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By Ralph B. Stevens

INTRODUCTION Underground fires continue to be one of the most serious hazards to life and property in the mining industry. Although underground mines are analogous to high-rise buildings where persons are isolated from immediate escape or rescue, application of technology to locate and control fire hazards while still in their controllable state is slow to be implemented in underground mines. Even in large surface structures such as hotels, often only fire protection systems which meet minimal laws are implemented due to the high cost of adding extensive extinguishing systems, isolation barriers, alternate ventilation, escape routes and alarm systems. Incomplete and ineffective protection occasionally is evidenced where costs would not seem to be a factor, such as the $211 million MGM Grand Hotel fire November 21, 19801. Paramount in increasing fire safety and decreasing the threat of serious fire is early warning followed by proper decision analysis to perform the correct action. However, very complex fire situations can be produced in structures such as high-rise buildings and underground mines simply because of the distances between the numerous fire-potential locations and fire safe areas. Other complexities arise when normal activities occur that emit products of combustion signaling a fire condition to a sensitive fire/smoke sensor. For example, the operation of diesel equipment or the performance of regular blasting can produce combustion products that reach the sensitive alarm points of many sensors2. Smoke detectors for surface installations provide fire warning when occupants are at a distant location or when sleeping, thus greatly reducing injuries and property damage. However, when installed in the harsh environments of underground mines, fire and smoke detection equipment soon becomes inoperative, unreliable, or requires excessive maintenance. The U.S. Bureau of Mines has performed many studies and tests to improve fire and smoke protection for underground mine workers3. This paper describes several USBM safety programs which included in-mine testing with mine fire and smoke sensors, telemetry and instrumentation to develop recommendations for improving mine fire safety. It is hoped that the technology developed during these programs can be added to other programs to provide the mining industry with the necessary fire safety facts. By recognizing fire potentials and being provided with cost-effective, proven components that will perform reliably under the poor environmental conditions of mining, mine operators can provide protection for their working life and property equal to that which they provide for themselves and their families at home. The basis of this report is two USBM programs for fire protection in metal and nonmetal mines4,5 and one coal program6. The data was collected beginning in May 1974 and continuing through the present with underground tests of a South African fire system installed at Magma Mine in Superior, Arizona, and a computer-assisted, experimental system at Peabody Coal Mine in Pawnee, Illinois. The conduct of each program was as follows: • Define the problem and its magnitude in the industry • Develop concepts to solve or diminish the problem • Review available hardware or systems approaches to fit the concepts • Install and demonstrate the performance of a prototype system through fire tests in an operating mine. MINE FIRE FACTS Whether in coal or metal and nonmetal mines, the potential severity of fire hazard is directly related to location. As shown in Figure 1, fire in intake air at zones A, B, C or D can cause contamined air to route throughout the mine quickly if not detected, isolated or rerouted. Causes and location of former metal and nonmetal fires are represented in Table 1; the cause and location of fatalities and injuries is shown in Table 2. Coal-related fires and their impact on deaths and injuries are graphed in Figure 2; their locations are described in Table 37. Significantly the table shows that the hazard to personnel was three times greater for fires occurring in shaft or slope areas, and the percentage of deaths and injuries was four times that of other areas. Number of Persons Affected A 129-mine sample indicated that from 8 to 479 employees per shift work in underground metal and nonmetal mines, and that deeper mines have larger populations, as shown in Figure 3. Coal mining relates similar employment, and a 16-state sample of 670 mines employing at least 25 persons shows the distribution in Figure 4. Drift mines accounted for 58 percent of the sample but employ only 45 percent of the underground workers.

Jan 1, 1982

By W. L. Penberthy, H. J. Ramey

Experimental work on the combustion oil recovery process has consisted of both laboratory and field studies. Although field experiments are the ultimate test of any oil recovery process, they are costly, time consuming and difficult to analyze quantitatively. Laboratory combustion tube experiments can be opertzted far more rapidly and cheaply, but are subject to scaling and interpretation problems. This paper points out some important design problems, operational criteria and considerations in2portunt to interpretation of results. An analytical hcut model of movement of a burning front axiully along a cylinder with heat loss through an annular insulation was developed. The result was used to identify steady-state temperatrrre distributions both ahead of and behind the burning front, with and without heat loss. Results indicate potential operating limitations on the minimum burning front rielocity (or air flux) which may be used for any given combustion tube. Results also enable estimating the effective thermal diffusivity and over-all heat loss from experimental data and thickness of the brnning zone. Resu lts of operation of a combustion tube constructed recently verify this preliminary theory in the region immediately ahead of and behind the burning front surprisinRly well. INTRODUCTION Many field and laboratory studies of the forward combustion oil recovery process have been conducted since the early publications of Kuhn and Kochl and Grant and Szasz2 in 1953 and 1954. In view of the complex and costly nature of this type of investigation, it is not surprising that no complete theory of the nature of the forward combustion Drocess is yet available. However, gross effects are understood well enough that reasonable design procedures are available for planning field operations. Nelson and McNeil 3,4 have published two comprehensive papers concerning design procedures. One major consideration in planning field operations is the fuel concentration at the burning front. Fuel concentration controls air requirements — an important cost factor in forward combustion. Although fuel concentration can be estimated from field test results by various methods, results are subject to great uncertainty in view of natural limitations on experimental observations. Nelson and hlcNeil4 recommend that fuel concentration be determined from laboratory combustion tube studies. Fuel concentration is only one of many important factors which can be studied by combustion tube experimentation. An obvious goal of imporrance must be development of a comprehensive theory of the forward combustion process. If a theory of this process can be established which matches controlled laboratory experimentation, it should be possible to apply this theory to field operating conditions with some confidence. Laboratory combustion tube studies have already yielded important information concerning the combustion process. However, details concerning the design, construction and operation of combustion tubes are rare. Combustion tubes used by various investigators vary in size, length and mode of operation. Therefore, one purpose of this paper is to present considerations important to design, construction and operation of a combustion tube. In regard to previous combustion tube studies, attention is called to Refs. 1 through 9. These references describe a wide variety of equipment types and present a great deal of pertinent experimental data. In general, combustion tubes usually consist of thin-walled stainless steel tubes containing an oil sand pack mounted within a pressure jacket. Provisions have often been made to heat the tube ex tern a lly by separately controlled heaters to reduce heat losses. This step usually permits operation at low air fluxes (air rate per square foot burning front surface) similar to those encountered in field operations. Burning is usually conducted from the air inlet end of the tube to the outflow end. The tube orientation used has been vertical or horizontal. For vertical tubes, burning has been conducted vertically downwards. As a result of laboratory studies, many of the

Jan 1, 1967

A plan which has just been approved by President Wilson, by, the Secretary of the Navy, and the Naval Consulting Board, provides for the active cooperation of the Associated Advertising Clubs of the World with the 30,000 engineers who will soon undertake the task of making a card index survey of American industry, so that it may be prepared for national defense, if need comes. Herbert S. Houston, President of the Associated Clubs of the World comments on the plan. "Through the great power of advertising we expect-to arouse manufacturers, workingmen, businessmen, in fact the whole country, to the vital need of making industry the basic line of defense so that, if necessity arises, it can supply munitions quickly and abundantly. "This is not a war measure, but a peace measure. The militarist will support it and so will the pacifist, as well as the great body of Americans in between. So the slogan `national defense and international peace, has been adopted believing that the two causes will be best served by linking them together. "While the primary thing, of course, is service to the country, it is manifest that this work of the engineers will be of the greatest service to industry in times of peace. If industry is mobilized for defense, it will be placed on a basis of efficiency to meet the keen competition that will surely follow the present war." Howard E. Coffin, one of the leaders of the American automobile industry, in outlining the far-reaching plans of his committee, the Committee of Industrial Preparedness of the Naval Consulting Board, said: "At the outset I wish to emphasize the absolutely non-partisan nature of this work. I am not even familiar with the political affiliations of the great majority of the members of the Board or of my committee. In setting out to, mobilize the industrial resources of the United States, we are concerned only with the benefit to the nation, and to that end we have called into being an organization made up of the best technical and business brains of the country, and that organization will work along business lines with strictly business methods. I think it reasonable to say that this is a movement perhaps unique in the history of national governments, and one geared up to the highest standards of twentieth century efficiency. "It is vitally necessary that American industry be made aware of the part it must play in the national defense. Our whole conception of warfare has been changed almost overnight. Our military heads at Washington are largely, of course, graduates of the very best technical schools, have been taught the profession of fighting, and are masters of that profession. As members of the Naval Consulting Board, we are unable to tell these men how to do their work. But while these departmental heads have lived with military problems all their adult years, we on the other hand have slept and eaten and lived with the industrial problems of the country. The two questions are wholly distinct, and the masters of one cannot possibly be the masters of the other. We are confronted then with the necessity of interlocking these two vast elements of our national life into a great working organization for the national defense. It is that which we are about to do.

Jan 5, 1916

By J. E. Fox Jr., J. L. Lummus, J. P. Gallus

Fresh water or brine drilling fluids may be kept free of suspended drilled solids by the addition of a water soluble acrylamide-carboxylic acid copolymer at the flowline. Addition of from .01 to 0.2 lblbbl of the polymer solution to drilling fluids containing less than 5 per cent clay solids by weight causes the solids to flocculate and settle rapidly to the bottom of the pits. Solutions of the polymer injected at the pump suction reduce the loss of water to permeable formations without impairing the permeability to oil. The use of drill-itlg fluids clarified with the polymer has resulted in increased drilling rates, extended bit life, and lower drilling fluid costs. INTRODUCTION Field experience and the results of a number of investigations have established that the accumulation of solids in drilling fluid reduces drilling rate.'-' Drilling with water makes possible higher drilling rates than can be achieved with mud but in many areas drilling with water may not be feasible because of the possibility of encountering high formation pressures or by-dratable formations. To combat these conditions, the drilling fluid must possess certain physical properties such as viscosity, density, fluid loss, etc., which require the presence of solids. The current trend in drilling fluid treatment is to maintain as low a percentage of solids as is possible without harmfully affecting the mud properties needed for drilling. Mechanical separating devices such as wet cyclones and decanting-type centrifuges are proving to be an economical means of controlling the percentage of solids and thereby maintaining low solids muds. Also: special muds have been developed for the purpose of retarding the hydration of drilled solids so that they may be more easily removed by shale shakers or settling pits. In some areas, such as West Texas, the characteristics of some formations will permit drilling with water. However, because of the dispersion of drilled solids, it is usually not possible to maintain clear water even with the aid of mechanical separators, or by utilizing large settling pits. For this reason the commonly used term "water drilling" is a misnomer since the water usually contains some solids. Because of the improved drilling rates and other benefits which might be effected, a laboratory and field study was made of the use of flocculating agents for maintaining clear water for drilling. PROCEDURE Laboratory—Solids Settling Two techniques were employed to determine the effectiveness of flocculating agents in settling solids from drilling mud. First, the rate of fall of solids was measured in graduated beakers containing mud treated with various flocculating agents. Natural gum, oil-in-water emulsions prepared with ethoxylated nonyl phenols and diesel oil. and a powdered synthetic acrylamide-carboxylic acid copolymer* (hereinafter referred to as "polymer") were tested as flocculating agents in both fresh water and salt saturated muds containing 4 per cent solids. The polymer was not added in the powder form directly to the muds but was first dissolved in water in a concentration of 3.5 lb/bbl. The polymer solution was then added directly to the mud. The concentration of the flocculating agents, including the polymer, was varied. High rates of fall of the solids indicated high flocculating efficiency. A second technique consisted of measuring the time in minutes required to obtain clear water at the pump suction after addition of the various flocculating agents at the flowline. These tests were made using a model mud circulating system having a total volume of approximately 10 gal. The natural fresh water and brine muds used contained 4 per cent solids. A sketch of the circulating system appears in Fig. 1. The circulating rate

By AIME AIME

MOST of us are far .from home, and yet our Japanese hosts- have made us feel very much at home. Here in the Orient we engineers are .learning a new meaning for the word "orientation"- hereafter that engineering term will be a synonym for gracious hospitality, and "to orient" will mean to turn a whole country over to the World Engineering Congress. Mere geographic distance is no longer able to separate nations, for the conquest of distance is one of the triumphs of 'modern engineering. We of the Americas are fortunate in the position of our continents: with their shores lapped by the waves of two oceans, we face' two great civilizations, the' Occidental and the Oriental, and thus we can share the intellectual resources of these two older cultures.

Jan 1, 1929

By S. M. Shelton

SINCE the Saar started. the real progress in scrap-metal recover is in the change of point of view regarding secondary metals. The tendency had been to regard scrap as the normal outgrowth of obsolescence, fluctuating somewhat from periods of depression to periods of prosperity. but nevertheless an unwieldy economic factor more to be contended with than embraced. Now, metals above the ground are being looked upon as semi-permanent reserves or stock piles in various stages of repeated use or revolving life cycles. The change in point of view is due to the forced realization that domestic supplies of new metals are limited and many foreign sources are at least temporarily closed. The stock piles must be cultivated. The reserves must be made more nearly permanent. Steps are being taken : (1) develop methods for recovery of scrap metals heretofore not recovered, and (2) restrict strategic metals to uses ensuring a large percentage of re-use, which in turn means substitute materials in the dissipative uses.

Jan 1, 1942

By Francis A. Thomson

T HE engineer of today is by his training, by his traditions, and by the service which he must render, irrevocably committed to taking his part in public life along with the members of the older professions of ministry, medicine and law. Nevertheless, in comparison with these: three, so long recognized as the "learned professions-all three of which grew out of the functions of the priesthood-engineering in any modern sense of the word is a youthful profession indeed. So youthful is engineering in its present significance, that it may be said to date from the labors of John Smeaton, the lighthouse builder; of Simon Newcomen and James Watt, the inventors of the steam engine; and of George Stephenson, the inventor of the locomotive; at the dawn of the 19th century. Great works of an engineering character had, it is true, been executed long before this, but practically all of them had been rule-of-thumb enterprises, dependent upon a plethora of slave labor for their accomplishment. For illustration it is said that at Rio Tinto in the days of Hiram, king of Tyre, 40,000 men worked for a year to produce three tons of silver from the rich outcrop ore. Such an operation can scarcely be called an engineering enterprise, however, when we remember that a fourth of this number of men in these same mines, from which the richest ore was long ago extracted, produce at present over 100 tons of copper per day.

Jan 1, 1925

By W. B. Mather

R. G. Wuerker (University of Illinois, Urbana)—Mr. Mather is to be congratulated for stressing the most urgent need for a program of testing the physical properties of rocks, as they are encountered by the petroleum engineers on their drilling jobs and by the miners on their excavating, roof control and mineral preparation tasks. Another valuable source of information is the Handbook of Physical Constants.22 It stresses the physicist's approach rather than the engineer's procedure. The study of hardness, and rock hardness in particular, is beset with many difficulties. There is no satisfactory definition of hardness yet, and the term hardness is used to describe a number of quite dif- ferent properties. Hardness tests are grouped into static and dynamic determinations. They should be expressed with reference to the mechanical action of the applied force, like indentation hardness, scratch hardness, abrasion hardness, rebound hardness. A discussion of all these various hardness tests and of the special difficulties encountered in hardness testing of such heterogeneous material as rocks is given in the U. S. Bureau of Mines' standard proposal. The more critical student may be referred to the book by D. Landau: Hardness, which is in my opinion the best existing treatise on this subject.

Jan 1, 1952

By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By Richard R. Zupp, David A. Stevenson

An experimental method to determine the carbon activity in various solid solutions was developed. Samples of the solid solutions and an Fe-C reference sample were equilibrated with respect to carbon content by annealing them in a Hz-CHI gas mixture in a closed cell. The carbon content of each sample was determined, and the carbon activity was obtained from the carbon content of' the reference sample and well-established data for the dependence of the carbon activity on the carbon content in Fe-C alloys. The influence of vanadium on the activity of carbon in austenitic Fe-C-V alloys at 1000°C was determined by this technique. A general semiempirical correlation was developed to describe the dependence of the activity coefficient of- carbon on the composition of ternary austenitic iron-base alloys containing interstitial carbon and a substitutional solute. The correlation is particularly useful in predicting the partitioning of- carbon between various alloys. THE influence of substitutional solutes on the activity of interstitial solutes in metallic solid solutions is important in the theory of alloy phases. Solid solutions of particular interest are the fcc austenite phases of ternary Fe-C-Z systems, in which carbon is the interstitial solute and Z represents any substitutional solute. Carbon-activity data are also needed in these solid solutions to solve practical problems; the quantitative treatment of diffusion-controlled transformations' is an examvle. Experimental information is available for ternary austenitic solid solutions containing Mn,2 Si,2 and A16 as the substitutional solute. Because qualitative preliminary studies indicated that vanadium appreciably decreases the carbon activity,14 the present investigation was undertaken to determine the influence of vanadium on the activity of carbon in austenite. Although Flender and ever" measured carbon activity over a range of compositions in the Fe-C-V system, they were primarily interested in determining phase boundaries in the ternary system, so most of their measurements were outside the composition range for stability of single-phase austenite. Petrova and Shvartsman' also made limited measurements of the carbon activity in Fe-C-V alloys. The dependence of the carbon activity on the carbon content of an alloy may be determined by passing COCOz or H2-CH4 gas mixtures of carefully measured composition over the alloys, determining their equilibrium carbon content, and utilizing the relevant equilibrium relationships. smith16 used this technique with both CO-COZ and HZ-CH4 gas mixtures to determine the dependence of carbon activity on carbon content in pure Fe-C alloys. His data, which are in good agreement with those of some previous and subsequent investigators,6'17 but not with those of others,lfl'ao are usually considered to be the most reliable. Although the same method can be applied to Fe-C-Z alloys, it is difficult experimentally, because the appropriate gas mixtures are almost pure CO or Hz. A simpler technique is to simultaneously equilibrate the Fe-C-Z alloys and pure Fe-C alloys with the gas mixtures, and then use Smith's data to determine the carbon activity in the pure Fe-C alloy. A number of investigators have employed this technique. others Have used the partitioning of carbon at the interface of a diffusion couple prepared from an Fe-C alloy and a Fe-C-Z alloy. In the present study, a closed-cell method was developed by which carbon was selectively transferred via a gas medium between pure Fe-C alloys and Fe-C-V alloys which were not in physical contact. A similar method was developed independently by Heckler and winchel14 and used to study the Fe-C-Ni system. EXPERIMENTAL METHOD A schematic diagram of the experimental arrangement is shown in Fig. 1. In a typical experiment, a 5-g Fe-C sample was placed in one compartment of a quartz cell, and a 5-g Fe-V sample was placed in each of the other compartments. The cell was evacuated, outgassed, backfilled with approximately 125 Torr of hydrogen, and sealed. After being placed in a fur-

Jan 1, 1967

By R. H. Adams, A. M. Khan

The Huntington Beach oil field is on the Pacific Coast, southeast of the City of Los Angeles (Fig. 1). It lies both onshore and offshore. Most of the onshore section is operated by Standard Oil Co. of California, WOI. The Tar reservoir is of upper Pliocene age, about 200 ft thick, and consists principally of fine-grained, unconsolidated, somewhat shaly sand, with thin inter-bedded shale stringers throughout (Fig. 2). The reservoir is a broad, highly faulted, elongated anticline, with an areal extent of about 370 acres. Most of the faults bisecting the structure are normal, trend north-south, and are the main cause of reservoir discontinuity (Figs. 3 and 4). From 1964 to Dec., 1967, 259 steam stimulations were performed on a total of 125 Tar sand wells. Eighty-six new wells were drilled and steam stimulated. Of the total, 96 have been stimulated twice, 34 three times and 3 four times. During this same period, a two-injector steam drive pilot has been in progress. The response obtained from this project has been compared with the response to cyclic stimulation. This paper presents an analysis of the field observations for the two methods of thermal recovery. History of Development Drilling to the Tar pool commenced in 1924 with an initial well production of 40 to 50 B/D of 12o API gravity oil. Complete primary development of the pool has been spread over several years. Approxi- mately 40 wells were drilled during the first phase of development, which was completed in 1945. The subsequent primary development started in 1960 with initial well productions of 30 to 40 B/D oil. Thirty-seven wells were completed in the Tar pool during this phase. For the most part, slotted, gravel flow packed liners have been used in the wells in this pool. A cyclic steam stimulation pilot was initiated in March, 1964. Based on the very successful stimulation in the pilot area, the cyclic stimulation project was expanded to include all of the Tar pool wells producing at the end of 1965 (Fig. 5). Also, a development drilling program was begun at this time. To date, 86 new wells have been drilled under this program. The number of wells drilled each year in this secondary phase of development is also shown in Fig. 5. New Well Completion Practices Most of the new wells have been completed to produce from both the Upper and Lower Tar zones. Generally, a casing stub is cemented from the top of Lower Tar to the base of clean Upper Tar sands to exclude intermediate water-bearing sands. The water string is then cemented from the top of Upper Tar to about 1,500 ft with neat cement and 30 percent silica flour. The annulus from 1,500 ft to surface is then filled with a petroleum-based gel through a high-temperature port collar. Once again, a history of sand-free production dictated the use of 60-mesh gravel flow packed liners. The Upper and Lower Tar

Jan 1, 1970

By John Wulff, J. H. Hollomon

Service failures in brass condenser tubes are often due to corrosion. One of the commonest types of corrosion reveals a surface structure of redeposited copper.' The study of the effect of alloy addition agents in preventing this kind of corrosion has received impetus from the extensive publication of Bengough and May.2 The mechanism of such inhibition gauged from immersion corrosion,2 cell corrosion,3 and electrolytic potential4 measurements is controversial. This controversy may be attributed in part to a lack of definite knowledge5 of the actual nature of the initial films formed in corrosion experiments. In our own corrosion work on copper and 70-30 brass this lack became apparent and necessitated an examination of surface films by X-ray and electron diffraction methods. The present paper is but an introduction to the subject of inhibition and reports the structure of films formed in active corrodents. Experimental Procedure The arsenical coppers and brasses used in this investigation were made by one of the writers* in the plant of the Revere Copper and Brass Co. at Rome, N. Y. Standard commercial melting practice was followed. O.F.H.C. copper and electrolytic zinc were used and all arsenic additions were made by additions of a master copper alloy. The final analyses are given in Table I. Likewise, the extrusion, cold-rolling, and intermediate anneals employed followed standard usage. Final heat-treatments were given to all materials to produce a similar grain size (0.035 to 0.045 mm. for brass and 0.015 to 0.025 for copper) for the alloys containing various percentages of arsenic. Samples 1/2 by M by 1/4 in. were cut from sheet material resurfaced and finished with 0000 metal-lographic papers. The surfaces were all degreased in alcohol and benzine before immersion. After immersion in the corrodent, they were washed gently in tap water, dipped first in alcohol and then in pure benzine and allowed to dry in the diffraction apparatus. The reflection electron diffraction apparatus used has been described by Burwell and Wu1ff.6 Fig. I is typical of the photo-grams obtained. The X-ray apparatus was

Jan 1, 1941

By John Wulff, J. H. Hollomon

Service failures in brass condenser tubes are often due to corrosion. One of the commonest types of corrosion reveals a surface structure of redeposited copper.' The study of the effect of alloy addition agents in preventing this kind of corrosion has received impetus from the extensive publication of Bengough and May.2 The mechanism of such inhibition gauged from immersion corrosion,2 cell corrosion,3 and electrolytic potential4 measurements is controversial. This controversy may be attributed in part to a lack of definite knowledge5 of the actual nature of the initial films formed in corrosion experiments. In our own corrosion work on copper and 70-30 brass this lack became apparent and necessitated an examination of surface films by X-ray and electron diffraction methods. The present paper is but an introduction to the subject of inhibition and reports the structure of films formed in active corrodents. Experimental Procedure The arsenical coppers and brasses used in this investigation were made by one of the writers* in the plant of the Revere Copper and Brass Co. at Rome, N. Y. Standard commercial melting practice was followed. O.F.H.C. copper and electrolytic zinc were used and all arsenic additions were made by additions of a master copper alloy. The final analyses are given in Table I. Likewise, the extrusion, cold-rolling, and intermediate anneals employed followed standard usage. Final heat-treatments were given to all materials to produce a similar grain size (0.035 to 0.045 mm. for brass and 0.015 to 0.025 for copper) for the alloys containing various percentages of arsenic. Samples 1/2 by M by 1/4 in. were cut from sheet material resurfaced and finished with 0000 metal-lographic papers. The surfaces were all degreased in alcohol and benzine before immersion. After immersion in the corrodent, they were washed gently in tap water, dipped first in alcohol and then in pure benzine and allowed to dry in the diffraction apparatus. The reflection electron diffraction apparatus used has been described by Burwell and Wu1ff.6 Fig. I is typical of the photo-grams obtained. The X-ray apparatus was

Jan 1, 1941

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation." The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation.76 The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By H. O. Hoffman, C. D. Demond

There are two methods of determining the fusibility or refractoriness of fire-clays, the theoretical and the experimental. In the former, conclusions are drawn from the chemical composition; in the latter, from the changes which the clay undergoes when subjeoted to intense heat. It is well to use both methods, beginning with the actual heat-test and explaining the results obtained from this by the help of the chemical analysis. In discussing the subject, however, it is better to reverse this order. I. The Theoretical Method.* Leaving out the hygroscopic and combined waters and any organic matter, as not directly affecting the fire-resisting property, the refractory constituents of fire-clay are alumina and silica, and the fluxing constituents magnesia, lime, soda, potash and ferric oxide. According to Bischof,† alumina is the least fusible component, and silica follows close upon it. If, however, a mixture of the two be heated, it will be found that its melting-point is much lower than that of alumina, as a silicate will then have been formed. The way in which silica affects the refractoriness of alumina has been strikingly presented by Seger 1 in a diagram reproduced in Fig. 1. The abscissæ represent the melting-points of Seger cones Nos. 26 to 36 (see p. 55); the ordinates, the relative amounts of alumina and

Jan 1, 1895

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc' and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By F. W. Davis

SOME idea may be gained of the tremendous consumption of refractories by the open-hearth steel manufacturers from a statement made by A. T. Green at a meeting reported by T11.e Industrial Chemist of London, as follows: "At a very progressive steel plant in the Midlands, with a battery of five open-hearth furnaces working. twelve months and making 3000 tons of steel per week, the cost of refractories per ton of steel produced averages about $0.50 for the actual open- hearth casting and $0.12 for those operations incidental to the rolling of the metal." .These figures, when translated into the annual tonnage of steel, represent a very considerable expenditure.

Jan 1, 1930

By Raymond J. Kujawa

For general purposes, insulating materials may be any of those mineral substances that provide a barrier between a desired human environmental feature and an unwanted condition. In this sense, radiation shields, electrical insulations, cryogenic insulation, and acoustical barriers would qualify. For this chapter only the thermal and acoustic insulations used for the median range of normal comfort control will be covered. Because of their magnitude and complexity the other fields are left to other chapters. In another sense, this section deals only with the ultra-lightweight aggregates and insulations, rather than the multitude of light-weight structural materials. Definitions and Uses The insulating materials covered in this chapter are the three groups of mineral products that provide thermal or acoustic barriers through the median temperatures encountered in home and industry. The three mineral categories are perlite, vermiculite, and the silicate wools whether they be categorized as glass, mineral, or rock. Perlites are those amorphous aluminum silicates with minor impurities that take the form of a felsitic, glassy lava possessing a pearl-like luster and concentric cracking. In a more commercial sense the term is used to describe either the natural or processed acidic, volcanic glass, containing from 2 to 5% combined water, that may be converted to a frothy mass by heating rapidly to the softening point. Vermiculites are micaceous, hydrated magnesium iron aluminum sheet silicates of varying composition. Commercial vermiculites are any of these sheet silicates that are capable of sufficient expansion on rapid heating to make an acceptable, highly porous product. Mineral wools, rock wools, silicate cottons, glass fiber are generic names for manufactured fibers in which the fiber forming substance may be slag, certain rocks, or glass. The fibers may be made by a blowing or spinning process. The resultant fibers may be felted or matted or gathered in the manner best suited to the use. The three groups may be used competitively to insulate ceilings and walls. The fibers have strong advantages in this area as they may be manufactured in batts that are stable in residential wall construction. The perlites and vermiculites are more suited to insulate cores and cavities of masonry walls and as plaster and concrete aggregates for thermal insulations. Vermiculite is widely used for insulating attic floors. Because of manufacturing techniques and controls, the glass fibers have made great strides as composites in the plastics industry but only a few of these uses classify in the insulation category.

Jan 1, 1975

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962