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By Klaus Detert, Joseph Ziebs

The progress of primary recrystallization has been studied in alloys of nickel with 0.01, 0.1, and 1.0 at. pct Ta. It can be shown that in one particular alloy containing 0.1 Ta and 0.02 02 a large grain structure (0.5 mm diameter) could he developed by primary recrystallization in thin sheetswhich were cold-worked to 97.5 pct reduction in thickness. Electron transmission microscopy demmstrates that this phenonmena was linked to the occurrence of fine precipitates at subboundaries. A discussion of how fine precipitates can exert under certain circumstances a rather distinct retarding effect on nucleation rate is included. IN a former investigation, the recrystallization and texture formation in a series of binary nickel alloys including pure nickel were studied.' Nickel alloys with some tantalum added displayed peculiarities during primary recrystallization which have been studied in more detail by the present investigation. The alloys were prepared by powder-metallurgy techniques similar to the previous investigations.' Pure metal powders were thoroughly mixed to obtain alloys with 0.01, 0.1, and 1.0 at. pct Ta, referred to as alloy A, B, or C, respectively. The metallic impurities were kept below 0.005 at. pct except iron and cobalt with slightly higher values, by using highly purified nickel and tantalum powders.' The mixtures were pressed into bars and sintered at a temperature of 1300°C. The sintering atmosphere was either high vacuum, dry hydrogen, or wet hydrogen. The sintered rectangular bars were rolled 60 pct to a thickness of 3 mm, then annealed under dry hydrogen at 1000°C and again cold-rolled to about 97.5 pct reduction of thickness. After this heavy deformation, the sheet thickness was 0.07 5 mm. In order to study primary recrystallization which occurred in measurable times between 400" and 600°C, samples of the rolled sheets were annealed in a salt bath at various temperatures for various times in order to study the progress of recrystallization by hardness measurements and microscopic examination. For optical observation, the samples were polished and etched in a solution of 65 cu cm HNO3, and 18 cu cm acetic acid in 20 to 100 cu cm H2O, depending of the particular sample and annealing treatment. For transmission electron microscopic observations, thin foils were prepared by the combined window and Bollmann techniques.273 The electrolyte consisted of 23 pct perchloric acid and 77 pct acetic acid held at 15°C. Polishing was performed at a current density of 0.4 amp per sq cm. The examination of the thin films was accomplished by a Siemens Elmiscope-type electron microscope operating with an accelerating voltage of 100 kv. RESULTS The progress of primary recrystallization was very accurately followed in these alloys in order to establish the time when recrystallization started and ended during an isothermal anneal. Table I gives some of the data obtained by these studies. The time for beginning is a mean value, where somewhat less than 5 pct of the matrix has recrys-tallized. The end of recrystallization is the time when at least 95 pct of the matrix has recrystal-lized. Listed are three different B alloys, with 0.1 Ta distinguished by different sintering atmospheres which influence the rate of primary recrystallization. By the above method, the state of the grain structure when primary recrystallization was completed, but grain coarsening had not started, could be clearly defined. The average grain diameter of the recrystallized matrix is also given in Table I. The grain size did not depend on the temperature of the isothermal anneal. With one exception the grain size of the primary recrystallized matrix was found to be rather fine

Jan 1, 1965

By J. W. Schroeder

SEAMLESS pipe, the product produced from piercing a solid round billet of steel by the Mannesmann process, was first produced in the latter half of the 19th century, the Mannesmann machine having been patented in 1885. The products of other processes also have been termed seamless pipe; for example, the cylindrical section produced by "cupping," which consists of forming a cup from a flat plate or disk and further elongating the cup into a tube by passing it through a set of reducing dies. The purpose of this paper is to discuss some of the more important metallurgical factors and their relationship to the economical production of seamless pipe produced by the Mannesmann piercing process. The first seamless tube plant in America was established at Shelby, Ohio, in 1891, and was employed in the manufacture of bicycle tubing. For a number of years the bicycle industry was the only user of seamless tubing, and this tubing was produced by hot-rolling pierced billets imported from Europe and finishing on the cold drawbench. At the turn of the century, the automotive industry was responsible for an increase in the demand for seamless tubing. The growth of this industry was the dominant factor leading to the phenomenal growth of the petroleum industry, which in turn created a tremendous demand for seamless pipe. In addition; the old lapweld iron boiler tubes for stationary and locomotive boilers were replaced gradually by seamless tubes. Since 1929, the production of seamless steel pipe and tubes has increased over loo pct. In 1929, 1,459,9031 net tons of seamless pipe was produced, including both hot-finished and cold-drawn material, as compared with 3,087,3122 net [ ] tons in 1948. Table I gives the distribution of seamless pipe by classes for 1948. METALLURGICAL PROBLEMS From a metallurgical standpoint, the production of seamless pipe has presented many problems. Practically every type of steel, carbon and alloy, with the exception of the superalloys developed during World War II, has been pierced and rolled successfully into tubing. This includes bessemer, open hearth, by the stationary and duplex processes, and electric steels. The range of sizes produced is no less staggering to the imagination, when it is considered that the hypodermic needle, which is 0.016 in. diam with a wall thickness of 0.004 in., and pipe for gas or oil transmission lines, with a 26 in. OD, are both seamless tubes. Between these extremes, the range of diameters and wall thicknesses meets most present-day demands for seam-

Jan 1, 1951

By F. H. Gilpin

SINCE Noah pitched his ark within and without with pitch, the use of asphalt in human endeavor has been increasing-for Noah's pitch was asphalt. Asphalt is a bituminous material found in nature, either pure or admixed with smaller or greater quanti-ties of mineral and non-mineral materials, or obtained by the refining of crude asphaltic-base petroleum under proper methods of control. Native or "natural" asphalts are scattered through-out the world, though the commercial value of the various deposits varies greatly, depending upon both their accessibility and magnitude and the quality of the material found. It is an acknowledged fact that such asphalts have been produced through natural causes by practically the same application of tempera-ture and pressure as are used in the modern refining of crude asphaltic-base petroleum. The best known of all the native asphalt deposits are those of Trinidad Lake in the Island of Trinidad, British West Indies, and of Bermudez Lake in Vene-zuela. Asphalt from Trinidad Lake, after refining to remove organic and some inorganic diluents, contains approximately 35 per cent, of inorganic residue, and the asphalt thus produced must be fluxed with lighter asphaltic or semi-asphaltic base oil to make it com-mercially utilizable. The refined asphalt obtained from the Bermudez Lake deposit contains from 4 to 6 per cent. of inorganic material which cannot be removed. This asphalt, also, must be fluxed to produce com-mercial products. Small quantities of similar materials are available in other locations. The best pure native asphalt' is known as. gilsonite and is mined in com-mercial quantities in the State of Utah. In numerous places in the United States, particularly Oklahoma and Kentucky, there are deposits of sand¬stone and limestone impregnated with bitumen, which are known as rock asphalts. These rock asphalts may be used, particularly in the paving industry, either as found or by slight fluxing; from some deposits the asphalt is extracted and marketed commercially.

Jan 2, 1923

By H. G. Doll

A new electrical logging method. called MicroLaterology is described. whereby the resistivity R of the invaded zone close to the wall of the bore hole is measured. This method essentially utilizes a system of concentric circular electrodes iml,edded in an insulating support which is applied to the wall of the hole. A beam of current of very small diameter is focused horizontally into the formations by means of an automatic control device. and then opens widely at short distance from the wall. with this method, R most often can be recorded directly. except when the mud cake is very thick. in which case a correction is easily provided. The basic role of factor R in the quantitative analysis of electrical logs in terms of fluid saturation and of porosity is explained. The paper is illustrated with field examples. INTRODUCTION In electrical logging. the resistivity of that part of the penneable and porous formations which is invaded by mud filtrate is an important factor in the interpretation. Measurements made with the conventional devices — normal. lateral — and also with improved systems as the Laterolog and induction logging' — are very often more or less affected by the presence of the invaded zone. and the knowledge of the resistivity of this zone is useful in the evaluation of the true resistivity of the beds. which itself is a basic element for the determination of fluid saturation. Moreover. the comparison of the resistivity of the invaded zone with the resistivity of the mud filtrate gives valuable indications on the magnitude of the formation resistivity factor — which in turn is necessary for the quantitative interpretation of the logs. both in terms of fluid saturation and of porosity. On the other hand. it is generally admitted that the invaded zone is not a homogeneous medium separated from the uncon-tamirlated part of the bed hy a well defined cylindrical boundary. but that the fluid distribution—filtrate. connate water. hydrocarbon — and hence. the resistivity. in the invaded zone varies progressively with the distance from the wall of the hole. The term "resistivity of the invaded zone" therefore corre-sponds to an average value which is a function of the distribution of the fluids Inasmuch as the law of this distribution is not exactly known, the resistivity of the invaded zone is not a well defined factor. A much better definition is obtained if the medium under consideration is limited to that part of the formation which is within a short distance from the wall of the hole. It seems likely a within a distance of at least two or three in., most of the fluids in in the pores of tile formation have been displaced by the mud filtrate. The connate water has almost certainly been flushed out. and the oil. if any has generally been reduced to a comparatively small amount. The resistivity witliir~ the radial limit of two to three in. is. therefore. prac.tically constant at an). given level: its value. at least when the proportion of conductive solids in the formation is negligible. is chiefly dependent on the resistivity of the filtrate and on the porosity of the formation, and is affected only to a relatively small degree by the presence of the small amount of residual oil. This part of the formation close to the wall of the hole will he designated in the following as the "flushed zone." a-distinguished from the more general term of "invaded zone'. which relates to the part of the formation extending from the wall out to the distance where the formation is completely uncontaminated. The symbol R,, will he used for the resistivity of the flushed zone. (The notation R is related to the radial distance from the hole. If x designates this distance. xo is the initial value of x, i.e., the value corresponding to the region very close to the wall.) The determination of R is difficult, if not impossible. from logs made with the conventional devices. The long normal and the long lateral are. of course. not suited for this purpose because their radii of investigation are by far too large. The short normal. and the limestone sonde—-after correction for the effect of the hole hole — give resistivity values which corre. spond to materials situated within a comparatively short distance from the hole, but this distance is still several time. as great as the thickness of tire flushed zone. The only value which can be obtained with these devices corresponds to an average resistivity of the invaded zone- — and this only provided the invasion is deep enough, since otherwise the meas "red values would also be affected by the uncontaminated region beyond the invaded zone. It should nevertheless be recalled that despite these limitations. the measurements given by the short normal and or the limestone sonde are always very useful for qualitative interpretation. and also in favorable cases for the qantitative analysis of the logs in terms of saturation and porosity. The MicroLog. which was primarily developed for the detection of permeable beds and for an accurate determination of their boundaries. provides a good approach towards the evaluation of R. In the case of hard formation.. however. The

Jan 1, 1953

By Herluf P. Nielsen, Robert I. Jaffee

IN recent years much attention has been given to high-melting alloy systems, It has been of interest in this respect to investigate the alloys of platinum and tungsten, which were known from the literature to have very high melting points up to about 50 pct tungsten, but about which little had been published on the high-tungsten side of the system. Powder metallurgical methods were used throughout this investigation for the preparation of the alloys, utilizing electrical sintering techniques such as are used for tungsten and molybdenum. In the course of the work it was found desirable to determine fusion temperatures of the alloys, and it was possible from these and other data to draw a tentative constitutional diagram (solidus, mostly) applicable to the high-temperature part of the system. No attempt was made to determine solid solubility vs. temperature data, nor to investigate the lower temperature transformations in the solid state. Data on the microstructure, hardness, and a note on oxidation resistance of the sintered alloys were obtained. PAST WORK Müller1 determined liquidus temperatures of platinum-rich alloys to 50 pct tungsten, using a radiation method employing a photoelectric cell, and found that the melting points increased progressively from 1771°C for platinum to 2350°C for the 50 pct alloy. Microscopic evidence by Müller that complete solid solutions exist to 50 pct tungsten was not checked by Kremer2 who, according to Vines and Wise,3 found that "although the 8 pct tungsten alloy was a solid solution, the 26 pct tungsten alloy contained a eutectic or an intermediate phase." Hultgren and jaffee4 using X ray methods found continuous solid solutions to at least 33.6 pct tungsten (35 at. pct) after annealing in vacuum for 6 days at 1000°C. Vines and Wise3 report work communicated to them by E. C. Rhodes on wrought alloys to 7 pct tungsten, which showed that tungsten hardened platinum extremely rapidly, and was one of the most potent hardeners of the binary additions to platinum. Considerable quantities of 4 pct tungsten platinum wire have been produced for grids in radar tubes and for aircraft spark plugs. Some of the alloy for the latter application is made by sintering, the remainder by smelting and casting. MATERIALS The platinum powder used in this work was kindly supplied by the research and Development Laboratory of the Owens-Corning Fiberglas Corp., Newark, Ohio, It was prepared from scrap platinum. After dissolving in aqua regia and evaporating almost to dryness, the solution was worked up several times with concentrated HCI. the resultant platinic chloride was diluted considerably, and metallic zinc was added, which precipitated the platinum in a very finely divided form. After dissolving the

Jan 1, 1948

By John V. Beall

There was optimism on 14th Street on April 22, Earth Day. We only have the report second hand because the demonstration conflicted with another appointment. Fifth Avenue was closed to vehicular traffic from 14th Street to the Park for a few hours and the crowd that showed up to promenade rivaled anything that can be imagined, even one at a country fair in Merry Old England. Certainly the domestic animals were there and the costumes were wild-as they are almost any day on 5th Avenue. However, the mood was friendly, happy and optimistic according to one of our neighbors who filmed and taped interviews with some of the characters. People think the air is going to be clean, and the water pure in the future. Land is going to be treated with respect. Even if the demonstration temporarily fouled the streets with litter, it served the purpose of dramatizing awareness. In talking to our friend about his experiences we didn't miss the opportunity to sound out his impression of whether or not people recognize that no group of people nor industry has a monopoly on pollution.

Jan 1, 1970

By Y. L. Yao

The solubility limit of oxygeu in a titanionn at 850°C has been determined by magnetic measurements as 12.5 + 0.5 pct (29.0—30,9 at. pct). Also in the susceptibility-co~centmtion curve, there is n distinct but not sharp maximum at 19.0 * 0.5 z~t pet (40.5--42.1 at. pct), which indicates the presence of the 6 phase. The magnetic susceptibilities of the alloys of the titanium-oxygen system were determined byEhrlich in 1939.' is alloys were prepared by sintiring mixtures of titanium and its oxide at high temperatures. On the titanium-rich side, despite the fact that the alloy compositions he measured crossed two phase boundaries, the limited results obtained

Jan 1, 1960

By Clarence A. Seyler

The technical difficulties of cutting thin sections of coal for examination by transmitted light have hitherto restricted the investigation of the important subject of the microstructure of coal to the few possessed of the requisite skill and time. Apart from this, the method fails with anthracites and other coals rich in carbon, owing to the opacity of the material. Occasional use of the method of polishing a surface, with or without etching, has been made, but it was not until Winter' published an account of his results that attention was seriously directed to the method. In May, 1923, a specimen of dull anthracite came into my hands; I tried Winter's method on it and the presence of megaspores and other vegetable structures became clearly visible. A preliminary notice was published by me;2 but I soon abandoned the use of Schulze's solution, having found that a mixture of chromic and sulfuric acids gave far better results. In the meantime Turner and Randall, in America, had independently developed the method of flame etching, as applied to anthracite, with great success. I have spent a year studying the method of chromic etching, which gives excellent results with bituminous coals and camels, as well as with anthracite. For anthracites, I have used the chromic method and Turner's method of flame etching, whichever was the more convenient or as a check one on the other. The polishing is done, according to metallurgical practice, by the use of a polishing machine and successively finer emery paper, followed by polishing on cloth moistened with a suspension of levigated green oxide of chromium, and a final rubbing on "selvyt" (a cotton velvet polishing cloth) moistened with alcohol. The polished sample is examined by reflected light with a 2/3 and 1/6 in. objective. Bituminous coals usually show considerable structure, and even anthracites show it faintly in places. The sample is then etched by immersion in a boiling solution made by adding 10 c.c. of concentrated sulfuric acid to 30 C.C. of a saturated solution of chromic acid; enough water is then added to dissolve

Jan 1, 1925

By Frank C. Aplleyard

The two calcium sulfate minerals-gypsum and anhydrite-occur in many parts of the world, and gypsum has long been of economic importance in the family of industrial minerals. Gypsum, the dihydrate form of calcium sulfate (CaSO4•2H2O) and anhydrite, the anhydrous form (CaSO4) are frequently found in close association, and it is seldom that a calcium sulfate deposit will consist exclusively of one mineral or the other. Although known gypsum deposits are extensive, anhydrite makes up the largest part of total calcium sulfate reserves. However, it has very minor economic use, and most of the following discussion will be devoted to gypsum. Calcium sulfate is one of the principal constituents of evaporite deposits, and when pure, has the following composition: [Sulfur Combined Lime Trioxide Water (CaO) (SO,) (H2O) Gypsum 32.6% 46.5% 20.9% Anhydrite 41.2% 58.8% -] Deposits of pure gypsum or of pure anhydrite which are large enough to be considered commercial have never been found because of both the metastable relationship between the two minerals, and the presence of impurities such as calcium or magnesium carbonates, chlorides, other sulfate minerals, clay minerals, or silica. As a result most mine production of gypsum will range between 85 and 95% pure. Often it is used as mined, although in certain cases, one or more forms of mineral beneficiation are employed to upgrade the product. End Uses The largest use for gypsum is based upon the unique property which calcium sulfate has of readily giving up, or taking on, water of crystallization. With the application of a moderate amount of heat in a process known as calcining, gypsum is converted to plaster of paris (the hemihydrate of calcium sulfate, CaSO4 ½ H2O) which when mixed with water will set or harden as the calcium sulfate returns to the dihydrate form. This semifinished product, usually called stucco, is then manufactured into a large variety of plasters, wallboard, and block for construction use, or into plasters for industrial applications. About 75% of the gypsum used in the United States is calcined for these purposes. Uncalcined uses of gypsum are principally as a retarder for portland cement, as a soil conditioner, as a mineral filler, and other minor industrial applications. About 25% of the gypsum mined in the United States goes into these markets; however, in less developed countries where construction and other industrial uses may be quite limited, the use of uncalcined gypsum for portland cement retarder may well be the dominant-if not the only-market for the mineral. It has often been noted that calcium sulfate constitutes the world's largest reserve of sulfur, and minor use of both anhydrite and gypsum has been made to produce sulfuric acid or other sulfur compounds such as ammonium sulfate. However, because sulfur is readily available at lower cost from other sources, use of calcium sulfate has been limited to only a few locations where it could compete economically. No such use is reported in the United States at this time. Mineralogy Anhydrite, CaSO4 because of its geologically rapid conversion to gypsum, and relatively high solubility (about 0.2 g per 100 g H2O) is not often found outcropping in climates wet enough to support abundant vegetation except on steeply dipping slopes or other places where hydrated material is continuously removed. Anhydrite rock is most often light to bluish gray in color, and under the microscope, varies

Jan 1, 1983

By R. E. Ogilvie, N. L. Peterson

DURING the past few years there has been considerable effort devoted to the understanding of radiation effects on materials. The concept of the Frenkel defect and other lattice defects suggests that radiation may alter the rate of many metallurgical phenomena, especially those which are diffusion controlled. In 1953 R. R. Coltman and T. H. ~lewitt' found an appreciable effect on the ordering rate of Cu,Au due to fast neutron bombardment. Since then several rather comprehensive theories have been proposed on radiation enhanced diffusion in solids.2"4 If the energy of the radiation is above the threshold energy for the removal of atoms from their lattice sites, Frenkel defects will be produced. These defects can be produced uniformly throughout a relatively thick specimen by high-energy X-rays permitting bulk property studies without the limitation of sample dimensions. In this work high-purity arsenic containing 30 ppm of impurities was allowed to diffuse from the gase- ous phase at 700°C into single crystals of p-type germanium containing 0.1 ppm of indium. As the arsenic diffuses into the P-type germanium, an n-type layer will form in the diffusion zone. At the p-n junction the concentration ratio of the arsenic to the indium is constant. Experimental Procedures—The germanium specimens, 10 mm by 10 mm by 5 mm, were polished and etched to a mirror finish. The specimens were then sealed off in a vycor glass capsule at 3 x 10"5 mm Hg pressure with a sufficient amount of arsenic powder to produce a one-half atm pressure of arsenic at 700°C. Specimens were annealed at 700°C without radiation. The diffusion coefficient determined from these samples agrees within 8 pct of previous work done by Fuller.' Three specimens were given diffusion anneals at 700°C in a small tube furnace centered beneath the target of a 2-mev Van de Graaff generator. The specimens when in the furnace were 10 cm directly below the target of the generator. These specimens were irradiated continuously during the diffusion run with the Van de Graaff operating at 2 mev with a tube current of 225 to 250 pamp. The intensity of the x-radiation at the surface of the specimen inside the furnace was approximately 4.5 x l05 roentgens per hr. The temperature was controlled within m2°C by a chromel-alumel thermocouple throughout this work with no observed temperature change due to the radiation. By careful lapping, the samples were polished at an angle of 5 deg to the diffusion zone, giving a XI0 increase in the visible diffusion zone. The location

Jan 1, 1960

By J. J. Gilvarry, B. H. Bergstorm

The first part of this paper describes a new approach to the problem of energy relationships in fracture and comminution. The basic theoretical method used (as contrasted to previous empirical or semi-empirical approaches) is an attempt to verify or disprove the hypothesis of von Rittinger, In the second part of the paper, theoretical conclusions for the three headings of single fracture, plural fracture, and comminution are tested. Agreement between theory and experimental results is demonstrated. The classical hypotheses on the energy relationship in brittle fracture are those of von Rittinger-that the energy required is proportional to the new surface formed— and the alternative one of Kick.' Over the years, repeated attempts have been made to discriminate experimentally between the two assumptions, or to replace both of them, as has been done by Bond? However, no semblance of agreement seems to exist among different investigators. This paper is the first in a series essaying a new approach to the entire problem of energy relationships in fracture and comminution. The purpose of this program of research is to verify (or disprove) the hypothesis of von Rittinger. In contrast to previous empirical or semi-empirical approaches to the problem, the basic method adopted is theoretical. The prime aim is to determine the distribution function for fragment size theoretically and to verify the predicted distribution experimentally. This approach should make possible determination of the total surface of the particles by integration over the corresponding distribution function; one may hope that this direct procedure will yield more definitive results than use of gas adsorption or other methods. The surface area so obtained can then be compared with experimental energies, as obtained by Bergstrom, Sollenberger, and Mitchell,4 for example. It is convenient to distinguish between single fratture, plural fracture, and comminution. Single fracture of a brittle solid is defined as fracture by an external stress system which is removed instantly and permanently when fracture is initiated. Plural fracture consists of single fracture of the original specimen, followed by a sequence of only a few secondary fractures; comminution differs in that the sequence of secondary fractures consists of a large number of repetitive steps. For single fracture, Gilvarrys has given a rigorous derivation of the proper distribution function for fragment size, based on a closely defined physical model and deduced strictly by the laws of probability. Gilvarry and Bergstrome have compared the predictions of the theory with experiment, and have found excellent agreement. The prior work of Gilvarry and of Gilvarry and Bergstrom considers only single and plural fracture. The purpose of the present paper is to extend the discussion to the case of comminution. For prefatory purposes, the theory of Gilvarry for single fracture will be outlined. The considerations will then be applied to the cases of plural fracture and comminution. SINGLE FRACTURE The derivation is based on the Poisson law.7 For Points distributed with mean density y over a domain, this law states that the probability p(t)dt of one point lying in the range t to t + dt with none in the interval 0 to Ms p(t)dt = ye-yt dt. For this distribution to be valid, it is necessary and sufficient that the points be distributed at random, individually and collectively in the sense of ~~~.7 The former qualification requires that the position of One Point be independent of another, and the latter implies that the probability of a region containing a

Jan 1, 1961

By AIME AIME

NEARLY two hundred 'engineers attended the dinner given at the Hotel Pennsylvania on Monday-evening, Oct. 10, to the delegation from the American l3nginiering Societies to Great Britain and France when the John Fritz Medal was presented to Sir Robert Hadfield and to Eugene Schneider. Representatives of the British and French Governments ' and of foreign engineering societies gave to the event an international aspect unique in gatherings of engineers. Messages from men distinguished in science, statesmanship and diplomacy were read. Medals struck by the French Government were presented to the general chairman of the deputation, to the chairman of each' individual delegation and to the president's of the four Founder Societies. The meeting was regarded by engineers as formally ushering in a definite movement for world unity in the engineering profession. J. Vipond Davies, president of the United Engineering Society, acted as toastmaster. The speakers ,were Ambrose Swasey, Charles F. Rand, F. B. Jewett, A. S. Dwight, John R. Freeman, all members of the deputa- tion; and M. Gaston Liebert, French Consul General; Captain G. H. Armstrong, British Counsel General; G. G. Clapperton, representing the British Institution bf Electrical Engineers, and Prof. Jacques Cavalier, spokesman for the French universities. Among the engineers from other cities was Governor. James Hartness of Vermont.

Jan 1, 1921

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By H. L. Ames, P. H. Jennings, R. W. Stanley

A process has been developed for leaching copper, lead and calcium from molybdenite concentrate. The leachant is a solution containing an oxidizing chloride (e. g., CuC12, FeC13) and an alkaline earth metal chloride (e. g., CaC12). Cupric chloride and ferric chloride, in the presence of 20-30% calcium chloride, are effective oxidants for chalcopyrite and galena. Calcium chloride, in addition to promoting the rate of leaching, serves to lower the solution pH and raise the boiling point. Leaching for two hours at 110'~ with a 1 % CuC12-10% FeC13- 30% CaC12 solution results in the extraction of up to 98% of the copper in molybdenite, 98% of the lead, and 79% of the calcium. Less than 0. 5% of the molybdenum is dissolved. The leach solution can be rapidly and effectively regenerated with gaseous chlorine and recycled. Build-up of copper and lead in the leach solution is controlled by discarding about 30% of the leach solution each cycle.

Jan 1, 1973

By A. F. Taggart

OLIVER C. RALSTON, Salt Lake City, Utah (communication to, the Secretary*).-This paper has appealed to me as being one of the most lucid, well-connected and complete papers on this subject which has been published. To be sure, the concepts called upon in an explanation of the flotation process by these authors are mostly old ones which have been more or less discussed in previous literature, but they have nevertheless been assembled in a most constructive and suggestive manner. We find a new contribution to flotation theory in the effect of fine particles increasing the viscosity of the interfacial film between a liquid and a gas. This phenomenon has been variously hinted at but never definitely stated in accepted scientific terms. The discussion of "contact angles". is very clear and will doubtless be welcomed by those who have not had the opportunity to investigate the literature on this subject, but it is unfortunate that the "hysteresis of the contact angle," observed by Sulman and reported some years ago, is not mentioned or explained. A few other points need discussion in order to call attention to the fact that, while this paper is the best discussion of the subject which has yet appeared, all of the truth has not yet been told.

Jan 12, 1916

By W. M. Myers

THE hydraulic properties exhibited by the calcination products of certain limestones were recognized at an early datemore than 2000 years ago. It was known that calcined limestone with the addition of other minerals would react with water and produce an insoluble and stable product. This material could be cast in desired forms or could be used as a cement for the unification of other materials in large masses or for bonding brick or masonry structures. Cements are essentially mineral glues and it is their ability to unify other materials plus their fluidity when first mixed with water, enabling the mass to assume any desired shape, that has made them so extraordinarily useful to modern industry. Like other glues, cements do not exhibit their maximum strength when used alone and only when mixed with proper aggregates do their optimum properties appear. The resulting concrete, a mixture of cement, mineral aggregates and frequently of reinforcing steel, exhibits the most desirable properties of the individual constituents with regard to tensile strength, stability and permanence. The speed with which such mixtures can be -prepared and installed in place with mechanical equipment has facilitated their adoption by the engineering profession concerned with the construction industries. The development and application of improved methods of manufacture have resulted in such economies that the finished product can be sold at a remarkably low price. In addition, the necessary raw materials are of such common occurrence and wide geographic distribution that the manufacture of cement was established in 34 of the 48 states by 1946. Plants under construction will add to this number. In recent years the industry has been characterized by the development of a number of new cements designed to possess special properties essential for use in unusual environments. These have introduced the use of some new raw materials and also have complicated the processes of manufacture. In the following pages, the major varieties of cement of commercial importance are treated in the chronological order of their appearance on the market.

Jan 1, 1949

By Charles W. Chesterman

Perlite is a glassy volcanic rock which will, upon rapid controlled heating, expand or "pop" into a frothy material of low bulk density, valued as a lightweight aggregate. The term perlite also is applied to the expanded product. The chemical composition of perlite ranges from that of rhyolite to that of andesite; the water content ranges from 2 to 5%. Most perlite is pale gray, but some is black, brown, or even green. Inclusions in perlite are common and include phenocrysts of quartz, feldspar, biotite, and hornblende, and miscellaneous rock fragments. Occurrences of perlite are restricted to areas of Tertiary and Quaternary volcanic rocks. Perlite occurs as flows associated with thick accumulations of pyroclastic debris and other flow rocks, as dikes, sills, domes, and as selvages of intrusive bodies of volcanic rock. Individual flows of perlite range in thickness from a few feet to as much as 100 ft and commonly cover several square miles. Dikes and sills of perlite generally are small, but domes generally are substantial in size and may be as much as several miles in diameter. Most perlite deposits are large enough and topographically situated so as to lend themselves to low-cost open pit mining methods. Conventional equipment is employed in the mining of perlite. Although milling procedures may appear to be simple, care is exercised in order to produce a carefully sized product and to minimize the production of excessive quantities of fine materials, which have limited use and are considered as waste. Perlite is processed, or "popped," in one of two basic types of furnaces: horizontal rotary or vertical stationary. Both types of furnaces include product collection and dust control systems. Many commercial deposits of perlite are known to occur throughout the world, and although no exact estimate of reserves is available, there appears to be an adequate supply to meet current and future worldwide requirements. End Uses The uses of expanded perlite are many and varied and are based primarily upon its physical and chemical properties. Because of its (1) low bulk density, which generally ranges between 2 and 20 lb per cu ft; (2) low thermal conductivity "K" factor (Btu per hr per sq ft per OF per in, of thickness), which ranges between 0.267 for loosely packed perlite (bulk density of 4.48 lb per cu ft) to 1.25 for perlite gypsum plaster; (3) high resistance to fire; and (4) low sound transmission, expanded perlite is used to a great advantage as aggregate and insulating material in the construction industry. Early uses of perlite were related exclusively to the construction industry, which now consumes about 60% of the domestic production. The primary use of perlite now is as aggregate in insulation boards. Other uses of perlite in 1971 were as aggregate for plaster, horticultural aggregate, low-temperature insulation (cryogenics), and concrete. Because of its low thermal conductivity ("K" factor), high adsorption of sound, low bulk density, and fire resistance, perlite aggregate plasters hold many advantages over conventional plaster. Perlite aggregate plaster lends itself to machine applications, dries quickly, and has relatively high elasticity which reduces cracking after drying. These same features make perlite useful as aggregate in portland cement concrete and asphalt concrete for construction wherever weight reduction, insulation, and acoustics are of prime importance. Perlite-portland cement concrete offers up to 20 times more thermal insulation than conventional concrete, and because of this it finds wide application in roof decks and floor fill in multistory buildings, in

Jan 1, 1975

By Persifor Frazer

The rocks which cover the east flank of the South Mountain are chloritic schists typical in character. A specimen of this rock from near the Bechtel shaft, Hamilton Ban Township, Adams County, Pa., was selected and analyzed in my laboratory by Mr. C. Hanford Henderson, with the following results: Ignition,........2.740 CaO,..........7.040 SiO,,..........41.280 MgO,.......... 7.486 AI,O,,.........18.480 K,O,..........2.208 Fe,Os,.........9.440 Na,O,.........3.523 FeO,......... 8.200 100. As one penetrates the range by moving westvard, these schists are replaced either by epidotie quartz or by orthofelsite. In the former case, a belt of copper-bearing rock is traversed, but not in the latter case. Inasmuch as this junction of the chloritic schists on the southeast and orthofelsite on the northwest, separated by the epidotic quartz, is several times repeated, we find two or three copper belts arranged in general parallelism to the axis of the chain, because the copper horizon is generally at this junction. Thus, in going west from Fairfield, after entering the low spurs on the South Mountain, one is fairly within the chlorite measures. At the " Virginia Mills " a chlorite schist comes in with a dip of S. 1.5 E.-74 Half a mile up Middle Creek, large numbers of fragments of chlorite schist, decoruposed epidotic matter, and quartz are encountered. The former rock, where in place, dips E. 40" S.-57o. About 4000 feet west of the intersection of this road with the so-called Tape-Worm Railroad, near the house of one Singly, large masses of chloritie schist are found loose on the road. A hundred yards farther west, near a triangle in the road, the latter is less in quantity and much epidotic quartz appears, after which a very large display of orthofelsite succeeds on the left bank of Middle Creek. All these last-mentioned rocks, however, are in fragments. Crossing the stream again a few hundred yards farther On, the chlorite fragments at first preponderate, and then large numbers of both rocks

Jan 1, 1884

By W. Hurst

What is entailed here is the extension of the sinzplified material balance formulas to encompass interference between oil fields. As previously reported, the ex-plicitness as so revealed for the cunzulative pressure drop as a function of all factors contributing to its change in the material balance equation, is now transcribed through the inter-conzmunicating aquifer to effect an increased pressure drop on an adjoining field by interference. Such is performed by mathematical analyses and the application of the Laplace transformations. What is accomplished is that the reiteration problems previously associated with interference studies are nullified, since volumetric changes for the fluids in situ are automatically adjusted by the explicitness so expressed, and what pertains to the superposition principle applies only to the impeded water drive upon a su.bject field, which is likewise incorporated in the over-all pressure drop that results. The mathematics treats with the rigorous solution of the problem, as well as with methods easily amenable to numerical interpretation by the practicing engineer. In all cases, however, what is deduced for areal extents, reveal interference between wells when time becomes large that further substantiate the analyses. Probably of equal significance, all variables and for/nation characteristics are accounted for. This applies to the differences in PVT analyses that occur from field to field and the physical parameters associated with the lithology of the reservoirs. The latter is deduced from a rigorous interpretation of the unsteady-state flow problem for sands of different permeabilities in series. Thus, what purports to be a trial-and-error calculation to include variations in sand conditions within the intercommunicating aquifer to define water drive has little importance compared to the designation of such paranzeters at the reservoir to constitute the essential criteria. INTRODUCTION In a recent publication, the reader has been introduced to the simplified material balance formulas,' It has been shown that the complexities formerly associated for identifying and determining reservoir pressure in the material balance relationship can be resolved by treating with the Laplace transformations, the inversion of which reveals pressure as an explicit function of all factors contributing to its change. For an under saturated oil reservoir, this constitutes an integrated effect from the inception of production; and for a saturated oil reservoir, such represents a survey traverse. However, what is most important, for the first time we are able to express the pressure change in a reservoir directly to the oil, gas and water produced, and to the physical parameters of the formation, in the same manner that reservoir pressure has served in the past to define well interference — which opens up this avenue of endeavor for investigating interference between oil fields. The occurrence of interference is by virtue of the juxtaposition of two or more oil reservoirs producing in the same aquifer. Thus, in any one field, the extended production so incurred creates a pressure lowering in the field, as well as in the aquifer, which can now be transcribed by these simplified material balance formulas to the adjoining reservoir to observe the increased pressure change so induced. These effects are retroactive from field to field, to reveal a pressure drop far in excess of normal depletion to evidence the interference pattern that can result. Such is the purpose for the present undertaking — to develop the mathematical physics treating with this phenomenon of interference between oil fields, employing the simplified material balance formulas. Since Ref. 1 often will be referred to in the text, it is identified as "The Simplification", in the same connotation that another paper has been referred to as the "Laplace Trans-formation. However, the amount of material to be covered in these passages is substantial; therefore, the total emphasis will be placed upon developing these fundamental ideas treating with interference rather than attempting to offer work curves, which always can be prepared. For the practical application of these simplified material balance formulas that form the framework of the present development, the reader will find a comprehensive treatment in the Appendix of Ref. 1, illustrating a factual field example. In essence, what is proposed by this presentation is to make available to the practicing engineer a simplified means to treat with interference between oil fields, independent of the complex machine computations that have attended such undertakings in the past. As the problem unfolds, a common pattern will be discernible, whereby the many reiteration processes that previously required computing devices are eliminated.

By A. D. Brokaw

The so-called "paraffin dirt" of the Gulf Coast oil fields has been considered an indication of the possible presence of oil and gas, and not a few wells have been brought in solely on the basis of such evidence. In a sense, it may be empirically justified as evidence of the presence of oil or gas, though it cannot be said to be infallible. If the writer is correctly informed, its association with oil and gas was pointed out by Lee Hager some years ago, and while it is commonly mentioned by geologists and operators in conversation, no discussion seems to have found its way into print. The present interpretation is based on laboratory study rather than on field investigation, and is put forth with the hope of stimulating discussion which shall lead to more complete understanding. The term "paraffin dirt" has been applied to soils with a peculiar texture, which has been described as "curdy" or "rubbery." When moist, the material breaks much after the fashion of "green" cheese. It is rubbery under compression, but does not resemble rubber in tenacity or cohesion. When dry, the material ranges from hard clods to a horny mass of high tensile strength. The shrinkage in drying is very great, especially in the hornlike matter. The moist material ranges in color from dark brown in the specimens rich in organic matter to grayish in specimens containing more inorganic matter. All of the specimens studied were readily attacked by molds, which in some cases grew in great profusion on the samples. Samples exhibited a rather characteristic "swampy" or "mucky" odor when wet, and a characteristic odor of humic soils when moist. If the material is brought into suspension in water, very fine sand settles out and may be recovered by successive washing and decantation. The sand is almost entirely quartz, but contains occasional fragments of feldspar—more or less kaolinized and iron-stained. Practically all of the sand passes through a 100-mesh screen and the grains are extremely sharp —possibly below the limit of rounding. A flocculent mud, of clay and organic matter, remains in suspension for days. Some material is taken into solution in the water, imparting a slight tendency to froth when vigorously shaken. The results of partial analyses of four samples of "paraffin dirt," and, for comparison, one of a coastal plain soil are given in Table I.

Jan 1, 1920