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By Timothy W. Ellis

Wire Bonding is the dominant IC interconnection process presently used in the semiconductor assembly industry (1). The flexibility, adaptability and cost of wire bonding will continue to keep it as the key process for the interconnection of integrated circuits to substrates. However, wire bonding still has certain technological hurdles to overcome if it is to continue following the semiconductor roadmap (2). Particular issues which need to be addressed include low overall tensile strength, low elastic modulus, low shear per unit area and mechanical loop stability of Gold based micro-alloys. The ability to produce ?Deformation Process Metal-Metal Matrix Composites? (DMMCs) is based upon the deformation nature of immissible metallic systems. For reference, the Gold (Au)-Molybdenum (Mo) phase diagram is shown in Figure 1 (3). By inspection of the diagram, Au has a very low solubility for Mo, while Mo has essentially no solubility for Au. This is the metallurgical analog of oil and water. In the Au-Mo case, this is particularly troublesome when producing precursor ingots of the alloy to be formed into wire products. In Table 1, the melting points and densities are shown for Au and Mo. As shown, the melting point of Mo is significantly higher than Au, and is very close to the boiling point of Au (2856°C). However, Au?s density is higher than that of Mo. As such, conventional casting techniques are not suitable, since solid Mo would float off the surface of an Au melt thus depleting the matrix of its alloy addition. In this work, two-phase composite wires were produced by deformation processing to develop an interconnection wire with elevated tensile strength, modulus and shear to those commonly available in the market (4). This technology has been used previously in the production of high strength electrical conductors particularly for high field pulsed magnets (5).

Oct 1, 2003

By J. C. Bradbury

The year of the Centennial is upon us. Not only is AIME marking its 100th birthday, but the cement industry is also celebrating 100 years of activity (see article by Roy Grancher, page 48). Fort Dodge, Iowa, and gypsum also tried to get into the act but missed by one year. Frank Apple-yard's gypsum article (page 53) informs us that the Fort Dodge area has been producing gypsum continuously for 99 years. That would seem to make AIME and the industrial minerals doddering oldsters. Not so-our Institute shows more energy than ever, and the word for industrial minerals is growth. These are the mineral resources of the future, the raw materials for the abundant life to come

Jan 1, 1971

ECONOMICS In the preceding pages you will find an attempt to judge the direction of one phase of the mining industry in Drift, and following that a quick round up of what happened to production in 1958 in Trends. Next, Charles Merrill presents a comprehensive price history for the mineral products of greatest importance, complete with figures for the past 50 years. On the following pages Nathaniel Arbiter and Charles Will Wright take a look at price trend prospects and the cold war in mining, respectively. MINERALS BENEFICIATION Fifty years progress is reviewed as a springboard for a look ahead. In the past decade the art has moved forward, but the author fears that the science is not progressing as promisingly.

Jan 2, 1959

PRESIDENT PRYDE: I am sure we have all listened with interest to the presentation of this subject. Anything that promises economy in coal mining today is welcomed by all of us. We will now have a discussion on this paper. If any of you gentlemen want to ask any questions, you may do so. I think we will develop something of interest and along the lines of economy. That is the first consideration of a coal mining man. MR. H. D. RANDALL: It is an interesting fact that in manufacturing we find the greatest economy results from giving a man the simplest possible act to perform, while there is nothing too complicated for a machine. If we want to put up a set screw we find it cheaper to let one man set it up and the other screw it in. The maximum economy is what we are after. Similarly, one of the points of greatest interest which Mr. Ickis has emphasized, is that this automatic equipment not merely dispenses with a manual operator, but also performs certain functions which the operator cannot do. It provides an inherent protection to the apparatus and service not possible under manual operation. We very rarely have cases of failure with these automatic equipments, .and consequently have the advantage not only of having eliminated the operator's salary, but also his mistakes. We have had a large number of these equipments in use for several years, so that their practicality is now thoroughly proven, and the trend of practice now indicates that the automatic idea will be further extended and will become universal for such classes of service. MR. D. C. McKEEHAN (Union Pacific Coal Company) : My notion of an automatic sub-station is one that does not necessarily require new equipment beyond the control equipment; so that any of you that are interested in it can take up with the manufacturers and find out how much it would cost to change any equipment. The greatest point I think is the fact it eliminates the several nationalities from operating the set, either on day shift or night shift. They can so lock the control as to make it impossible for anyone to start or stop it, except the one who has the authority. Another point I do not believe was brought out very clearly: It would be particularly advantageous to people who buy power, and if you could have several sets in parallel, it would allow you to start the shift with one set and cut in the additional sets as the shift progresses. There are various operations that stop at the end of each shift, and-one or two or three sets can be cut out, leaving the load on one set, providing the size of the copper is sufficient to supply all the points of the mine. Another point I want to bring out: In case you have quite a number of sets distributed along transmission line, the switch trips, the operation restores the service, and you may have several hundred-or in case with us, we would have several thousand-K. V. A. of Motor Generator Sets and Rotaries, that would be starting at once, and the switch would automatically trip out again. MR. RANDALL: Another form of control was described as the so-called supervisory control. This control could be started up so the starting would not be synchronous, but could be spread out over a sequence. MR. McKEEHAN: I think that is rather a theoretical consideration for coal miners. They are standing at the controller ready to shut it off unless there is some selective method of starting various sets- MR. RANDALL: I had in mind this supervisory control, one man, a central operator who would determine which station should start and he would take time enough to have his load come on gradually. He would not permit all the installations to come on simultaneously, but come on in succession: MR. McKEEHAN: You misunderstand me. Suppose we had the main switch at Rock Springs, which supplies several camps, and there are several

Jan 1, 1924

it may be clearly seen that one of the most rapidly increasing items in mining operations is the cost of the timber alone, to say nothing of the cost of installation. Consequently, any practical means that may be used to lengthen the life of mine timber will greatly tend to decrease mining costs and result in important economies in operation. The four principal agents by which mine timbers are destroyed are, decay, insect attack, fire and mechanical abrasion. Decay and insect attack are credited with more than 50 per cent of the total amount of timber destroyed in the mines. Numerous methods may be used to conserve mine timbers, such as better selection, preparation, storage and segregation. It frequently happens that good timber goes into places where poor timber would do as well, and timber of inferior quality is sent into places where only the best grade should be used. However, the most effective method of conservation is by treatment with some standard preservative to prevent decay. Some of. the benefits to be noted from the use of preserved timbers are; the reduction in operating costs by decrease in timber purchases; cuts down interference with mining operations due to timber failures on main haulageways; prevents excessive falling of roof in entries by maintaining timber in sound condition; conserves timber supplies and makes possible the utilization of inferior woods; reduces the danger of mine accidents; improves mine ventilation; lessens fire hazard. Our experience thus far with preservatives, while not of a sufficient period of time to establish just what length of life we may obtain from timber so treated, results obtained during the past four years indicate that the intelligent use of preservatives will effect sufficient economies in mine timber costs to justify the expenditures made for this purpose. MR. BAKER (Concluding): Now, if there are any questions you gentlemen would like to ask about our particular operations, I will attempt to answer them. J. H. EMRICK (Sullivan Machinery Company, Denver, Colo.) ; I was wondering how much penetration you get. MR. BAKER: We get between one-sixteenth and one-eighth of an inch; it is a dipping process. With pressure treatment you get-a greater absorption; that is, better than one-sixteenth of an inch. As long as there is no mechanical abrasion, it seems to serve the purpose. MR. EMRICK: Does that apply to the condition of the timber before it is treated? If it is perfectly dry, will it absorb more treatment than if it is partly green? MR. BAKER: Certainly; one of the things we do is to have it thoroughly seasoned before it is put into the preservative. We put some green timber into the mine once, and the fungus went after it right away. MR. EMRICK: What was the difference in the depth reached by the preservative? MR. BAKER: It hardly penetrated at all when it was green. It has to be sound and well seasoned. MR. EMRICK: How long was the timber dipped or treated? MR. BAKER: According to the seasoning. If it was well seasoned, it was left in the hot bath for an hour; if not so well seasoned, it was left for about a couple of hours. C. M. BILLINGTON (General Superintendent, Rocky Mountain Fuel Company, Lafayette, Colo.): Have you found it necessary to treat timber that has been charred? MR. BAKER: No. However, I suppose it has the sane effect; in lots of places they char timber for the purpose of treatment. MR. BILLINGTON: Have you ever tried lime and salt? MR. BAKER: No, this is the only thing we have tried, the creosote and the Aczol; the Aczol is a foreign product. WM. LITTLEJOHN: Which I is preferable, the Aczol or the creosote? MR. BAKER: I couldn't say as to that. MR. LITTLEJOHN: Have you had any tests as to the value of either? MR. BAKER: We have had some of the Aczol timbers in service for a little over four years; we have had some creosote timbers in service

Jan 1, 1926

By F. C. Miller

The briquetting of fuel is an industry centuries old and has followed the hammer and tongs method of making use of any by-product fuel by the simple process of sticking the mass together with anything that will stick. If fuel briquetting, as an industry, once in the lead over coal mining, had kept pace by introducing science, there would not at this time be the mad scramble to look up the fuel briquette family tree and accept every new method as fruit without the cultivation that makes fruit worth while. Cultivation of industry is a mass of evidence showing a tremendous expenditure of money for mistakes paving the way to success. Cultivation of the mining industry is practiced by nations and low temperature distillation and fuel briquetting will in the near future receive the same consideration. Fuel briquettes were used as a winter fuel in Ireland and Scotland before the discovery of America' or the introduction of coal as a fuel to replace briquettes in Ireland. This industry was practiced by the peasants who collected peat from the bogs and cut it into brick-shaped blocks, which were set up to dry in the sun and stored under cover for use or for sale. Demand for peat briquettes led to competition that resulted in a highly refined fuel. In some localities the peat was ground and purified from the earth by washing before placing in presses to squeeze out the excess moisture and form a block of peat about four inches thick. These blocks, after standing in the sun for a few weeks, were cut into briquettes about four inches square by twelve inches long and moved under cover where they remained until thoroughly dry. In this form peat makes an excellent fuel with considerable heat, small amount of smoke while burning, and tough enough to stand hauling in carts and boats without breakage. Slack from domestic coal, non-coking and anthracite, has until recently commanded a very low price and the attention of briquette men has centered on ways and means of preparing this class of fuel for the market in the form of briquettes. Industrial plants with automatic stokers have taken kindly to cheap slack or slack that was cheap because the price has been boosted to a figure where the cost of slack plus the cost of binder and operation makes fuel briquettes somewhat expensive. However, fuel briquettes are being turned out in commercial quantities to compete with prepared lump coal and the demand is in favor of the briquette man. Science has been called to aid the briquette and it is possible to purchase a complete coal briquetting plant that will turn out between four tons per hour and thirty tons per hour of briquettes at a calculated cost per ton to cover material and every item down to insurance on the plant. A few briquettes are being ' made with a mixture of- Portland cement and pulverized coal, where this class of briquette is cheap in the making, there is the increased amount of ash due to the cement to contend with and the briquette is not one that can compete with lump coal. Most binders have a fuel value, such as coal tar, pitch, asphalt residium, flour, glue and secret binders. Most briquettes are of an egg shape, weighing between one and one-half ounces and five ounces, pressed to form with a pressure varying between 1,000 pounds and 2,500 pounds per square inch. This' pressure, together with the binder, make a lump of fuel harder than most grades of soft coal. Most of the briquettes are free from pitch odor, and any tendency to leave a trace of the binder on the fingers, easy to handle, quick to, ignite, high in heat value and capable of indefinite storage without any change. Evaporative efficiency of briquetted fuel in stationary, marine and locomotive boilers has proved that a great many low-grade coals can be fired successfully in the briquetted form, where the same fuel without briquetting failed to give boiler rating.

Jan 1, 1923

Brace yourself-what used to be a 1 billion ton deposit is now a 1 Gt deposit. And that 1520-hp ball mill is now a 1.134-MW ball mill. Beginning with this issue, all engineering units and statistics in MINING ENGINEERING will be reported in SI units. The exception to this is the Technical Papers section, where units may still be reported by dual notation. For the past four years, ME has reported all units of measurement first in SI, followed in parentheses by the equivalent English value. This metrication policy, adopted by the SME-AIME Board of Directors in September 1975, was designed to aid magazine readers through a transitional period from English unit reporting to SI unit reporting. In October 1979, the SME-AIME Publications Board completed the English-to-SI transition by requesting the editorial staff, beginning February 1980, to report exclusively in SI. The Publications Board also requested the editors to prepare a chart of SI conversions useful to ME readers; this information follows on pages 156-157. The What and Wherefore of SI In 1960 the General Conference on Weights and Measures met in Sevres, France, and recommended that a new metric system-one that could uniformly cross all international borders-be adopted to replace all other metric systems. The outcome of this recommendation was the SI system of units, an abbreviation for le Systeme International d'Unites (the International System of Units). It replaces the more familiar cgs (centimeter-gram-second) system and the m/ksA (meter-kilogram-second-Ampere) system. SI consists of seven base units, two supplementary units, and a number of derived units. Other units, called allowable units, may be used even though they are not part of SI. The seven base units are: meter (length); second (time); kilogram (mass); mole (amount of substance); kelvin (temperature); ampere (electric current); and candela (luminous intensity). The two supplementary units are radian, a measurement of plane angle, and steradian, a measurement of solid angle. Supplementary units can be used in combination with SI units, e.g., radiant intensity is expressed in W/sr, watts per steradian. Derived units are combinations of base and supplementary units. Velocity is expressed as meters per second (m/s), and acceleration as m/s'. Using the relation established by Newton's second law of motion, force is expressed as kg-m/s2, more commonly known as the newton (N). Energy (work) is force times distance, expressed as kg-m/s2 and known as the joule (J). Power is work per unit time, expressed as kg, m2/s3 and known as the watt (W). Allowable units are the exception to the rule-they are not taken from base or supplementary units but, nevertheless, are used in the SI system. Volume units are normally expressed as the cubic measure of a length, such as cm 3. But a fluid volume of a cubic decimeter (dm3) is called a liter (L); the "L" is capitalized in another special SI rule to keep the lowercase "1" from being confused with a numeric "1". Other allowable units are degrees Celsius (°C) for temperature; and the minute (min), hour (h), day (d), and year (a) for time measurements. The prefixes in the table on the following page are used with SI units to express the magnitude of a measured quantity. A mill that processes 1000 tons of ore per day would be designated a 1 kt/d mill; a mine producing 10 million tons of ore per year would be called a 10 Mt/a mine. The rule here is to use prefixes that keep the value in a convenient range from 0.1 to 1000. In other words, it would be incorrect to write 25 000 kg-the prefix should be changed to indicate 25 Mt. One of the distinct advantages of SI is that it retains the decimal relation between multiples and submultiples of the base units for each physical quantity except for time. One more rule of SI syntax-numbers are separated into groups of three with a space between each group rather than a comma, e.g., 3,839,174 becomes 3 839 174. By the same token, a decimal number is also broken by spaces, e.g. 0.738153 is written as 0.738 153.

Jan 2, 1980

By Dan Nilsson

INTRODUCTION There are many mine planning factors in sublevel caving, as in the other mining systems, which when varied can substantially alter mining costs and profit¬ability. In this chapter, the following four topics are addressed with regard to economic optimization of sub¬level caving: production planning, haulage level spacing, orepass spacing, and extraction cutoff. The costs used here are the right order of magnitude but since each mine is unique, they should be considered only as examples. The objective is to demonstrate the tech¬niques which can be used. In a real mine, the evalua¬tions must be done using actual costs and conditions. It is difficult to predict exactly the costs involved, and therefore it is valuable to perform a sensitivity analysis to evaluate the effect of making incorrect as¬sumptions. Since the mining industry is very capital intensive, the effect of the interest rate must also be studied. PRODUCTION PLAN FOR AN IRON ORE DEPOSIT Introduction The first and most important thing to do before de¬signing an underground mine is to establish a long-range production plan. Such a plan is necessary for all eco¬nomic evaluations and should provide information about the lifetime of the mine, how much ore and waste must be handled per year, how much development per year is required, etc. An example is given in the following section. Problem In an iron ore mine sublevel caving is used. The iron content is 42%, and the mine supplies a pelletizing plant with an annual capacity of 3 million t/a. The ore body is shown in Fig. 1. The length of the ore body is 1000 m and the width is 100 m. Each slice is 10 m high, and there are 10 m be¬tween crosscuts, each of which has an area of 20 m2. The density of the ore is 3.5 t/m3. The spacing between rings is 2 m, and the extraction is 100%. The iron con¬tent is 66% in the pellets and 6% in the tailings. The problem is to develop a detailed production plan. A typical sublevel caving sequence is shown in Fig. 2. Solution Amount of ore per meter of crosscut: 20 X 3.5 = 70 t. Number of crosscuts per slice= 100. Length of crosscuts per slice: 100 X 100 = 10 000. Ore from crosscuts per slice = 10 000 m X 20 m2 X 3.5 = 700 000 t. Number of sublevel caving rounds per slice: 10 000/2 = 5000. Area for each blast in sublevel caving: 10 X 10 - 20 = 80 m2. Amount of ore per blast: 80 m2 X 6 m X 3.5 = 560 t. Extraction: 100% (see extraction curve Fig. 12). Loaded ore per blast: 75% or 420 t. Loaded waste per blast: 25% or 140 t. Total: 560 t. Total amount of rock from each blast in the sublevel caving: Ore: 560 t of which 2 X 70 = 140 t from develop¬ment work and 420 t from sublevel caving. Waste: 140 t. Total: 700 t. The ore needed per year is 3 X (66-6)/42-6 5 mil¬lion t. Necessary number of blasts per year= 5,000,000/ 560 = 8929. Distance to develop per year = 8929 blasts per year X 2 m per blast 17 858 m. Total amount/year: Ore from development work 17 858 m x 70 t/m = 1.25 million t/a Ore from sublevel caving: 8929 blasts per year X 420 tons per blast = 3.75 million t/a 5.00 million t/a Waste rock dilution: 8929 blasts per year X 140 tons per blast 1.25 million t/a Total amount to hoist 6.25 million t/ a The amount of ore from development work will in¬crease a little if the horizontal drift is placed in the ore body and not in the footwall. In this example the ore loss in 20%, and the waste rock dilution is also 20%. After taking the ore loss into account, the lifetime for 100 m of the ore body will be:

Jan 1, 1982

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By C. Gatlin, N. E. Garner

Results of impulsive wedge penetration tests on two synthetic, plastically deforming rocks are presented. Basic data obtained were force-time, displacement-time, and force-displacement curves for the impacts, plus the crater geometry. Wedge geometry and blow frequency were varied over a considerable range. The synthetic rocks consisted of wax-sand mixtures; two waxes of diflerent ductilities were used to provide variable "rock" characteristics. Conventional triaxial tests showed that these synthetic rocks exhibited force-deformation curves and Mohr envelopes quite similar to real rocks, except that strengths were much lower. Measured forces from static penetration tests agreed closely with theoretical values; however, dynamic force values were much higher than the static. These latter disparities are attributed to the viscous nature of the waxes. Thus the utility of these or similar rock models must depend on the scaling of rock viscosity, which is as yet unknown for impulsive loadings at elevated stress states. It appears, however, that some macroscopic, static phenomena may be studied with wax-sand rock models. INTRODUCTION The resistance of solid materials to indentation or perforation by projectiles or other penetrators has been studied by workers in many areas. Despite these efforts no universally accepted laws or formulas are available for describing experimental observations. In the metals field the force-deformation behavior of impacting bodies is often analyzed by the Hertz law for elastic collisions, the Meyer law if plastic deformations occur, or some combination of both.' The similarities of these expressions to empirical drilling formulas of the oil industry are apparent. Beginning with the basic contributions of Simon and co-workers at Battelle,' a number of experimental papers concerning the reaction of rocks to vertical impact have appeared in the U. S. mining and petroleum literature.'-' Most published data have, to date, been obtained at atmospheric pressure, although some early high pressure information was reported by Payne and Chippendale.8 Maurer" has recently utilized available brittle impact data to develop a drilling rate equation based on the experimentally observed proportionality between crater volume and blow energy. His result agreed with earlier efforts by both Somerton, who used dimensional analysis, and Outmans, who used plasticity theory. It has long been known that rocks exhibit different modes of failure depending on the state of stress. The literature in this area is considerable; however, papers by Bredthauer, Handin and Hager,13 nd Robinson", are adequate to illustrate the point. Since rocks flow plastically at certain triaxial stress conditions, the mathematical theory of plasticity has been used to analyze the rock drilling problem. Cheatham'" has altered the wedge identation solution of Randtl to rocks, and has developed useful equations for penetrator forces under a variety of conditions. Outmans" has utilized Hill's solution in a similar manner to develop a drilling rate equation. Both Cheatham and Outmans used the linear Mohr-Coulomb rule to relate rock strength and confining pressure. The actual stress at the hole bottom is not easily ascertained, although photoelastic studies by Galle and Wil-hoit," plus the analytical treatment of Cheatham and wilhoiti8 provide some insight. Consequently it is not clear to what extent the highly idealized rheological model of a perfectly plastic solid can be realistically applied to the rock drilling problem. This paper is the first report on a long range experimental study of crater formation in rocks at elevated stress states. The data presented here are from the first phase of the project. Data obtained from impulsive wedge impacts on two synthetic, plastically deforming rocks are presented. MODEL ROCKS Geologists have long been faced with modelling the behavior of the earth and, as a consequence, have studied scaling problems in some detail.' In general, their main problem is handling the wide disparity between laboratory and geologic time. In our studies the time effects (blow velocity or rate of loading, blow duration, etc.) were essentiafly the same for both. model and prototype, as were were geometry and tooth penetration. Thus application of available scaling laws suggests that Similarity is obtained if the stress-strain curves of model and prototype are similar." For this reason Hubbert and Willis''

By R. E. Utting

INTRODUCTION Until recently, gamma doses had been largely ignored in Ontario uranium mines. This has been due to the assumption that these doses are small and have been more or less unchanged with time and hence their effects have been included automatically in the epidemiological studies that led to the establishment of radon daughter exposure limits. This assumption had to be challenged for two basic reasons. The first was that radon daughter exposures to miners have been progressively reduced over the years due to improved ventilation and ever more stringent regulations, while gamma exposures have presumably remained relatively unchanged. Therefore it must be assumed that the ratio of gamma to radon daughter exposure has gone up. The second reason is more philosophical. It is clearly inappropriate to make judgements on the significance of a potential industrial hazard when the magnitude of that hazard has not been fully assessed. Having decided that some sort of assessment of gamma exposures to uranium miners must be made, it was than necessary to determine how this should be done. Several options were available, for instance: (i) Wholesale personal gamma dosimetry for all mine and mill workers, (ii) Personal gamma dosimetry only for those workers suspected of receiving the higher doses, coupled with area monitoring to estimate the exposures of other workers, (iii) Area monitoring coupled with dose rate times time calculations for all. This would correspond to the generally prevalent method of assessing radon daughter exposures. It was argued that since radon daughter exposures are the major radiological hazard in uranium mines, to invest resources for assessing a lesser hazard to a greater degree of precision was not cost effective. (iv) Since gamma dose rate is related to ore grade, individual doses could be assigned from knowledge of work location and ore grade. Before deciding which of these options would be most appropriate, it was necessary to have some idea of the magnitude of the problem. Very few data were available in the literature and with the exception of a few spot dose rate measurements, and the results of a few gamma dosimeters issued to selected individuals by some of the mining companies, nothing was available. A rule of thumb of obscure origin is often quoted within the industry indicating that gamma dose rates underground will be about 0.25 mR/h per lb/ton or 5 mR/h per % U. This had been used by some to justify neglecting gamma radiation at least for ore grades of the order of 0.1% or 2 lb/ton, on the grounds that gamma dose rates would be of the order of 0.5 mR/h and therefore give rise to annual doses of only about 10 mSv (lrem). That is, it was assumed that gamma radiation was of limited concern compared to the hazard associated with the inhalation of radon daughters. We were thus faced with the situation of just assuming that no regulatory limits were being breached. This situation could not be allowed to continue. A program was initiated to investigate the gamma doses absorbed by uranium miners in three mines in Ontario, and extensive gamma surveys were conducted in the Quirke 2 mine of Rio Algom Ltd, Elliot Lake; Denison Mine, Elliot Lake; and Agnew Lake Mine, Espanola. Negative reaction was received from several mine company officials to the possibility of all miners being required to wear personal gamma dosimeters due to the logistical difficulties involved, and therefore part of the project was aimed at determining if a reliable correlation between gamma dose rate and ore grade in the work location could be deduced, in order that dose rate times time calculations might be used for gamma dose assessments. The results of these programs provided evidence that the gamma dose for some employees in the three mines investigated may be a significant fraction of the current maximum permissible annual dose of 50mSv (5 rem). When combined with radon daughter exposures in the manner recommended by the ICRP at their 1980 Brighton meeting (ICRP 80) the results indicated that some individuals will come close to the resulting limit and may even exceed it. The results also indicate that is probably not feasible to develop a reliable formula for

Jan 1, 1981

By Elmer Weber, W. M. Baldwin

Solid lead obeys a single parabolic weight increase vs. time law. In contrast, liquid lead undergoes three successive parabolic weight increases vs. time laws, the first of which has a low constant relative to the latter two. The conversion times for the change from one parabola to the next decrease with increasing temperature. IN recent reports on the subject,1,2 it was noted that zirconium and titanium scale in air by a complex mechanism. The scale first forming on the metal is protective to the extent that it gives a low constant, K, for Tammann's, and Pilling and Bedworth's parabolic equation: w² = Kt [1] relating weight increase, w, due to chemical reaction of the metal with the air, and time, t. After hundreds of hours of apparent stability in some cases the first scale yields to another that offers little protection to the metal. This transition from one scale to another, from a slow parabolic oxidation reaction to a fast one, was not due to impurities in the atmosphere or incidental effects (changing environment, etc.) but was a specific behavior of the metal itself, the transition occurring at definite times (dependent on temperature) and showing other reproducible traits. In view of this behavior how can long-time service behavior be predicted from short-time laboratory tests, not only in the case of these metals, but in any case? Certainly a systematic study of the type of scaling behavior described above—wherever it is found—would help to answer this question. The present paper is a report on the behavior as it is found in lead—the only metal to the authors' knowledge for which the behavior has been described at all, if inadequately, for our present purpose.* At least four oxides of lead are known, of which one occurs in two allotropic forms. They are ß (red) tetragonal PbO stable up to 486°C;8 a (yellow) orthorhombic PbO stable from 486°C up to its dissociation temperature in air at about 2300°C;9 minium or Pb3O4 which from the dissociation pressure data given in Fig. 1 decomposes to PbO at 540°C in air; lead sesquioxide or Pb2O3,; and lead dioxide or PbO2 which, according to Fig. 1, decomposes in air at 400°C to minium. In view of the high dissociation temperature of PbO, lead will scale up to at least its boiling point. Further, it is known that oxygen is almost insoluble in liquid lead.'V his implies a fair probability that an oxide scale would not dissolve in the molten metal and would afford the same protection to lead in the liquid state as in the solid. All of the oxides of lead for which specific gravity data are available are more voluminous than an equivalent weight of metal or a lower oxide from which they might form, hence the scales will be in compression. Lead oxides are known to be ductile, so it would be anticipated that they would form coherent nonporous scales. It is not surprising to learn, then, that both solid and liquid lead scale according to the Tammann, and Pilling and Bed-worth law.14,15 (Gruhl states that at 600°C and above lead oxidizes linearly with time because of "spitting" of the scale.) The parabolic constants K reported by various investigators3,14-16 are badly scattered, however, as shown in Fig. 2. The oxides formed on solid lead were described as being reddish-brown but were not chemically identified by Pilling and Bedworth.15 Gruhl's descripdin³ of the appearance of the scales On his liquid samples indicates that a (yellow orthorhombic) PbO is formed initially on the specimens but gives Way eventually—at least at temperatures below 486 °C— to .ß (red tetraunal) PbO, and that below 540°C minium—Pb3O4 :is firmed at an even later time as an overlay on either the red or yellow PbO. Fig. 3 is a graphical interpretation of Gruhl's description. Gruhl does not indicate any change in the parabolic scaling rate as yellow PbO converts to red. He does indicate that minium reduces the scaling rate, al-

Jan 1, 1953

By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV 's of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.' The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham's process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N's were quite fast. Similarly, the turn-off time of the N-P's increased rapidly with forward current while that of the N-N's was independent of forward current. Both N-N's and N-P's were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.' The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By E. Wainer, K. D. Burnham

A wet beneficiation technique for producing wollas-tonite from its ore in high yield and purity has been evaluated in a pilot plant operation at the rate of 75 tons per month. Finely crushed, unsized wollastonite ore mixed with water is passed through a high in tensity oscillating wet magnetic separator of unique design and in a single pass over 90% of the wolla-stonite exhibiting a crystal purity of 99.8% is obtained irrespective of size of feed fraction. Thereafter, the material is processed by closed cycle standard wet milling and classification techniques to yield a 1µ size product, though any mesh size up to and including 50 mesh may be obtained, if desired. Costs appear to be significantly lower than those available from dry processed techniques. Wollas tonite made by this unusual wet process appears to have potential utility in the following fields: ceramics, paints, plastics, paper, organic finishes, reinforcement of portland cement items, controlled porosity refractory ceramic foams, cinder and concrete block paint, and the like. The 1µ and certain chemically processed varieties of wollastonite may have unusual utility in the paper industry both as a filler and as a coating material and in the organic finish industry. Extensive deposits of wollastonite ore equivalent to an average tenor of 50% to 60% of this latter mineral in easily separable form exists in and around Essex County in northern New York State in reserves of the order of several tens of millions of tons. While important portions of these deposits are susceptible to open pit mining techniques, one operation near Wills-boro, N.Y., involves tunnel mining and dry milling and beneficiation techniques. This mill and tunnel mine is presently being operated by The Cabot Corp. and a variety of particle sizes are now sold into markets in the ceramic, paint, plastic finish, floor tile and in similar fields in substantial tonnages on a repetitive basis. Serious investigation and study over the past several years has indicated that, outside of the obvious economies of open pit techniques for mining purposes, wet beneficiation and milling procedures applied to the ore not only represent a potential for greater economies in the production of a superfine finished product but yields products of improved properties exhibiting increased market potential which may not be available from the dry ground product. The Lewis and Deerhead deposits, controlled by the Adirondack Development Corp., appear to be identical to the Wilisboro deposit. Utilizing ore taken from the Lewis and Deerhead deposits, a pilot plant process for the wet beneficiation, milling and classifying of wollastonite ore has been operated for several months. After scalping a marketable garnet product from a minus 16 mesh dry crushed feed on a high intensity roll magnet the balance of the material is then roll crushed in a closed cycle until it will pass a 50 mesh screen. The product constitutes the feed of the wet magnetic separator. The heart of the new beneficiation process is a cyclically operated wet magnetic separator which exhibits the unique feature that unsized feed is easily handled. Product yields of higher purity are equal to that obtained with dry magnetic separations which use closely sized dry ore and multiple passes, but only produce wollastonite of about 98% mineral purity as determined by sink float techniques. It was anticipated that the wet processing through the grinding, milling and classification stage would yield a low cost 1µ ground product which should make available greatly increased applications for the mineral beyond those presently enjoyed. The improved purity was also expected to provide coarser sizes which might be utilized as a raw material for chemical modification which again would expand the uses of wollastonite. The evidence thus far collected appears to indicate that this premise may be expected to be fulfilled. There are on the surface of wollastonite particle sites at which cheinical reactions may occur1. It is believed that wet ground material provides a better base which will allow wollastonite a deeper entree into the field of chemical raw materials. Wet ground at 20µ and finer permits with certainty a number of chemical reactions, some of which are mentioned later in this article. While well crystallized wollastonite makes up the majority of the ore, the balance consists mainly of very weakly magnetic diopside of the hedenbergite-

Jan 1, 1965

By L. S. Allen, R. L. Caldwell, W. R. Mills

Borehole models used in the study of nuclear well logging are reviewed and the merit of heterogeneous us homogeneous formation simulation is discussed. .A heterogeneous model for simulating sandstone formations of variable porosity is described. Simulation adequacy was checked by steady-state and pulsed-neutron measurements. INTRODUCTION In the course of developing new methods of nuclear well logging, the problem of testing new logging instruments under controlled conditions always arises. This testing is usually done in wells of known lithology, porosity and fluid saturation, or in laboratory test facilities which simulate the borehole environment. Although the former approach is possibly more satisfying, it is frequently difficult or inconvenient to find wells with enough variation in the cited parameters for a truly comprehensive study, On the other hand. laboratow- test facilities can simulate a wide variety of formation and borehole conditions if care is exercised to maintain adequate simulation under all conditions. Workers concerned with the development of nuclear well logging methods have reported several types of research facilities in the past. Tittle, et a1 used cubical tanks filled with Ottawa silica sand to study the steady-state behavior of thermal and epithemal neutrons in simulated sandstone logging environments.1 In addition to the effects of fresh vs salt water, a wide variety of casing sizes and compositions were investigated. Tittman also used a large tank of Ottawa sand to measure the slowing down length of sio2;2 for making the same measurement in CaCO3, however, an assembly of solid Vermont marble blocks was used. More recently a very useful and carefully planned test pit for nuclear logs was constructed under the auspices of the API.3 This facility consists of three massive limestone sections, each 6-ft thick and more than 5 ft in diameter. The blocks are buried, one on top of the other, in a concrete- lined pit having a total depth of 24 ft. Each section is made of a different limestone to achieve porosity variation, the selection being Carthage (2 per cent), Indiana (19 per cent) and Austin (26 per cent). The blocks are traversed by a 7 7/8-in. diameter borehole and are saturated with fresh water. Great care was taken to insure total saturation of the stone. Homogeneous mixtures and materials have not been used exclusively for simulating earth formations. Tittle, et a1 4 showed that a heterogeneous lattice of water and graphite could be used to simulate Liquid furfural with very little effecton measured thermal and epi thermal neutron distributions. Subsequently, a lattice-type model for simulating limestone earth formations was designed and built by Berry This limestone model was constructed of 7/8- x 11/4- x 36411. marble rods glued together with a plastic resin to form a 36-x 42- x 42in. cube. The cube was honeycombed vertically with 7/8- x 7/8- x 3641-1. holes for porosity and had a 111/2-in. diameter hole in the center to serve as the borehole. Lower porosities were simulated by placing marble rods in the square holes. The finished cube was used with the borehole vertical and set in a tank to hold liquid for filling the holes in the rock matrix. A second type of heterogeneous borehole model has been proposed by Kukharenko, et a1.6= In this concept the model is composed entirely of solid material. The hydrogen equivalent of formation fluids is simulated by making the model of alternating layers of dense rock and celluloid. Additional hydrogen is included by drilling vertical holes in the rock sections and filling them with solid forms of hydrogeneous material. The volume of the holes is equal to the volume of the celluloid layers, so an axial and radial dispersion of the hydrogeneous material is thus obtained. One such model was composed of alternate 50 mm-thick sand layers and 2 mm-thick celluloid sheets. Approximately 200 appropriately spaced plastic tubes were used in each sand section. The plastic tubes were filled with paraffin for additional hydrogen concentration. This arrangement yielded a model with a water-equivalent hydrogen concentration of 10 per cent. Experimental data taken in this model and in a model consisting of the same material but homogeneously dispersed showed that the heterogeneous system adequately

Jan 1, 1966

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By C. E. Kemp, A. B. Dyes

Results of a field research project on the thermal recovery of oil by movement of a combustion front are presented. This field test was conducted in the South Belridge field, This The war paitern was a Southsing1e 2.5-acre five-spot pattern in the 700-ft deep Tulare sand. Results of this project indicate the technical feasibility of producing high viscosity, low-grallity crude oils by thermal means. It was demonstrated that heavy oils could be moved rapidly over considerable distances by thermal drive, and that high percentage recoveries of oil could be effected. The bulk of the oil recovery came after arrival of the burning front at a production well. However, rapid corrosion and high-temperature failure of conventional pipe and equipment both below and above surface occurred. Stainless steels gave more satisfectory performance under these conditions than did conventional steels. Oxygen was seldom observed in gas from wells ahead of the burning front, and it appears that the front was continuous throughout the life of the experiment. INTRODUCTION During late 1953 and early 1954, industry-wide attention was focused on the thermal recovery of oil by movement of a combustion front through an oil zone. Two separate Oklahoma field tests were described in publications by Kuhn and Koch, and Grant and Szasz. To obtain basic information needed for making engineering and economic appraisals of commercial recovery of heavy oil by this thermal recovery method, a new field research projecta3,4 was started May 31, 1955. Twelve oil companies contributed to this project with General Petroleum Corp. as operator. Since combustion recovery experiments* with heavy oils in other areas had been conducted in small patterns,"' an important purpose of this test was to determine whether the process could be operated in a pattern of near-commercial well spacing. The south Belridge field, located 30 miles north of Taft, Calif., was chosen because its oil sands are similar to many heavy oil sands which typically have low primary recovery and leave a large amount of oil in place. such fields are not particularly suited for common secondary recovery methods. DESCRIPTION OF TEST SITE The test interval was a Tulare sand at a depth of about 700 ft. Nine test wells were drilled, cored and completed from Oct., 1955, through Jan., 1956. The initial pattern shown on the map, Fig. 1, consisted of an injection well (II)', four producing wells (1P-4P), and four observation wells (IT-4T). An old well (81) was also recompleted for use as an observation well. The area enclosed by the original four production wells was 2.5 acres; the distance from the injection well to each production well was 233 ft. During the combustion period, Well 5P was drilled to replace Well 2P, and Well 6P was drilled to replace Well 3P. The new wells were 25 ft beyond the old production wells along a diagonal from the injection well, and resulted in an increase in pattern area to 2.75 acres. Isopachs are shown in Fig. 1. The average thickness of the oil sand in the test pattern was 30 ft. Fig. 2 presents two cross sections through the test pattern. Oil sand is represented by white and claystone by gray. The dashed lines indicate layers of conglomerate grading to claystone. The sand thickness was fairly uniform throughout the test pattern except in the 1P area. The sand body dips gently from the northwest to southeast, about 3 degrees from horizontal. The sand is unconsoli-dated, and grades from very fine material to pebbles as large as 2 in. in diameter. Table 1 presents the average initial properties of the formation. The in-place porosity of 37 per cent was estimated from the porosity of coke-consolidated cores taken after combustion. Original core analyses data were adjusted to 37 per cent, giving pore volume saturations of 60 per cent oil, 37 per cent water, and 3 per

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.' At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.