vessels, as perhaps you have seen, are cast one by one in moulds made of white tuff. Several pieces fastened together are then put on the iron axle of a wheel rotated by hand, and [138v] they are turned with a slightly bent tool which has a cutting edge. In this way they are made thin and of a good shape. Then they are polished with a piece of linen cloth and a little powdered tripoli, and thus they are finished. The letters for printing books are made of a composition of three parts of fine tin, an eighth part of black lead, and another eighth part of fused marcasite of antimony.t The desired quantities of these metals are melted

Jan 1, 1942

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;&apos;-&apos; and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.&apos; The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-&apos; cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

The following additional notes about prices of coal in the early days were collected from the sources shown. Several data about canal tolls and labor conditions are also included. 1796, November: "The inhabitants lay it (coal) in at about 3;d. (83¢) sterling per bushel." (Ref. 73: p. 147.) 1804, March: "In March, 1804, I sent a person accustomed to mining to open the vein of coal, and to load the ark, which was accomplished, and early in the month of April the ark, with the first cargo of bituminous coal passed safely the Conewago falls, and landed her coal at Columbia, Lancaster County. The coal was sold at 31¢ per bushel at Columbia." ($7.75 per ton). This was the first coal from Clearfield County near the town of that name. (Letter from William Boyd: Pa. Senate Jour., 1833-1834, vol. 2, p. 561.) 1807: The following notice appeared in the Bedford Gazette: "Huntingdon, June 4. "Stone Coal.-Such of the farmers as wish to make experiment with stone coal as a substitute for plaster, in manuring their Indian corn, may be supplied with coal gratis upon application to Peter Hughes, at Mr. Riddle&apos;s mines, on the Raystown Branch. The proprietor of the mines offers not only to refund the carriage, but to pay the expenses of applying the coal, if upon a fair experiment it is found to be inferior to plaster, which now sells at two dollars per bushel." (Ref. 735: p. 708.) 1809: Coal was delivered in Pittsburgh at 5¢ per bushel or $1.25 per net ton. (Ref. 444: p. 50.) Coal was delivered in Connellsville at 4¢ per bushel or $1.00 per net ton. (Ibid.: p. 185.) 1810: Pittsburgh.-"Coal may be obtained of a good quality, ready delivered at 5¢ a bushel." ($1.25 per net ton.) (Ref. 315: vol. 2.) 1811: "It (coal) costs 6¢ a bushel at your door." ($1.50 per net ton.) (In Pittsburgh.) (Ref. 277: 1811, p. 68.) 1814: At Columbia, now part of Donors, Washington County, Pa., an original sale of lots in 1814 gave the purchaser of each lot the right to mine stone coal gratis from a bank on the property. (Ref. 410: vol. 1, p. 547.) "A laborer is able to dig upwards of 100 bushels per day." (4 tons.) (Ref. 277: 1814, p. 109.) A paper about the early newspapers in West Virginia says: "Collier Wanting. From 10 to 20 steady and industrious men, who understand digging coal, may obtain high wages in Kenhawa for that business, if immediate application is

Jan 1, 1942

By C. R. Wohrman

A MELT of pure electrolytic iron with about 0.4 per cent. sulfur and 7 per cent. manganese was prepared in connection with a study of inclusions in iron. The alloy darkened rapidly when etched with a 10 per cent. alcoholic solution of nitric acid, and microscopic examination revealed the presence of a semimartensitic, semi-Widmanstättian structure (Figs. 1 and 2) closely resembling the structures found by Benedicks in his artificially prepared "meteoric iron." 1 The structures found by Benedicks were readily explained by the presence in his alloy of the two well known iron-nickel solid solutions, taenite and kamacite, and of their eutectoid (?) aggregate, plessite. By analogy, one would infer the existence of similar phases in the iron-manganese alloy just described, such as inference being strengthened by the similarity displayed in many ways by nickel and manganese in their effects on iron. IRON-MANGANESE ALLOTS ARE REGARDED AS HOMOGENEOUS Heterogeneity of iron-manganese alloys has not been recognized heretofore, judging from the data of standard metallographic books and those of original papers. In fact, iron and manganese are quite generally regarded as completely miscible in the solid state. Dr. Rosenhain,2 for example, writes: Alloys of group (a), of which those of gold-silver, iron-manganese, and copper-nickel are examples, when allowed to crystallize sufficiently slowly to attain their condition of final equilibrium, present a microstructure exactly similar to that of a pure metal-the homogeneous character of the molten solution is in that case so completely maintained that the microscope cannot detect the presence of any second constituent.

Jan 1, 1927

By Hon. Tasker Oddie

DURING the closing days of the last Congress a resolution was passed, creating the Senate Com-mission of Gold and Silver Inquiry. The resolu-tion charges the Commission with the responsibility to investigate and report to the Congress on Jan. 1, 1924, upon the following subjects: 1. The causes of the continuing decrease in the production of gold and silver. 2. The causes of the depressed condition of the gold and silver industry in the United States. 3. The production, reduction, refining, transportation, mar-keting, sale, and uses of gold and silver in the United States and elsewhere. 4. The effect of the decreased production of gold and silver upon commerce, industry, exchange, and prices. The personnel of the Commission is as follows: Senators Pittman, Sterling, Goodling, Walsh and Oddie. At a meeting on May 8, H. N. Lawrie, a mining engi-neer and economist, was appointed as Assistant to the Commission. The present situation with respect to the gold and silver mining industries is well illustrated by the follow-ing data: The total world production of gold (in dollars) for 1915 was $468,724,918, and for 1921, $329,915,101; as shown by the reports of the U. S. Mint; and for the year 1922, $306,793,000, which is based oh a prelimi-nary estimate; this indicates a decrease of 34.5 per cent. between 1915 and 1922. The total world production of silver (in fine ounces) for 1915 was 178,850,000 oz.; for 1921, 175,268,234 oz., a decrease of 2 per cent.

Jan 6, 1923

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.&apos; is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968