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By K. G. Kreider, J. H. Brophy, J. Wulff

The technology of nickel-activated sintering of tungsten powder has been successfully applied to the densification of plasma-sprayed tungsten. Nickel was added by infiltration in a zinc solution followed by evaporation of the solvent. After sintering one hour at 1300°C density 95 pct of theoretical and transverse rupture strength of 74,000 psi were obtained. Shrinkage was found to be anisotropic and the mechanism of densification was comparable to that found in the nickel-activated sintering of tungsten powder. 1 HE use of a plasma spray gun for the fabrication of massive tungsten parts has become increasingly interesting. Applications now exist where a deposit in the as-sprayed condition is satisfactory. However, these deposits are generally characterized by a lamellar anisotropic microstructure containing 15 pct porosity of which, typically, two-thirds is open to the surface. Mechanically, the as-sprayed deposits fail at relatively low stress levels with a biscuit-like fracture. As a result of these problems the possibility of improving structure and strength by sintering treatments subsequent to spraying is particularly attractive. Preferably this sintering treatment should be adaptable to large bodies of sprayed metal. The similarity between the as-sprayed tungsten structure and that of a powder compact suggests that the relatively low-temperature activated sintering technique1 might be profitably employed in the densification of plasma-sprayed tungsten. It was the purpose of the present investigation to develop a technique for introducing the nickel-activating agent into the sprayed structure, to evaluate the amount and mechanism of densification obtained as a function of time and temperature, and to obtain an indication of the relative strength before and after sintering. EXPERIMENTAL PROCEDURE Powder used for spraying was purchased from the Wah Chang Corp. in several size fractions ranging from an average size of 4 to 150 . These powders were sized further for an explicit study of the influence of average feed size on densification. All powders were dried at 200°C before use. Spraying was accomplished with a Plasma Flame unit manufactured by Thermal Dynamics Corp. Several modifications of the unit were helpful in conducting the investigation. A variable speed auger feed mechanism coupled with the carrier gas mecha nism facilitated the use of fine particle sizes. A coil of ten turns of copper tubing in series with the arc power and concentrically would around the nozzle improved nozzle life and extended the range of operating currents available. The function of the auxiliary coil was to cause the arc to spin and to prevent impingement at only one point in the nozzle. Normally air sprayed deposits were made with an arc maintained at 400 amp at 50 to 70 v. The arc was blown by a gas mixture containing from 5 pct H, 95 pct N for the finest powder feed sizes ranging to 20 pct H, 80 pct N for the coarsest size. The flow rate was maintained at 100 cu ft per hr NTP through a nozzle of 0.25 in. ID. When apraying in air, the powder stream was directed toward an aluminum substrate for ease of mechanical removal of the deposit. The substrate was cooled by diverting the plasma flame with an air jet, and a second jet was directed on the deposit surface. In this configuration a gun-to-work distance of 2 to 3 in. was found to be satisfactory. Fig. 1 represents a typical as-sprayed deposit micro-structure. Laboratory studies of protective atmosphere spraying were carried out in cylindrical chamber 8 in. in diam by 18 in. in length. In operating the nozzle attached to such a chamber, particular care was required to avoid nozzle burn out due to reduced gas flow. The structure and density of the chamber sprayed deposits varied over wide ranges depending on substrate temperature. For the purposes of this investigation, flat deposits were made approximately 2 in. sq by 3/8 in. thick. From these deposits individual samples were cut an ground to a rectangular shape typically 1 1/2 in. by 1/8 in. sq such that the long dimension was perpendicular to the spraying direction. For the study of shrinkage anisotropy deposits up to one inch thick were produced. From these, rectangular samples were cut having a longer dimension parallel to the spraying axis. Prior to the addition of activating agent, the samples were deoxidized in hydrogen at 800°C for 20 min. No detectable dimensional or microstructural change was observed after this treatment. The addition of nickel was accomplished by infil-

Jan 1, 1963

By John C. Smock

The question of the proper valuation of mines of iron ore was suggested to me by the difficulties experienced in getting answers for the United States Census Office, while I was engaged in the work of collecting the statistics of mines in New Jersey and New York. The answers to the questions relating to values of real estate of mine properties varied so greatly that it was necessary to revise them according to some general principles of valuation. Generally the returns of mine proprietors seemed to be too low. There were, however, examples of what would be termed excessive valuation. The subject appeared to be of practical importance, and led to the paper here presented. The following table of selected mine statistics is given, prefacing the discussion of the principles of valuation. It is in part made up of census returns and partly of data obtained directly from mine owners and managers. The mines which were selected for the several groups and mining districts include nearly all of those from which the more full and carefully filled returns were received, and are also representative of their respective districts. Hence the averages obtained from them become good types of these groups or districts. The mines of New Jersey appear in six groups, each containing from three to eleven mines, or, in all, thirty-four mines. The magnetic iron ores of New York are in four well-marked groups, and there are twenty-six mines in them. Then follow the red hematite mines of St. Lawrence and Jefferson counties; and, lastly, the brown hematite groups of Dutchess and Columbia counties, and those of the adjacent parts of Connecticut and Massachusetts. The whole number of mines represented by the table is eighty-eight, of which twenty-eight are hematite mines. The first column gives the value of the real estate; the second that of the plant; the third is the sum of these two, or the capital invested. Then follow the number of men employed, the amount of wages paid during the census year, and the value of materials used in mining and preparing the ores for market." The seventh column gives the total expendi-

Jan 1, 1882

By Henry M. Howe

I NOW call your attention to two directions in which very important progress may be confidently hoped for—pyrometry and the heat-treatment of steel. We already find in the market more than one pyrometer which, in spite of serious defects, may lie used advantageously for determining and controlling the temperature of many of our metallurgical processes. It is to be hoped, and with much confidence, that by the rapid extension of the use of such instruments, the economy and efficiency of these processes may undergo an increase which, in the aggregate, will be of the greatest importance. In this connection, the lucid paper of Prof. Roberts-Austen," and the learned bulletin of Mr. Barus, are most welcome. But much remains to be done in the way of devising pyrometers suitable for manufacturing purposes. While some of the present pyrometers are most convenient and accurate in the laboratory, serious difficulties attend the use, in factories, of those which I have

Jan 1, 1895

By G. A. Koehler

The Hiawatha mine, a producer of iron ore, is near the City of Iron River, in Iron County, Michigan. This mine, operated by The M. A. Hanna Co., has been chosen by the author as a typical iron mine in this district that is using the cut-and-fill mining system. General Geology The Hiawatha ore body lies along the steeply dipping north limb of a syncline that closes around on the east end to form a bathtub-shaped structure. Throughout this major structure there are very many smaller wrinkles or folds, which vary the direction as well as the thickness of the ore body. The total length of the ore formation with minor interruptions so far developed is about 3600 ft. The ore body throughout the entire present depth of 2000 ft. has averaged approximately 40 ft. in thickness; it is somewhat narrower at the upper levels and shows a marked increase in thickness on the bottom levels. This increase in thickness probably indicates that the bottom of the trough is near or that a major monoclinal fold has been encountered, which flattens the ore and gives apparent horizontal thickening. The footwall of this ore body is generally a black, graphitic slate, very rich in iron sulphides, quite combustible when exposed to air, and very treacherous to handle during mining operations. The hanging wall, in most places, is a cherty, fairly hard iron formation, and in general stands quite well ill open stopes. There are places, however, where black slate is found in both the hanging wall and the footwall, which makes mining difficult, as the black slate tends to slough off after being exposed to air. In these places it becomes necessary to leave a scale of ore 5 to 6 ft. thick on both hanging wall and footwall, which is not recovered. Fig. I shows a typical vertical cross section through the Hiawatha ore body. Type of Stoping Because of the size and shape of the ore body and the hard, dense structure of the ore, sublevel stoping has been an efficient and economical method of extracting the ore. This method, with various minor changes, has been used since the mine was opened in 1893. There have never been any stope-filling operations, however, until recent years, when crushing of pillars and black-slate fires forced the issue and methods were arrived at to fill all stopes. Development of Deeper Levels Shaft sinking to deeper levels in development operations has been done successfully by two methods without interference or hindrance to production. These systems are: I. Sinking an auxiliary winze a short distance from the shaft, then drifting back to the shaft location and putting up a pilot raise through to the bottom of the shaft. This raise is always in the manway compartment of the shaft, so that no work is ever done under a cage or skip. A 20-ft.

Jan 1, 1946

By H. E. Brauer

PART I INTRODUCTION Among the zinc base alloys used for casting in metal moulds, particularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortness which facilitate casting. Objection to the use of these alloys may bee raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intercrystalline corrosion. In all cases which have come to our knowledge where the conditions of service were known, failure has occurred upon exposure to moisture and heat varying from a hot moist atmosphere to high pressure steam. Moreover, the alloys described in all such cases contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intercrystalline oxidation in zinc-aluminum alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Bauer2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the most part, and Rawdon's3 examinations were made on an alloy containing 0.4 per cent. lead also exposed to the Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to determine the exact nature of this phenomenon and the effect of other metals present as impurities or intentional additions in accelerating or-retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation.

Jan 8, 1922

By P. D. Southgate

VIBRATION, both ultrasonic and sonic, can affect the course of a variety of metallurgical processes. Reports of work on this subject have appeared at intervals over the last twenty years and a thorough review has been made by Hiedemann,' who gives a full list of references. It has been established that both refinement of structure and outgassing of the melt can be produced in most metals with sufficiently intense vibration. Many of the experiments in this field have been carried out using alloys of direct commercial interest in production- type casting equipment. Here a different approach is adopted, and simple binary alloys which exhibit different types of structure are used to facilitate examination of the effects produced under well-controlled conditions. Results from this kind of experiment should enable the basis of larger scale experiments with similar types of materials to be better substantiated. The alloys selected for this work are: 1) aluminum of 99.2 pct purity, the principal impurity being iron, near 0.4 pct; 2) A1-1.8 pct Fe, which is near eutectic composition; 3) A1-4 pct Fe—the second phase, of composition FeAl3, forms distinct acicular crystals; and 4) A1-12 pct Si—although this is of eutectic composition, the silicon normally appears in the form of large plates. Experimental Method There are three practicable methods by which acoustic vibration can be transferred to liquid metals: a) vibration of the whole of the container; b) electromagnetic induction; and c) insertion of a vibrating probe into the liquid. Method c is chosen here, and a frequency of 8 kc per sec is used. The end of the probe is electrically heated so that the metal near it will be the last to solidify. This ensures that vibration is transmitted directly to the liquid metal without passing through any solidifying and pasty intermediate region, which would attenuate acoustic waves severely. In addition, the heating prevents solid metal adhering to the probe, with consequent detuning. The transducer assembly is shown in Fig. 1. A stack of Permendur laminations 30 cm long acts as a half-wave vibrator and a winding along its length carries polarizing and energizing currents. It is joined by a half-wave coupling bar to a mild steel exponential horn, which tapers from 3.8 to 1.1 cm diam. A stainless steel stub 3 cm in length is welded on the free end. The assembly is supported by a plate located at the node of the coupling bar. Acoustic radiation losses are minimized by allowing the free end of the transducer to protrude above the surface of the cooling water. The exponential horn serves the function of matching the acoustic output impedance of the transducer to the radiation resistance of the probe into the melt. Electrical drive is provided by a 1 kw generator. Measurements of probe vibration amplitude during melt treatment are obtained from a gramophone pick-up with the needle attached to the wide end of the horn. This device is calibrated with a microscope before use. Liquid aluminum is very actively erosive and solution of materials with which the molten metal comes into contactcauses difficulties. Erosion of the probes in particular can be severe since it is greatly accelerated by the vibration. Tests of various acous-

Jan 1, 1958

By Frank Firmstone

IN the early decades of the past century the method of starting iron blast-furnaces by "scaffolding-down" seems to have been in universal use for coke-furnaces and, at least in this country, for charcoal-furnaces also. It was likewise used at some of the early anthracite-furnaces, as is stated in the important "Reminiscences" printed by the late Samuel Thomas. I It had been generally superseded in Great Britain as early as 1850, by some variations of the plan now used, and was rarely used when Percy wrote.' On the Continent it was still followed in the 60's,3 and was elaborately described by Valerius in 1852. I have never read any statement as to when and by whom '4 scaffolding" was first dispensed with, but the following extracts from journals of my father seem to fix an authentic date for an instance in this country:

Mar 1, 1907

By L. M. Pidgeon

The reactive metals are above manganese on the electromotive series. Their compounds are characterized by large heats of formation and they cannot be reduced from their ores by classical methods. Three general production methods have been used: a) Fused salt electrolysis, b) reduction of a halide by another metal, and c) reduction of the oxide by another metal. Method (a) is highly developed, as in the case of aluminum, (b) in the case of titanium, and (c) has been successful in the case of volatile metals such as magnesium and calcium. It is suggested that future improvements will take place in (a), and particularly in (c), but are rather less likely in the case of (b). THIS year of 1963 is the centennial of the birth of both Charles Hall and of Heroult, the founders of the aluminum industry. Aluminum is the one reactive metal which has reached massive stature in modern industry and perhaps the only such metal to have been produced in any quantity before the turn of the century. It has been joined by others, some on a very modest scale, but all of importance and all of fascinating interest. When invited to give the Fifth Extractive Metallurgy lecture, it seemed appropriate to look back upon the short history of this group to trace the developments which brought extraction methods to their present state and, at great risk, offer opinions as to future trends.

Jan 1, 1963

By AIME

One of the operations of the J. L. Shiely Co. is quarrying in a hard granite gneiss with intrusions of gabbro or trap. During the winter of 1948-1949 the quarry ramp was lowered about 30 ft and during the 1949 season practically all drilling was done from the quarry floor, developing a face from 72 to 83 ft for the entire quarry area. The performance and cost table shows our record for 1948 and 1949.

Jan 1, 1950

By W. W. Odell

Once it was believed that anthracite or coke were the only fuels generally available and suitable for the generation of water gas, particularly so when this gas was made in the generators of standard carburetted water-gas sets such as are commonly used in the manufacture of city gas. During the past 8 years, practice has changed considerably and it is now common to find gas plants operating without anthracite or coke and using bituminous coal in the generator. This change in fuel has appreciably increased the marketability and sales of certain coal producers' products; accordingly it is of interest to coal operators and others to know the reason for this change, the present trend in practice and the adaptability of various coals for generation of water gas. This paper briefly discusses these conditions and some of the factors relating thereto. Bituminous Coal not Ideal but Cheaper than Coke In spite of many changes which have been made in both process and generating apparatus for using bituminous coal as generator fuel more efficiently, in general it is not an ideal fuel for this purpose. It is supplanting coke because it costs less; it is so much cheaper per ton delivered at the gas works that water gas made therefrom costs less per unit-volume than that made from coke, even though the quantity of generator fuel consumed per therm (100,000 B. t. u.) of gas made is greater with coal. This is the reason why so many city gas plants, as well as others, are using bituminous coal instead of coke. Conditions Favoring Change from Coke to Coal The conditions which have made it possible and feasible, as well as economical, to supplant coke with coal may be summarized as follows: (1) Changes in methods of operating and alteration in generating apparatus; (2) lowering of the calorific standards for city gas, and (3) availability

Jan 1, 1927

By W. E. Coxe

In 1857 the Philadelphia and Reading Railroad Company, whose main line extended from Philadelphia to Pottsville, Pennsylvania, with branches into the coal regions of Schuylliill County, made a contract with the Fairmount Rolling Mill, at Philadelphia, for the rerolling of some four thousand tons of iron rails. The essential features of the agreement were that the old rails should be piled with puddled iron and rolled into flats for the rail pile, which latter was • to be of a section seven inches square, and after being heated, and reduced, by rolling, to a bloom of a section about fire inches by six inches, was to be reheated, before being finished into the rail of the T pattern, four inches high, weighing sixty-four pounds per yard. Great care was exercised in the execution of this contract, and the rails being distributed over all parts of the road, gave general satisfaction by their excellent wear. Five years afterward, the principal proprietor and manager of the Fairmount Rolling Mill was elected President of the Reading Railroad, and very many of the rails made under his supervision were still in use in the tracks of the company, of which he had just assumed the management. His first efforts were, therefore, directed to the procuring of more rails of the same quality wherewith to replace those worn out. Here he encountered some trouble, makers refusing to bid because of the details in the specification, the required reheating being the objectionable feature, for which it was generally intimated they would not be sufficiently remunerated for the increased labor, extra coal consumed, and the changes necessary from the established methods of working. Most of the new rails were, therefore, bought, and the old rails rerolled without regard to any particulars as to the manner of piling, heating, etc., each manufacturer furnishing what he deemed the best article possible for the money. As a consequence, rails of all imaginable grades were placed in the tracks, some giving out in six

By W. E. C. Coxe

IN 1857 the Philadelphia and Reading Railroad Company, whose main line extended from Philadelphia to Pottsville, Pennsylvania, with branches into the coal regions of Schuylkill County, made a contract with the Fairmount Rolling Mill, at Philadelphia, for the rerolling of some four thousand tons of iron rails. The essential features of the agreement were that the old rails should be piled with puddled iron and rolled into flats for the rail pile, which latter was to be of a section seven inches square, and after being heated, and reduced, by rolling, to a bloom of a section about five inches by six inches, was to be reheated, before being finished into the rail of the T pattern, four inches high, weighing sixty-four pounds per yard. Great care was exercised in the execution of this contract, and the rails being distributed over all parts of the road, gave general satis¬faction by their excellent wear. Five years afterward, the principal proprietor and manager of the Fairmount Rolling Mill was elected President of the Reading Railroad, and very many of the rails made under his supervision were still in use in the tracks of the company, of which he had just assumed the management. His first efforts were, therefore, directed to the procuring of more rails of the same quality wherewith to replace those worn out. Here he encountered some trouble, makers refusing to bid because of the details in the specification, the required reheating being the objectionable feature, for which it was generally intimated they would not be sufficiently remunerated for the increased labor, extra coal consumed, and the changes necessary from the established methods of working. Most of the new rails were, therefore, bought, and the old rails rerolled without regard to any particulars as to the manner of piling, heating, etc., each manufacturer furnishing what he deemed the best article possible for the money. As a consequence, rails of all imaginable grades were placed in the tracks, some giving out in six

Jan 1, 1877

By O. Vartianen, R. T. Hukki

A preliminary investigation of the collecting effects of various fatty acids in tall oil has led to a conclusion that the collecting power of fatty acids used in flotation increases with increasing un- saturation of the hydrocarbon chain. Linoleic acid was found to be an excellent collector for oxide minerals. TALL oil is a mixture of fatty and resin acids extracted as byproducts in the sulphate pulp industry. In the field of flotation a well-known example of this type of product is Reagent No. 708 of the American Cyanamid Co. Its successful use as a flotation collector with many nonsulphide minerals has been described by Falconer and Crawford.' The composition of crude tall oil varies within wide limits.' " By a number of methods the crude oil may be refined to produce a variety of refined products. This investigation presents a preliminary comparative study of collecting properties of the fatty acids in tall oil. In Finnish tall oils these constituents are primarily palmitic, oleic, linoleic, and linolenic acids.:' The first is a saturated fatty acid having 15 carbon atoms in its hydrocarbon chain, plus one in the carboxyl group. The others have 17-carbon-atom chains and are unsaturated. It is of particular interest to note that palmitic, oleic, lino-leic, and linolenic acids represent increasing degrees of unsaturation with 0, 1, 2, and 3 double bonds, respectively. To test the collecting properties of the four fatty acids separately, the vacuum flotation technique described by Schuhmann and Prakash4 was used. By this method the boundary between flotation and non-flotation conditions was approximately delineated, with the use of ilmenite and several other minerals. Collector concentration and pH were the principal variables. On the basis of information obtained, actual flotation tests were run on an ilmenite-bear-ing ore in a laboratory flotation cell. Through the courtesy of P. Kajanne from the Department of Chemistry, Finland Institute of Technology, the following reagents were obtained for this investigation: 1—Palmitic acid, of Judex, had a purity of 95 pct as determined by parallel iodo-metric and spectrophotometric measurements. 2— Oleic acid, product of May and Baker Ltd., indicated purity of 98 pct. By iodometric and spectrophoto-metric determinations the oleic acid content was found to be 83.8 pct. In addition, it contained 6 pct linoleic, 1 pct linolenic, and 9.2 pct saturated fatty acids.' 3—Linoleic acid was prepared from soybean oil by low-temperature crystallization. Its linoleic acid content was 95 pct by the methods indicated above. 4—Linolenic acid was prepared from linseed oil by low temperature crystalIization. Its linolenic

Jan 1, 1954

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By Joseph E. Pogue

NEW economic forces are at work in the petroleum industry.. In order to visualize these forces and clearly see their bearing on the producer, refiner and marketer, it is necessary to see in perspective the economic evolution of the business. For several decades prior to 1913 the outstanding feature of the petroleum industry was a trend toward integration, culminating in a huge combine, the Standard Oil Co. An important aspect of this integrative trend, however, was its concentration on the combination aid control of refining and marketing, leaving crude oil production, for the most part, to the exigencies. of small-unit competition. It is a noteworthy coincidence that during this era the law of oil and gas was formulated and applied, whereby these substances had to be reduced to possession to establish ownership; and the forces of competition in crude oil production were thereby intensified. It was to the interest of an industry, safeguarded in its control of manufacturing and markets, to have supply stimulated by legal convention as well as by individual initiative in order that the growing demand could be met without interruption. And so over-production of crude oil during this era was no handicap, but rather an aid, to the progress of the industry.

Jan 1, 1929

By F. Weinberg

Measurements have been made of solute segregation during dendrilic growth by using radioactive solute elements and ,measuring the activity of den(12-ites cut from decanted specimens. This has been done for both lead awl tin based binary alloys contaitzing the following solute additions: Ag, T1204, was dependet on ko, the equilibrium distribution coefficient in the following way Fay k &apos;c 0.1, C/C 0.6; for k0 >0.1. 0.6 <c,/c,< I. Qualitative obse?-vations were madc of dendritic segregation, by using autoradiographic techniques, for the Sn + Ag110 and Sn + Tlo4 systems. The observation were found to he in general agreement with the measurements ofCA/Co. Autoradiographic were also obtained of scctiolccl delzr11-iie stalks. These indicated that the stalks had a substructure, dclileated by solute corzetlt?atio?zs nlolg the substructure walls. A new dendrite growth direction <JI2> is reported for tila. SOLUTE segregation in dilute binary alloys has been investigated by Pfann,&apos; Smith, Tiller, and Rut-ter,&apos; and others. They considered the case of a slowly advancing plane solid interface, and derived expressions for the distribution of solute in both solid and liquid during solidification. To determine these expressions, they assumed no diffusion in the solid and either complete mixing in the liquid:&apos; or diffusion controlled solute movements in the liquid without any convective mixing.&apos; The present investigation considers solute segregation during dendritic growth, in which case the solid-liquid interface is not plane, and the growth rates are rapid. Segregation under these growth conditions has not been treated mathematically, because of the relative complexity of the system. It has been suggested by Chalmer, on the basis of preliminary results, that an alternative to the diffusion and heat flow controlled conditions during growth is &apos;diffusionless" dendritic growth in which solid is formed with the same composition as the liquid. He suggests this type of growth may depend upon a solvent-solute relationship that permits some solid solubility without excessive increase in internal energy, as is the case for solutions of tin in lead. On the other hand, Montariol,4 and others, have shown experimentally that some segregation does occur during dendritic growth in metals using etching and radioactive tracer techniques to indicate the concentrations of the solute. The present investigation was undertaken to determine, both qualitatively and quantitatively, the extent of solute segregation associated with dendritic growth in a series of binary alloys, as a function of solute concentration. PROCEDURE The solvent materials used were Vulcan Electrolytic tin (99.997 pct purity) and Tadanac lead (99.998 pct purity). The solute materials were Zn, Sn, and Sb (better than 99.998 pct purity), Ag and Co (99.5 pct purity), and T1 (Fisher "purified" metal sticks). Activation of the solute metals was carried out in the reactor at Chalk River, Canada. Master alloys were prepared by induction heating from the radioactive solute metal and the pure solvent, under argon, in graphite crucibles. Pieces of these alloys were then added to the solvent to give the required solute concentration. Dendrites were grown in essentially the same manner as that described by Weinberg and Chalmer, , in which controlled orientation single crystals were grown dendritically in horizontal graphite boats, and the liquid decanted. The crystals were grown and decanted in an atmosphere of tank argon. Before decanting, a sample of the liquid was drawn up in a glass tube and allowed to solidify rapidly. The orientations of the single crystals were such that <loo> was parallel to the growth direction, and (100) in the horizontal plane for lead, and [1101 and (110) respectively for tin. With these orientations long dendrite stalks formed along the bottom of the boat in the dendrite direction (<100> for lead and [I101 for tin) from which secondary branches grew. Only these secondary branches, which grew freely in the liquid from the dendrite stalk to the liquid surface, were used in the measurements. Accordingly, effects due to substrates and oxides on the surface of the liquid need not be considered. In order to measure the solute concentration C, of the dendrites, individual dendrite stalks were cut from the decanted specimens, remelted, and formed

Jan 1, 1962

By R. P. Agarwala, M. S. Anand

Using residual activity technique, the diffusion of palladium, silver, cadmium, indium, and tin in alunzinum has been studied in the temperature range of 400" to 630°C. The diffusivities (in units of square centimeters per second) have been expressed as: IMPURITY diffusion in aluminum,1-9 silverand lead5 for cases of low solid solubility of the impurity in the host metal has yielded frequency factors in the range of l0-6 to l0-9 sq cm per sec whereas the activation energy is practically half the self-diffusion activation energy value. From the observed values of frequency factor, activation energy, and entropy of activation, it has been suggested&apos; that these solutes are not diffusing by vacancy or interstitial mechanisms but by a mechanism which should be consistent with such low values of the diffusion parameters (Do and Q). However in spite of extensive work on these types of systems, the mechanism of diffusion is still not well understood. The present investigation on the diffusion of palladium, silver, cadmium, indium, and tin in aluminum has been carried out to throw further light on the diffusion mechanism in systems, where the solid solubility is very low (except for the case of silver). The results are discussed on the basis of solid solubility and the structural changes involved owing to the presence of the solutes in aluminum solid solution. An attempt has also been made to apply the existing theories of charge5-8 and size8 difference between the solute and the solvent. EXPERIMENTAL PROCEDURE Specimens (1/2 in. diam by 3/8 in. high) were machined out of pure aluminum (99.995 wt pct) rod obtained from Johnson Mattheys. They were sealed under vacuum in quartz tubes and annealed at 620° C for several hours; the grains thus developed were sufficiently large to eliminate the possibility of diffusion along the grain boundaries. The flat ends were prepared carefully after polishing as described previously,10 Radioactive nitrates of cadmium, indium, and tin and chloride of palladium containing, respectively, cd115, 1n114, sn113, and pd103 were dissolved in distilled water and mixed with 30 pct acetone. By means of a micropipet a drop of this solution was placed on a smoothly polished and lightly etched surface of the specimen. Due care was taken to see that the solution spread uniformly on the surface of specimen without trickling down its sides. Radioactive silver was elec-trodeposited using a AgCN-KCN bath. The amount of sample deposited in all the cases was not more than 0.1 µ thick. The samples were then sealed in quartz tubes in vacuum. The cadmium samples were sealed in a purified argon atmosphere to avoid evaporation. The samples were then diffusion-annealed. The temperature of annealing varied between 400° and 630°C and was controlled to ±5°C. On heating to -400°C,the deposits of cadmium, indium, and tin, which were of the order of 0.1 p in thickness, were converted to their respective oxides. The contribution of oxygen present in the lattice of aluminum due to these oxides has been calculated and found to be less than 10 ppm in all cases. Oxide method has already been used by other workers11&apos;12 in diffusion studies without any controversy on the issue. However, in some of these investigations, metallic deposition was also tried. The diffusivities calculated from these measurements were found to agree very well with the diffusivities obtained by using the oxide method. Thus it is assumed that the measured diffusivities represent true diffusion coefficients. Since palladous chloride decomposes at about 500°C, the deposited samples which were to be diffusion-annealed below 500°C were heated in vacuum for a very short time at 500°C to allow the decomposition of palladous chloride to palladium metal. Time taken in decomposition of nitrates to oxides and chloride to metal was negligibly small as compared to the period of the diffusion anneals. The residual activity technique13 was used to study the diffusion profiles where thin layers from the specimen surface were removed by grinding it parallel to a flat surface on a 600-grade carborundum paper. The specimen was washed, dried, and weighed, the differ -ence of the weight being the measure of the thickness of the layer removed. After each such abrasion and weighing, the total residual activity on the surface of the specimens was measured by counting 0.656, 0.94,

Jan 1, 1968

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH&apos;S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.&apos; The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By Stanley D. Michaelson

The selection of the proper size of grinding mill for a given installation has long been a subject of discussion by mill manufacturers, consulting engineers, and their clients. It would be presumptuous for the author to propose a simple cure-all. Instead this paper describes a method that has been used over a period of years to determine mill size with a reasonable degree of accuracy. Furthermore, this method claims no theoretical background, for ball milling, as practiced today, is still an art. The selection of the proper size and type of mill must, therefore, be made on an empirical basis. A ball mill, in order to grind, must deliver power through its grinding media to the material to be ground. Assuming that a mill is properly supplied with grinding media, ore pulp, and power, the amount of grinding done is closely proportional to the power expended. With this as a basic premise we can, for the moment, forget about type of mill (i.e., overflow, low-level mill, or other design) and base our calculation of mill size on the total power required to grind a ton of a particular ore from a given size of feed to a given size of product. When this is determined the type and size of mill, its speed, and the weight of the load of grinding media can be selected to absorb this amount of power. Development of Technique Some years ago, W. L. Maxson, F. Cadena, and F. C. Bond, working in the Minerals Research Laboratory of Allis-Chalmers Co., Milwaukee, developed and described a laboratory technique for comparing grindability (or relative ease of grinding) of various ores at different mesh sizes of grind.&apos; Additional papers2 have described the work done since that time, and the most recent paper3 summarizes results for hundreds of tests on many ores and materials. The essentials of the testing method are: a 12 by 12-in. laboratory mill operating at a constant speed of rotation, using a constant volume of ore, and a constant ball load having a relatively constant grinding surface. Tests are run at 250 per cent circulating load with the feed, circulating load and products screened on calibrated Tyler standard screens. Certain ores from operating mills, representing various mineralogical types, were selected for reference and designated "standard ores." In most cases, detailed studies of the grinding circuits were made when samples of mill feed were taken for grindability tests. Each analysis formed a basis for comparison of the grindability in the laboratory with actual power requirements for a particular grinding circuit. In addition, a critical study was made to evaluate the differences in the various grinding circuits so that two or more field installations having different layouts (single-stage grinding, two-stage grinding, or others), and using mills of various diameters operating at various speeds with differing circulating loads, etc., could be compared. Large-scale tests by mill operators complemented by laboratory investiga-

Jan 1, 1947

By Stanley D. Michaelson

The selection of the proper size of grinding mill for a given installation has long been a subject of discussion by mill manufacturers, consulting engineers, and their clients. It would be presumptuous for the author to propose a simple cure-all. Instead this paper describes a method that has been used over a period of years to determine mill size with a reasonable degree of accuracy. Furthermore, this method claims no theoretical background, for ball milling, as practiced today, is still an art. The selection of the proper size and type of mill must, therefore, be made on an empirical basis. A ball mill, in order to grind, must deliver power through its grinding media to the material to be ground. Assuming that a mill is properly supplied with grinding media, ore pulp, and power, the amount of grinding done is closely proportional to the power expended. With this as a basic premise we can, for the moment, forget about type of mill (i.e., overflow, low-level mill, or other design) and base our calculation of mill size on the total power required to grind a ton of a particular ore from a given size of feed to a given size of product. When this is determined the type and size of mill, its speed, and the weight of the load of grinding media can be selected to absorb this amount of power. Development of Technique Some years ago, W. L. Maxson, F. Cadena, and F. C. Bond, working in the Minerals Research Laboratory of Allis-Chalmers Co., Milwaukee, developed and described a laboratory technique for comparing grindability (or relative ease of grinding) of various ores at different mesh sizes of grind.&apos; Additional papers2 have described the work done since that time, and the most recent paper3 summarizes results for hundreds of tests on many ores and materials. The essentials of the testing method are: a 12 by 12-in. laboratory mill operating at a constant speed of rotation, using a constant volume of ore, and a constant ball load having a relatively constant grinding surface. Tests are run at 250 per cent circulating load with the feed, circulating load and products screened on calibrated Tyler standard screens. Certain ores from operating mills, representing various mineralogical types, were selected for reference and designated "standard ores." In most cases, detailed studies of the grinding circuits were made when samples of mill feed were taken for grindability tests. Each analysis formed a basis for comparison of the grindability in the laboratory with actual power requirements for a particular grinding circuit. In addition, a critical study was made to evaluate the differences in the various grinding circuits so that two or more field installations having different layouts (single-stage grinding, two-stage grinding, or others), and using mills of various diameters operating at various speeds with differing circulating loads, etc., could be compared. Large-scale tests by mill operators complemented by laboratory investiga-

Jan 1, 1947