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By W. B. Plank, A. C. Callen

WAR and normalcy do not walk hand in hand, whether it be in industry, the educational field, or in the daily lives of individuals. Schools and departments offering curricula in mineral engineering have been seriously disrupted, beginning with 1942 and reaching a low during 1944. Selective Service regulations and voluntary enlistments have effectually stopped the flow of college-trained men into the mineral industry, and the flow into the colleges is little more than a dribble. The year just closed has been a most serious one for our institutions. Until March many of our faculties had been kept reasonably intact because of the large training programs of the Army and Navy. Although the number of

Jan 1, 1945

By David R. Maneval, H. B. Charmbury

At the turn of the century, iron and coal were the keys to industrial prosperity. At that time, Pennsylvania was the leading mineral producer in the Country, producing 200,000,000 tons of coal in a typical post-World War I year. Close to 90% of the Nation's energy was generated by coal. Today, coal accounts for but 22% of the energy generated, leading to a drastic reduction in Pennsylvania coal output. In contrast with the post-World War I days, 1964 figures showed a drop in production to 93,846,480 net tons. This huge decrease has created a serious economic problem in a state so much dependent on the coal industry. Along with the reduction in coal production, employment has dropped considerably through these years (the number of miners alone has gone from 280,011 to 43,149), thus causing a heavy burden of supporting the unemployed on the taxpayers. As far back as 1939, coal operators and economists saw the problems on the horizon and the need for improvement. Realizing that research was a way to improve and stabilize the industry they demanded legislative action. The Legislature reciprocated with a small grant to The Pennsylvania State University with the provision that each State research dollar be backed with one from the industry. This initial grant laid the foundation for the further growth in coal research.

Jan 3, 1966

A Discussion of the papers of James Gayley, on "The Application of Dry-Air Blast to the Manufacture of Iron" (see Trans., XXXV., 746, 1022, also pp. 315 and 745 of the present volume, and of J. E. Johnson, Jr., on "The Physical Action of the Blast-Furnace," p. 454. Chas. B. Dudley, Altoona, Pa.:—I am not a blast-furnace man, and this always puts me at a disadvantage because I cannot go into the details of the making of iron and steel. I have not the experience, and have to take the statements of other people, so what I say regarding the subject of this paper is not in the sense of an expert. When I first heard of Mr. Gayley's experiments, I said to myself, a I fear they will result in failure, since, apparently, Mr. Gayley has forgotten one chemical fact, namely, that carbon does not combine with oxygen in the absence of mater-vapor." This fact which was so astonishing when it was first brought out some years ago, and which those who are interested may find in the Journal of the Chemical Society of London, for 1885, page 349, and 1894, page 611, led me to think that the drying of the air would be a mistake. The general subject of the influence of water-vapor on chemical action is a large one; but the special point in which we are, for the moment, interested, namely, the influence of water-vapor on the combustion of carbon, was especially treated by Mr. H. B. Baker, in the papers referred to. Apparently, however, as the result of Mr. Gayley's experiments, we are to learn that the amount of moisture still left in the desiccated air is sufficient to secure perfectly satisfactory combustion. In thinking over Mr. Gayley's paper, it occurred to me that there were two alternatives, either of which might be chosen, namely, we might dry the air as Mr. Gayley does, or possibly we might, in a very much easier way, simply saturate the air at a constant temperature, and thus get uniform working and

Jan 1, 1906

By Carl F. Floe, Hung Liang, Michael B. Bever

DATA on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Sims1 have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan,2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett6 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid - iron were reported in 1910-1911 by Sieverts and Krumbhaar8 and by Sieverts.9 They found that 100 grams of iron absorbs 28 C.C. of hydrogen at 1550°C. and one atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 c.c. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon

Jan 1, 1946

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By R. Dawson Hall

LONG regarded as nearly worked out, the anthracite region still shows promise of a hundred years of life, for means are being found to get bottom, top, pillar, and other coal that earlier generations disregarded as too expensive to mine. Rock drivages and, still more, machinery are making it possible to get such coal. Mechanical methods enable the owner of thin beds to mine these with profit, and the miner recognizes that he must permit the use of machinery or the inexorable laws of economics will deny him opportunity to work. E. L. Dana, Jr., well outlines this situation, which in the past year became definitely established. Stripping also is recovering, safely and inexpensively, coal that past generations regarded as too hazardous and costly for mining.

Jan 1, 1935

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By E. S. Machlin, Morris Cohen

The isothermal formation of martensite in a 71 pct Fe, 29 pct Ni alloy is found to take place mainly by the nucleation of new plates rather than by the growth of existing ones, and is dependent on the temperature and time of the isothermal hold, the amount of atherrnal martensite present, the state of internal strain, and the application of tensile stress. The conclusion is reached that the isothermal nucleation is activated by thermal fluctuations superimposed on localized regions of very high strain. The reaction-path concept, involving martensite nucleation at strain embryos by athermal activation on cooling, or by thermal fluctuations on holding, reconciles the athermal and isothermal modes of transformation, and offers a unified picture of the kinetics of martensite formation. THE phenomenon of isothermal martensite formation has been the subject of considerable study lately,'-' and its reality has been thoroughly established. The existence of such isothermal transformation has been claimed to confirm the nucleation and growth hypothesis as applied to the martensitic reaction.1 " However, the isothermal formation of a martensitic phase is also compatible with the reaction-pathw escription of the transformation. The purpose of this investigation is to examine the isothermal mode of the martensitic reaction, both theoretically and experimentally, in order to test the likelihood of the above two mechanisms. Material and Methods The alloy used in this study contained about 71 pct Fe and 29 pct Ni. The complete analysis was 29.5 ± 0.2 pct Ni, 0.036 pct C, 0.02 pct N, 0.19 pct Mn, 0.09 pct Si, 0.008 pct P, and 0.006 pct S. The amount of isothermal transformation was determined by electrical resistance measurements using a Kelvin double bridge. The specimens were in the form of rods 1/16 in. diam x 4 in. long. Aus-tenitizing was performed at 1095°C for % hr either in a pre-purified nitrogen atmosphere or in an evacuated Vycor tube, followed by oil quenching to room temperature. After this treatment, the samples were completely austenitic, and the transformation studies were conducted at subatmospheric tempera- tures. Lineal analysis and X-ray determinations of retained austenite were used to calibrate the electrical resistance changes in terms of the percentage of martensite. The martensite range curve for this alloy is given in Fig. 9 of ref. 6. The M, temperature occurs at about -18°C (255°K). Reaction-Path Theory The nucleation and growth description of the martensitic transformation that occurs isothermally has already been given by Kurdjumow.','2 However, no comparable treatment exists using the reaction-path concept." Consequently this section presents the reaction-path description of the isothermal mode of the martensitic transformation. According to the latter theory, there is a reaction path (a strain) which describes the relative motion of the atoms during their transference from the austenitic to the martensitic state. The possibility exists, therefore, that the nucleation of a martensitic plate is accomplished by an embryo that comprises a state intermediate between that of austenite and martensite. This state may be attained within a finite volume by means of a homogeneous strain of the austenitic matrix. There is a free-energy barrier (F.) along the reaction path, corresponding to a critical strain in a critical volume. When activation is achieved, a spontaneous increase in strain and volume of the embryo takes place to generate the full-size martensitic plate. This mode of nucleation is to be distinguished from the more conventional mode involving embryos of the martensitic phase that merely grow in size by an interface motion. There are two ways whereby embryos in the austenitic phase can achieve the critical state of strain for isothermal nucleation: 1—through the formation of internal strains by plastic deformation or by stress; and 2—through thermal fluctuations, preferably superimposed upon existing internal strains. The activation free energy F,, must be supplied either mechanically by internal strains or thermally by energy fluctuations, or by a combination of both.

Jan 1, 1953

By Kenneth A. Gutschick, Robert S. Boynton

Lime has become a general and loosely used term to denote almost any kind of calcareous material or finely divided form of limestone or dolomite, as well as burned forms of lime. However, according to Webster, lime is only calcined limestone (known as quicklime, unslaked lime, or calcium oxide). It also embraces the secondary product of quicklime, i.e., hydrated lime or slaked lime (calcium hydroxide). There are two basic types of limestone used for lime manufacture-high calcium and high magnesium (dolomitic). The dolomitic quicklimes and hydrated limes correspond to their "high calcium" counterparts. The only difference is that the dolomitic types are a combination of the elements calcium and magnesium, in varying percents, whereas high calicum limes contain less than 5% MgO down to 1/2%. In either case a pure form of limestone of at least 97% combined carbonate content is needed to make salable lime, barring a few exceptions. The calcination of both types is diagrammed chemically as follows: [ ] In the foregoing reversible reactions the limestone is burned (calcined) in lime kilns, with the carbon dioxide content of the stone expelled as a gas. The weight loss during calcination of pure high calcium limestone is 44%; with equimolecular dolomitic limestone, the weight loss is 48%. Since lime has a strong affinity for CO_, particularly if moisture is present, it will readily revert to its original carbonate form. This occurs when quicklime "air-slakes" and adsorbs CO.. from the air. Thus, quicklime is perishable and should be stored in dry, water-tight areas. Depending upon the type of kiln used and the physical structure of the stone, the size of the quicklime may range from sandlike granules to 8 in. lumps. However, pebble sizes ranging from 1/4 in. to 2 in. are the most common. Screened quicklime fines are also com¬pressed (pelletized) into 1 in. pellets. For some purposes ground or pulverized forms of quicklime are used, ranging from No. 10 mesh to dust. Generally a pebble of quicklime is about the same size as the pebble of limestone before calcination (perhaps shrinking slightly). A more stable form of lime is hydrated lime. This is obtained by adding water to quicklime, slaking it into a dry, fine, subsieve size white powder. Because its affinity for moisture has been satisfied, it is not vulnerable to further moisture like quicklime. However, it has the same strong affinity for CO_. The following reversible chemical reactions illustrate how hydrated lime when heated (or dehydrated) can revert to the original oxide form:

Jan 1, 1975

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By Owen Thornton

Recently equations have been presented by Rose and Bruce' and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"' multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately': — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By Owen Thornton

Recently equations have been presented by Rose and Bruce' and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"' multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately': — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By John D. Price

R. W. Campbell (Jones and Laughlin Steel Carp., Pittsburgh)—As usual John Price has presented an excellent paper. I know of no one who has devoted more time and conscientious thought to this subject than he has, and his efforts have produced scientific data and conclusions of real value. Results of similar studies made by the Jones and Laughlin Steel Corp. on the blending of Pennsylvania coals may be of interest. During 1935 the late F. W. Wagner and the present writer developed an empirical physical fuel value formula for evaluating the combined physical tests of metallurgical coke, see Table IV. In the development of the formula, the tumbler test, shatter test, screen test, and porosity of coke have been taken into consideration. Each of these tests brings out some physical property not expressed by the others, and in estimation of the importance of these tests as a medium for evaluating coke for the blast furnace, their worth has been graded as follows: It was thought that some additional penalty should be applied to cokes that do not show a uniform screen size, assuming that coke larger than 4 in. was not desirable and that this size was an indication of irregular size. Therefore the screen test factor is further corrected by applying a penalty of 1 pct for each 1 pct material greater than 4-in. size as shown by the screen test. The physical fitness of coke for blast furnace use depends upon four fundamental characteristics: l—gen-era1 strength, as indicated by the shatter test; 2— abradability, or the resistance of cell walls to reduction in size by attrition, as indicated by the tumbler test; 3—porosity; and 4—size and uniformity. Each of these characteristics is not of equal importance, but surely, in an attempt to determine an accurate physical value, the individual value of each should be taken into consideration. The formula is used as a yardstick, so to speak, in determining variations in the normal production of metallurgical coke and in making comparisons between normal coke and experimental blends with other coals. Table IV gives results of coking tests on raw and washed high volatile coals and these same coals with blends of coke breeze, anthracite coal, char and low volatile coals, all from Pennsylvania. The table also gives the source of the coals and coke breeze, as well as their proximate analyses. It will be noted that the washing of the raw high volatile coal increased the physical fuel value from 26.17 to 39.16, showing the effect of removing shale and slate which produces a detrimental fracturing and weakening of the coke. It is a well known fact that many Pennsylvania high volatile coals contain an excess of resinous material or binder which has a tendency to weaken the coke, owing to its high evolution of gases during carbonization. Tests were therefore made with coke breeze, an inert material, in an attempt to alleviate this condition. Blends of washed coal with 5 pct and 7.5 pct coke breeze collected from the coke plant quenching sump (82.9 pct through 1/8-in. screen) resulted in cokes with a physical fuel value of 20.75 and 16.73 respectively, lower than results obtained from 100 pct raw high volatile coal. It will be noted that the percentage of + 4-in. coke increased but that the tumbler test was very low. Undoubtedly better results could have been obtained if the coke breeze could have been crushed extremely fine. During World War II the government asked the coking industry to consider the use of anthracite coal as a substitute for high quality low volatile coal, which was extremely scarce at the time. The next series of tests was made with blends of raw and washed high volatile coals and 5, 10, and 15 pct Pennsylvania No. 5 buckwheat anthracite (100 pct through l/8-in. screen). It was necessary to use some raw high volatile coal in these blends because of insufficient washer capacity at the time. It will be noted that the physical fuel values

Jan 1, 1954

Edward Dyer Peters, the only child of Henry Hunter Peters and Susan Barker Thaxter, was born in Dorchester, Mass., June 1, 1849. From his father he was a descendant of the Peters family of Ipswich and Andover, Mass., whose earliest ancestor settled in Essex County in 1659; while upon his mother's side he descended from several old Hingham families, as well as from the Quineys and from Governor Bradford. Between the ages of fourteen and sixteen he was a student at the Episcopal School for boys in Cheshire, Conn. Near the school was an old tin mine, and he used to spend his Saturday afternoons exploring it. When Edward was sixteen, his father sold his property in South-borough, and for the next three years lived in Europe. Sept. 26, 1865, Edward entered the Royal School of Mines at Freiberg, Saxony. In the summer of 1867 he joined his family on Lake Geneva, and spent a part of the season in that vicinity, going to Chamounix and taking other trips. Extract from a letter to his father: Elbingerode, Harz, Aug. 30, 1868: I left Freiberg with my friend Lilienthal, on Wednesday the 19th of August, reached Leipzig in the evening and spent the night in that city: the next morning we took the cars and in the afternoon reached Eisleben, in Prussia, which was to be our first stopping-place; there are immense copper-mines and smelting-works at this place, and the method of working the mines is very peculiar ... The next morning we got up at five and spent the whole day in the smelting-works where I obtained a number of drawings of the furnaces they use here and a good many valuable data. Saturday morning we got up at four o'clock, and descended a mine about three miles from the town; the Director of this mine was one of the most intelligent and agreeable men that I ever met; he accompanied us in the mine and explained everything that was new to us. The system of mining at Eisleben is peculiar to this town, and is not used at any other place in the world; the copper ore comes in narrow, flat veins eighteen inches high, at the utmost, consequently the men work lying flat on their left side and using the pick with both hands: the ore is carried out of the side passages into the main ones, in very low waggons about twelve inches high, and four by two feet; the boys who pull these waggons have a board buckled to their left thigh and their left arm; they pass their bare foot through a strap in the waggon and wriggle along on their side dragging the waggon after them, with their foot, almost as fast as a man can walk above ground. In the afternoon we walked over to Hittstadt, about twelve miles, and remained there Sunday and Monday. Monday night, at ten o'clock we went out to one of the smelting-works, to see the refining of the copper; this is only done at night, so we worked there from ten in the evening till eleven the next morning, and came home all blackened up and with blistered hands, for our skin was not quite so tough as that of the workmen: at noon the same day we took the stage to Ascherls-leben, and then the train to Stassfurt, where there are immense salt-mines, as well as factories for the manufacture of bromium, which latter process is, however, kept a profound secret, so we had very little hope of seeing anything but the salt mines; we were talking with our landlord about our disappointment, that evening, when he told us that the director of the Bromium works was sitting in the next room with no company but his glass of beer, so we went over to him, introduced ourselves as Americans, and actually succeeded in persuading him that it could do his business no earthly hurt if he showed us his works; at last he consented, after making us give our word of honor

Jan 1, 1919

By C. S. Finney, John Mitchell

The introduction of ovens for the production of metallurgical coke is believed to be due to L. L. Norton who operated an iron foundry in the vicinity of Connellsville, Pa. Persuaded by his foreman, an English immigrant named Nickols from Durham, L. L. Norton put up a 12-ft square oven which produced coke in 1833. The coal used was taken from a local mine at Mounts Creek. The oven seems to have been used in conjunction with the customary method of coking in mounds. It was in the Connellsville district also, in 1841, that two carpenters, Provence McCormick and James Campbell, formed a partnership with John Taylor, a stone mason, for the manufacture and sale of oven coke. The task of the mason was to construct the ovens, while the carpenters were to build the arks by which the coke could be taken by water to the market at Cincinnati. The following account of the enterprise was given by McCormick: "James Campbell and myself heard in some way that I do not now recollect that the manufacturing of coke might be made a good business. Mr. John Taylor, a stone mason, who owned the farm on which the Fayette coke works now stand, and who was mining coal in a small way, was spoken to regarding our enterprise, and proposed a partnership-he to build the ovens and make the coke and Mr. Campbell and myself to build a boat and take the coke to Cincinnati, where we heard there was a good demand. This was in 1841. Mr. Taylor built two ovens. I think they were about 10 feet in diameter. My recollection is that the charge was 80 bushels. The ovens were built in the same style as those now used, but had no iron ring at the top to prevent the brick from falling in when filling the oven with coal, nor had we any iron frames at the mouth where the coke was drawn. The top and mouth had to be repaired when they fell in. In the spring of 1842 enough coke had been made to fill two boats 90 feet long-about 800 bushels each-and we took them to Cincinnati down the Youghiogheny, Monongahela, and Ohio, but when we got there we could not sell. Mr. Campbell, who went with the boats, lay at the landing some two or three weeks, retailing out one boatload and part of the other in small lots at about 8 cents a bushel. Miles Greenwood, a foundryman of that city, offered to take the balance if he would take a small patent flour mill at $125.00 hi pay, which Mr. Campbell did. He had it shipped here. We tried it, but it was no good, and we sold it to a man in the mountains for $30.00, and thus ended our coke business." So successful did the coke subsequently prove to be in use that the three partners were asked to deliver more. Evidently they had had enough of the coke business, however, for they refused to have anything more to do with it. Few ovens were built between 1841 and 1855, and it is reported that in the latter year, "there were only 26 coke ovens along the river above Pittsburgh". Successful coke makers of these years included Mordecai Cochran, Richard Brookius, and Colonel A. M. Hill. It was the use of coke in 1859 in the Clinton furnace erected by Graff, Bennett and Co. in a plant on West Carson Street, Pittsburgh, that brought the real beginning of the coke-iron era in America. Here the successful use of Connellsville coke as a blast-furnace fuel was demonstrated beyond all possible doubt, and from the year 1859 the coking industry expanded tremendously. The era of beehive coke ovens During the latter half of the nineteenth century and the early years of the twentieth, the major percentage of metallurgical coke produced in the United States came from beehive ovens. It was not until 1893 that the first battery of by-product ovens came

Jan 1, 1961

By John B. Hastings

THE origin of the watery vapors of vulcanism has always been an object of interest and speculation to the seismologist, and as theories of the genetic origin of ore-deposits have of late years been pretty well narrowed down to the expiring forces of plutonic action, the same question has had a lively interest for mining engineers and geologists, as is well shown by the discussions of the subject in our Transactions. The important part taken by volcanic emanations in the origin of pegmatites and quartz-veins, described in my paper, Origin of Pegmatite,1 and their latent power to concentrate into useful deposits such scattered gold as occurs in the Hartsel granite, make a discussion of their derivation but a natural third and final step. It is conceded that enormous amounts of vapor accompany volcanism, though perhaps we are apt to forget that steam has 1,700 times the volume of water, besides which the column seen over Vesuvius and other volcanoes is greatly mixed with air; the immensity of such volumes compared with solids and liquids is shown by the experiment of Gautier, who, by heating dessicated granite to 100° C., evolved from it uses 20 times, and steam 90 times, its own volume. Dana appraised the average amount of water left in ordinary rocks as 2.5 per cent. T. M. Read estimated that the Mississippi river carries to the sea annually 150,000,000 tons of rock material. If these Mississippi sediments, as deposited, contained 20 per cent. of water, it would be 600,000,000 cu. ft., or 4,500,000,000 American gallons, annually. Allowing the vapor suspended over a volcanic cone to be mixed with 80 per cent. of air, this amount of water converted into steam would replenish anew, every 9 min., a column 15,000 ft. high, 2,000 ft. in diameter at the base, and 10,000 ft. at the top. Read's estimate is only half of the amount given in a more recent and probably correct one .2

Jan 5, 1908

By E. M. Wise

THOUGH known as the platinum-group metal- the sextuplet, platinum, palladium, iridium. rhodium, osmium, ruthenium, might well be called the American metals or perhaps Pan-American metals, as the ore containing them eras first discovered in South America, and in recent years the largest production has come from North America. The South American alluvial deposits, which also, contain gold, are in active production, as are the alluvial platinum deposits of Alaska, but the main production is from the copper-nickel ores of Sudbury, Ontario. The Russian deposits in the Urals were the source of most of the worlds platinum for about 100 years, but since 1934 have assumed second place. For a time considerable amounts of platinum came from several rather rich deposits in South Africa but these were exhausted quickly. However, a tremendous reserve of lower-grade ore exists there, which could be worked profitably if the price of platinum were considerably higher.

Jan 1, 1942

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936