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By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By G. Howell Clevenger

FORMERLY great divergence of opinion existed in regard to the influence of copper in steel, as affecting its various physical properties. More recently the investigations of Stead,1 Breuil,2 Wigham,3 Burgess and Aston,4 Ball and Wingham,5 Miiller,6 Dillner,7 and others have shown fairly good agreement in the major points. Copper steel has been shown by these investigators to possess special properties which make it valuable for certain uses. The general range of composition of the useful alloys of copper and iron, and of copper, iron, and carbon, has been quite definitely established, for the former by Burgess and Aston,8 and for the latter by Breuil 9 and Stead.10 Stead 11 has removed one difficulty in reconciling certain of the earlier data by calling particular attention to the influence of carbon in copper steels. Another point which caused confusion in the earlier investigations, particularly in regard to " red-shortness," was the presence of sulphur. Failure to note the presence of sulphur often led to attributing " red-shortness " to the presence of small amounts of copper. Turner 12 has called attention to the fact that where copper exists in an iron ore it often occurs as the sulphide, so that the presence of copper in steel made from such ores might also, necessarily, mean the presence of sulphur. It is evident that the effect in this case might be quite different than where pure copper was added.

Jan 10, 1913

By P. D. Frost, H. A. Robinson, J. R. Doig, M. W. Mote

The mechanism of hardening in heat-treatable zirconium alloys was foUNd to be analogous to that for titanium alloys. Zirconium containing a relatively large addition of a ß -stabilizing element such as molybdenum or columbium can be hardened by the following transformation: Lean alloys, having insufficient alloy content to retain ß at room temperature are hardened by the following transformation: Application of these findings in Zr-Mo-Sn and Zr-Nb-Sn alloys produced strengths as high as 190,000 psi with reasonable ductility. PRIOR research on zirconium alloys has been concerned with development of greater strengths and creep resistance by solid-solution hardening or by dispersion hardening. Although solution and aging heat treatments had been applied earlier to zirconium alloys, quenching frequently produced low ductility. The possibility that the ß-to-w transformation, discovered earlier in titanium alloys,' might also occur in zirconium alloys and cause low ductility was considered, and, indeed, was found as predicted2 to be the case. In the earliest experiments, the heat-treatment response of titanium, too, was disappointing. However, by avoiding the formation of the embrittling w phase, it became practical to obtain room-temperature strengths higher than 180,000 psi, with elongation values of 10 pct.3 Based on the present concept of titanium heat treatment, the principal requirement for a heat-treatable zirconium alloy is that it contains a certain minimum amount of one or more ß -stabilizing elements. Only molybdenum, columbium, and tantalum, when present in sufficient amounts, are known to stabilize ß zirconium to room temperature during rapid cooling from the ß field. Tantalum was undesirable because of its high thermal-neutron cross section. Aluminum and tin are effective a stabilizers, but aluminum has been shown to seriously decrease the corrosion resistance of simple zirconium alloys in hot water. Therefore, for the present study, tin was used as the stabilizer addition. The alloys selected for this evaluation are presented in Table 1 along with their analyses and ß-transus temperatures. The analyses indicated that intended compositions were usually realized. EXPERIMENTAL PROCEDURES All of the alloys were melted from sponge zirconium and fabricated to sheet for heat treatment

Jan 1, 1960

T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—Mr. Killian is to be commended for his inquiry as to why a decrease of 15.3 pct in coke consumption was accompanied by a decrease of only 1.9 pct in the CO/CO, ratio of the top gas. Although I encouraged him in his efforts to find a more significant and meaningful carbon-gas ratio, the method, calculations, and conclusions originated entirely with the author. Whether we agree entirely with the assumptions underlying his corrected ratio, I think we can all agree that a better ratio is needed, and that he deserves credit for recognizing the need and for doing something about it. To be most useful, the CO/CO, ratio for the top gas should reflect the way in which the carbon is gasified in the furnace, particularly the degree of oxidation and the extent of heat release. The effect of CO, from the decomposition of the limestone and the effect of the reaction of CO and water vapor in the upper part of the furnace on the quality of top gas should be isolated from the effect of more basic reactions such as ore reduction and solution loss. The reduction of sufficient iron oxide to produce a ton of pig iron and the accompanying changes in the proportions of the carbon gases can be expressed on a mol basis as follows: 16.5FeA + 16.5CO - 33FeO + 16.5CO, [1] 33FeO + 33.0CO = 33Fe + 33CO. [2] The CO, from eq 1 normally escapes from the furnace because it does not react with coke at the temperature of its release. However, as much as 50 pct of the CO, from eq 2 may react with coke because it is released at temperatures above 1000°C: 16.5CO. + 16.5CO2 = 33CO [3] Thus we see that the gasification of 16.5 mols or about 200 lb of C in solution loss will regenerate as much CO as is required for the last stage of reduction. The pronounced effect of reaction 3 on the final proportions of CO and CO, in the gas stream is obvious. It also follows that reaction 3 materially alters the heat release but it cannot be entirely eliminated in Lake ore practice. A previous study indicates that 100 lb of solution loss may be necessary to maintain the reducing power of the gas. A reduction of 100 lb from the normal level of 200 lb would mean that over 1,-000,000 additional Btu are released in the process. The 100 lb of additional carbon which will be burned at the tuyeres will release 437,000 Btu and the absorption of 583,000 Btu by eq 3 would be prevented. One of the chief objectives of sized ore burdens and more uniform distribution of the gas stream is to minimize solution loss by completing reduction higher in the furnace and in turn to release the maximum amount of heat from the carbon charged. It was odd, indeed, to find that the use of sized ore and sinter in the careful tests reported by Dobscha had changed the CO/CO2 ratio very little. The author has stressed the close correlation between his corrected CO/CO, ratio and production. A correlation of fuel consumption and the CO/CO, might be more logical. Fuel consumption on the prepared ore burden decreased 15.3 pct whereas the corrected CO/CO2 ratio decreased 19.0 pct. Although this agreement between the reduction in fuel and the reduction in corrected CO/CO2 ratio is not as close as the correlation with tonnage, it indicates the corrected ratio is superior to the normal ratio which decreased less than 4 pct. Some adjustment should be made for the reaction: CO + H2O = CO2 + H2 —700Btu [41 because there is evidence to indicate that about one half of the hydrogen is formed in the upper 21 ft of

Jan 1, 1953

By L. W. Strock

Metallurgists handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. 'lore preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The howledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Expcrience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,' but the incentive has gradually changed since the summer 0. 1940 to the specific practical problem of searching for domestic sources of rare and stratcgic metals. The

Jan 1, 1949

By Arthur Lake

Within the past few months I have had occasion to visit and examine the area of country in Gunnison county locally called the Gold Belt and extending from the Cebolla river on the west to the head of Taylor Park and the Sawatch range on the east. The region including the "belt" may be hided topographically into two parts, a northern and a southern one. The former is characterized by lofty mountains and deep canons, with occasional parks and wide valleys. Most of it is included in the granitic system of the Sawatch range, with local patches of the Palaeozoic sedimentary rocks, more or less traversed by great bodies of porphyry and other eruptive rocks. The southern portion, on the other hand, is characterized by comparatively low, rounded hills of schist and sahistose gneisses, underlain by coarse, massive granite, which outcrops locally in small, and sometimes in large, patches. These hills also sometimes form table-lands by reason of overflows of lavas, such as andesitic breccia, rhyolite, trachyte and basalt. The leading geological feature is that of a schistose area of width and extent unusual for Colorado. These schists and gneisses are of pre-Cambrian age; but whether assignable to the Algonkian or to some older system has not been determined. The granite which occasionally outcrops from beneath these schists is, I think, of true eruptive character, since its mode of occurrence indicates a once molten, or at least highly viscous or plastic, condition. Thus, we may observe, included in its mass, numerous fragments of schist, almost like a coarse, volcanic breccia. Again, at its immediate contact with the schists, which often stand vertically upon it, the pediments of the latter are fused into the granite, and granite tongues and veins run up amongst the schists, as only a molten or viscous

Jan 1, 1897

By Hans Lundberg

IN ORDER to comprehend the help and information that may be expected from electrical prospecting, it is necessary to have at least a general knowledge of the methods and principles involved in preparing and interpreting results obtained in the field. Electrical prospecting is rather complicated, both in theory and practice, and in order to make a brief description clear to the practical mining man it has been necessary to idealize and generalize the problems, at the risk of having such simplification criticized by the theoretical man. This simplification must not be misinterpreted as showing a lack of theoretical knowledge. FIG. 1.-FLOW OF CURRENT IN AND AROUND A CONDUCTING BODY. For its operation, electrical prospecting mainly, depends on the fact that most metallic ores conduct an electric current much more readily than barren rocks. If an electric current flows through a block of ground within which a body of chalcopyrite is enclosed in country rock of. schist, the current will find less resistance to its passage through the chalcopyrite than through the schist, even though the passage through the latter be much shorter. This is because the longer path through the chalcopyrite offers less resistance, owing to the superior electrical conductivity of the chalcopyrite (Fig. 1).

Jan 1, 1928

By E. A. Breitenbach

A computer program has been developed to afford rapid and complete quantitative log analysis for exploration and production decisions. The computation consists of automatic selection of tops and bottoms of porous intervals from the digitized data, and then point-by-point calculations within each selected interval. Nearly all log types can be analyzed. This paper presents the calculation techniques found to be appticable to machine evaluation and gives examples of their use. INTRODUCTION As the quantitative interpretation of well logs entails repetitive use of charts and equations, it is natural that digital computer programs would be written. A Universal Log Interpretation Computer Program (ULICP) has been developed to afiord rapid and complete analysis for exploration and production decisions. Application of this program enables the log analyst to: (I) apply rapid quantitative log analysis for exploration and production decisions on either a field, a well or on a single zone basis; (2) apply concepts of interpretation requiring detailed numerical analysis; (3) analyze all porous intervals on each log, rather than a few selected zones, and complete the analysis in less time than previously required. Computations are reported for every digitized point in each zone; (4) use empirical techniques applicable to a given area as an integral part of the computation; (5) experiment with the empirical coefficients and exponents in the interpretation equations to find the best possible solution; and (6) automatically plot both the original and computed data to scales analogous to the field prints. The primary utility of a log interpretation program stems from its ability to do an overwhelming amount of work with very little man-power. If a calculation procedure or thought process can be formalized to the extent that step-by-step logic can be written, a computer program can be developed that follows this logic. The major question is one of economics. A feasibility study of the costs for such a program indicates that digital processing is economical primarily as a means of increasing the productivity of the log analyst. In effect, the probability of missing productive intervals in any well, because of a lack of time to do detailed calculations, is greatly reduced. The nucleus of ULICP is programmed to compute large sections of a suite of logs by selecting zones automatically and then performing all pertinent computations on a data point by data point basis within each zone.'.' An entire suite of logs can be processed in this manner with very little manual intervention. Sufficient programming logic is available so that each log analyst can request computations pertinent to his area. These requests are made by simple additions or deletions of information on the input header cards. Hence, the log analyst is always in complete control of the computation process. The evaluation of a suite of logs requires pre-editing, digitization, computation, presentation of results and interpretation. Work by the log analyst is reqilired only in pre-editing and interpretation. Thus, he is allowed more time for comprehensive interpretation, rather than calculation. For continuity, the discussion of ULICP is organized sequentially: pre-editing, digitization, computation and presentation of results. DISCUSSION PRE-EDITING The extent of pre-editing prior to computation is dependent on the format of the original data. For analog prints, it requires inspection, correlation and editing of the logs, plus the entering of required data an special forms. For digitized data such as magnetic tape field recordings, only the special forms are necessary. The process for analog prints will be given here. The inspection and correlation process involves the selection of sections for digitization and the correlation of the traces to a common depth. To decrease the cost of digitization, traces that exhibit large variations in shale formations can be redrawn to a non-zero baseline. The next step is to enter all pertinent data on the input header cards. The header cards presently used for ULICP are presented as Figs. 1 through 6. Cards 1, 2, 3 and 4 (Fig. 1) are defined as the Main Header Cards. They describe the particular well for output identification and give basic information. Cards 5 through 15 (Figs. 2 through 6) are defined as the Block Header Cards. As such, they define the log types and the interpretation parameters for the block of data immediately following. Cards 1 through 10 are required for every computer run. Cards 11 through 14 pertain only to nuclear logs. Card 11 is required if any nuclear log is supplied, and cards 12 through 14 are required only when gamma-ray, density or neutron log data, respectively, are supplied. Card 15 (Fig. 6) must be supplied when cross-plot calculations are required. Either two- or three-component

Jan 1, 1967

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson's discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 79 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612' F. (322' C.), they redoccd the 79 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statenlent just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson's time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totsally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced colisumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opirlions advanced by different authorities in the scientific world to account for the apparent anomaly, bat none,

By Lawrence P. Bonicatto

The steel industry's increased demand for higher grade pellets has caused the pellet producers to investigate methods of upgrading their product and the Hanna Mining Co.'s Groveland plant on the Upper Peninsula of Michigan is no exception. The low grade iron deposit is a complex mixture of magnetite and hematite with chert, quartz, jasper and various iron silicates.1 Beneficiation is by Humphrey spirals and anionic flotation of the iron minerals.2 Flotation of the spiral tailings makes up about 75% of the concentrate, while a minor amount of concentrate (less than 3%) is produced in magnetic circuits. The concentrate is pelletized at the rate of 1.6 million tpy. The initial concentrating facilities were constructed in 1958 and the concentrate was marketed as sinter feed until a pelletizing plant was added early in 1963. Grade improvement soon became a high priority research project, and several methods of concentration were investigated.

Jan 3, 1968

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By L. E. Mannion

Sodium carbonate (soda ash) is one of two principal commercial alkalis. Its principal competitor is sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines and solid salts provided impure soda for early glassmaking. Until the 19th century, soda ash (as well as potash) was recovered mainly by leaching wood or other plant ashes. In 18th-century Europe, for example, leaching seaweed ash with hot water produced a brown laundry lye. One of the better grades of this material was a Spanish product, barilla, which analyzed 24 to 30% Na2CO3 (Hou, 1942). The modern chemical industry was born in 1691 with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. English industry used this process extensively in the 17th and 18th centuries. The next major advance was in 1863, when Ernst Solvay devised the ammonia-soda, or Solvay process. The first of many Solvay plants was built in 1874. These supplanted the LeBlanc method and dominated worldwide soda ash production until 1974, when mined sodium carbonate became predominant. Although considerably less important until recently, natural sodium carbonate deposits historically have supported small soda ash operations throughout the world. Shortages during World War II stimulated production of "natural" soda ash from such deposits, particularly at Searles Lake, CA and Lake Magadi, Kenya. More spectacularly, increased production from the vast trona deposits in Wyoming has virtually supplanted the Solvay process in the US. Principal producers of natural soda ash as well as the character of the source deposits are listed in Table 1. [ ]

Jan 1, 1983

By R. W. Smith, K. H. Lee

Bond type simulated closed-circuit grindability tests and batch grindability tests were run on six pure minerals plus a limestone and a taconite ore. The simulated closed-circuit tests were made at five different meshes of grind. The minerals tested varied widely in hardness and breakage pattern. For all simulated closed-circuit tests both Bond and Holmes work indices were calculated and compared. The Bond grindability testlm6 has been widely and quite successfully used for predictions of such items as ball mill power requirements and as an aid in plant comminution equipment selection. The test is interesting in that although run as a series of batch tests it is over-all a simulated closed-circuit test with a circulating load of 250%. The simulated closed-circuit feature is probably the primary reason for the notable success of the test. Perhaps the major criticism that can be brought against the test is that it is time consuming, since it normally takes a trained technician about an eight-hour shift to perform it.4 For many purposes this is an acceptable time requirement. However, if a grindability test is to be used for mill control purposes it should be performed in as short a time interval as possible, preferably under an hour. Sometimes in industry strictly batch tumbling mill tests are run and an attempt is made to correlate such batch tests with plant mill operation. Then an attempt is made to adjust operating tumbling mills based on data from the tests. The tests, however, frequently do not correlate well with operating data. The purpose of the present work was to explore some of the similarities and differences between a simulated closed-circui.t grindability test and a batch type test. Six different minerals plus a limestone and a taconite ore were tested in the experimentation. These materials varied widely in hardness, breakage characteristics, etc. Standard dry Bond grindability tests were mn on all materials at 48, 65, 100, 150 and 200 meshes of grind. Feed material was prepared by stage cmshing to -6 mesh. Initial feed volume was 700 cc. Care was taken to maintain the standard constant weight (about 20125 gm) and number of balls (283) during all the tests. Rotational speed was 70 rpm. Table I lists the materials studied along with pertinent data regarding the materials and Bond grindabilities obtained. In addition, dry batch tests were performed on all materials. These tests were made in the same mill as was used for the Bond tests. An identical ball charge and an identical feed volume were used. After rotating the mill for a predetermined number of revolutions at the same rotational speed as for the Bond test, the material was removed and separated from the ball charge. A screen analysis was performed on this product. Knowing the original size distribution of the feed and the size distribution of the product, it was possible to calculate the grindability or grams of a particular mesh produced per revolution of the mill. After the screen analysis of the product, the various fractions were recombined and placed back in the mill for further grinding. After grinding for additional revolutions of the mill the procedure was repeated. Thus, it was possible to obtain grindabilities for each material at a number of meshes of grind and for various revolutions of the mill. Grind-abilities obtained from batch tests are shown in Table 11. COMPARISON OF BOND AND BATCH GRINDABILITIES Figs. 1A through 1D show relationships between batch and Bond grindabilities. Figs. lA, lB, 1C and 1D show respectively graphs indicating the relationships for batch tests run for 100, 300, 500 and 700 revolutions of the mill. For a particular material on each graph, points are shown for 200, 150, 100, 65, and 48 meshes of grind except for several missing coarse meshes of grind for galena which did not fall conveniently on the figures. For each material and graph the point nearest the origin is for 200 mesh, the next for 150 mesh, the next for 100 mesh, etc. Considering Fig. lA, it is interesting to note that all relationships shown are essentially straight lines. There are, however, considerable differences

Jan 1, 1969

By W. M. Gray

The determination of the state of stress existing at a point in any solid body requires the determination of the six components of the stress tensor relative to a convenient set of axes. One general method of doing this in rock is to make strain or deformation measurements associated with local relief of stress in a number of boreholes penetrating a limited volume in the vicinity of the point at which the stress is to be determined. The stress is assumed to be constant throughout this volume. Leeman1 has described a number of the instruments that have been developed for making deformation or strain measurements in boreholes. Panek2 has described the application of statistical methods to the determination of the average components of ground stress from sets of measurements made in boreholes by means of deformation meters of the type developed by the U.S. Bureau of Mines. In this paper attention is given initially to the strain cell developed for use on the flattened ends of boreholes by the Council for Scientific and Industrial Research (CSIR) , South Africa. The equations required for evaluating the average components of ground stress from measurements made by means of the CSIR strain cell are derived. These equations are similar in form to those applying to measurements made by the borehole deformation meter developed by the U.S. Bureau of Mines. The results of an investigation of the properties of the equations are described. These results are important in the practical use of both the instruments mentioned above and any instrument based on similar principles.

Jan 1, 1968

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By E. W. Murbach

The oxidation of uranium carbide by oxygen at various pressures, and by air, has been investigated at temperatures up to 600°C. Arc-melted and cast uranium carbide displays oxidation behavior that appears to be dependent on its treatment after melting. ccReactive" uranium carbide, which results from exposure of freshly melted material to laboratory air, ignites in oxygen at about 275° to 350°C depending on pressure, and in air at about 350°C. The product of the initial oxidation appears to be UO2+.. Continued heating produces U30,. The initial oxidation rate is poportional, roughly, to the square root of the oxygen pressure. The activation energy determined for the initial oxidation reaction is 7.1 kcal, from 400° to 600°C in 10 mm of oxygen. AN investigation of low-decontamination methods for reprocessing uranium carbide reactor fuels is being carried out at Atomics International. One of the reprocessing cycles includes oxidation of the fuel at relatively low temperature (300° to 500°C) and reaction of the product oxide with carbon at elevated temperatures (above 1500°C) to produce uranium carbide. A number of small-scale experiments have been carried out in which uranium carbide was oxidized in air and oxygen at various pressures to measure reaction rates and to obtain other information concerning the oxidation process. In initial experiments with arc-melted UC, ignition was observed at about 275°C in oxygen or 350°C in air. However, similar experiments by Neymark' at 426°C in air showed no ignition. It was soon determined that the difference in oxidation behavior was due to the treatment of the UC following arc-melting. Neymark's experiments were carried out with freshly melted UC while those reported in the

Jan 1, 1963

By Robert D. Pike

In November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: Stone Completely Calcined CaO(Sro)a............. 30.35 57.806 Mgo................... 21.55 41.050 SiO2. ................... 0.30 0.572 R2O3................... 0.30 0.572 Ignition loss............. 47.50 a SrO about 0.06 pct. Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2'3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depending upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1948

By Robert D. Pike

In November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: Stone Completely Calcined CaO(Sro)a............. 30.35 57.806 Mgo................... 21.55 41.050 SiO2. ................... 0.30 0.572 R2O3................... 0.30 0.572 Ignition loss............. 47.50 a SrO about 0.06 pct. Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2'3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depending upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1948

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962