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By Saskia Duyvesteyn

For many applications in hydrometallurgy and water treatment it would be advantageous to use ion-exchange resins in stirred reactors. However, attrition of the resin may lead to significant losses of both resin and metal values and prevent water quality goals from being reached. We have studied the recovery of fine resin particles by froth flotation, using the model copper - Dow XFS4195 chelating resin system. As the functional group on the resin is a bis-picolylamine, the resin should be amenable to flotation by anionic collectors, such as sodium dodecylsulfate and sodium dodecylsulfonate. The kinetics of copper loading from dilute aqueous solutions in an agitated vessel were studied as a function of copper concentration, pH and resin bead size. The flotation of unloaded resin was investigated for different types of collector, collector concentration, conditioning time, and resin bead size. Potential applications are discussed.

Jan 1, 1995

By R. Mensah-Biney

The loading characteristics of gold-tetrabromide species onto activated carbon have been evaluated using a completely mixed batch reactor system. The overall loading of gold onto carbon was rapid for the first hour but continued slowly without cessation as a result of reduction of gold. Conventional equilibrium considerations were therefore not applicable. Although loading continued slowly after several days, abnormally high loading capacity values of 10-12 meq/g carbon (650-800 kgAu/tonne) could be attained within 72 hours. The loading of gold-bromo species by activated carbon was by the mass transfer of [AuBr4l-onto the carbon surface where reduction to metallic gold took place. Elution of gold from the loaded carbon was feasible provided the carbon had not been loaded to too high capacity values. If loading is carried to high levels, complete elution becomes impractical and the gold may be recovered by ashing the carbon. For the high loading capacities observed, this option would appear to be cost effective. The effect of several variables on the loading capacity of the activated carbon is discussed.

Jan 1, 1992

By Gamal Rashed, Zorica Radakovic-Guzina, Khaled Mohamed

"Underground coal mines use mechanical bolts in addition to other types of bolts to control the rib deformation and to stabilize the yielded coal ribs. Limited research has been conducted to understand the performance of the mechanical bolts in coal ribs. Researchers from the National Institute for Occupational Safety and Health (NIOSH) conducted this work to understand the loading characteristics of mechanical bolts (stiffness and capacity) installed in coal ribs at five underground coal mines. Standard pull-out tests were performed in this study to define the loading characteristics of mechanical rib bolts. Different installation torques were applied to the tested bolts based on the strength of the coal seam. A typical tri-linear load-deformation response for mechanical bolts was obtained from these tests. It was found that the anchorage capacity depends mainly on the coal strength. Guidelines for modeling mechanical bolts have been developed using the tri-linear load-deformation response. The outcome of this research provides essential data for rib support design.INTRODUCTIONThe design of rib bolting in U.S. coal mines is based on a trial-and-error process, which is insufficient to eliminate injuries and fatalities caused by rib falls. In the last 10 years, rib failures have resulted in 17 fatalities, representing 52% of the ground-fall fatalities in underground coal mines in the United States (MSHA, 2018). Recently, NIOSH researchers surveyed 90 sites in 14 underground coal mines in the Eastern United States and found that 11 mines are bolting coal ribs, with 4 of those mines using the conventional mechanical bolts and the others using fully-grouted bolts. NIOSH researchers are developing an engineering design procedure for rib support. Pull-out test programs for mechanical and grouted rib bolts were conducted to understand the rib control mechanisms of rib bolts. Only the test results of mechanical bolts are presented in this paper.Mechanical bolt (or point-anchored bolt) is a tensioned bolt anchored down the borehole with a mechanical expansion shell or a resin-grouted medium (Peng and Tang, 1984). The mechanical anchor bolt consists of a plug, a shell anchor, a headed bar with the top end threaded, a bearing plate, a hardened washer, and occasionally a friction-reducing washer. The shell anchor can be either standard or bail type (Figure 1). The standard type shell is held in place by a nut, while the bail anchor uses a strap to hold the shell in place (Peng, 2008). The diameter of the bar is generally 16 mm (? in) for the #5 bolt or 19 mm (6/8 in) for the #6 bolt. The diameter of the hole that the bolt is inserted into must be carefully controlled, since an oversized hole can result in poor anchorage (Moss, 1971). The anchorage is obtained by applying torque to the bolt head, which in turn pulls the plug down in the shell and expands the serrated leaves against the sides of the hole-wall. In the resin-grouted anchor, the resin replaces the mechanical expansion shell at the end of the hole. The anchorage is achieved by bonding between the resin, bolt, and the hole-wall."

Jan 1, 2019

By Linge HG, Klauber C

The key element in the carbon-in-pulp process for gold processing is the loading of dissolved Au(CN)2 from solution onto activated carbon. The mechanism and kinetics of this step have been examined by solution adsorption-desorption and X-ray photoelectron spectroscopy for both coconut derived activated carbon and peat-based activated carbon. The results show that these carbon types have the same mechanism and kinetics of adsorption. There is no contribution to the bonding from carbon-oxygen functionalities on the carbon surface, as has been invariably supposed in all previous theories for the mechanism of the reaction. It is shown that Au(CN)Z is reversibly adsorbed intact on and parallel to the graphitic planes of the carbon with the formation of a weak carbon-gold n-donor bond. The kinetic measurement of carbon gold loading reactivity is discussed and use of the Murdoch equation for this test is critically assessed.

Jan 1, 1989

By H Zorychta

Based on underground measurements made at the Nova Scotia coal mines of the Dominion Coal Company, Limited, this paper presents a comparison between the physical properties of hardwood packs and steel friction props when used for longwall support. The probable loads sup-ported by steel friction props on a longwall face at both the Dominion No. 20 Colliery and the Princess Colliery are delineated, and the results of the tests are presented in graphical form. It is concluded that the steel friction props are more efficient than the hardwood packs that they replaced as roof supports. Introduction AN evolution in the methods of longwall face support is taking place in the Sydney coalfield. Longwall face support had consisted primarily of timber props and hardwood packs. In 1957, however, at the Princess Colliery, Sydney Mines, Nova Scotia, the first longwall was equipped with steel friction props. At the present time, eleven longwall faces are supported on wood and sixteen faces are carried on steel friction props.

Jan 1, 1965

By A. M. Esteves

This paper offers an overview of local content policies and practice in the mining sector. Specifically, the paper aims to answer the question of how national and regional governments, industry and civil society can work together to seek an optimal outcome while pursuing their diverse objectives. The paper begins by defining local content and its scope at the subnational level. Specific recommendations for the design of local content policies to mitigate social, economic and governance risks are developed. The document then offers some recommendations regarding the role of partners in design, implementation, monitoring, and enforcement of local content policies.

Aug 1, 2013

By T O&apos, Sullivan

Reconciliation of metal production from a sublevel cave (SLC) mining operation is a complicated process. SLC reconciliation is unlike reconciliation for open stope operations, where a tonnage of extracted ore can be assigned to an exact volume of in situ ore, and a direct comparison made between the estimation of contained metal and actual metal production. In SLC operations the ore extracted from a particular SLC drawpoint will be composed in part from the parcel of freshly blasted in situ material, in part from varying components of ore material (from cave stocks) flowing down from other previously mined areas vertically above the current draw position and in part from external dilution. This leads to difficulties in reconciling production grades against estimated grades. The problem is that we know how much metal we have produced but we can not precisely say where it has come from. Metal production reconciliation is fundamental in assessing ore reserve estimation accuracy and performance and in determining a draw management strategy for SLC mining. In terms of contained metal, differences in extracted metal compared to in situ metal represent changes to cave stocks. To generate local estimates of the cave stocks, differences in metal for each ring are treated as additions to or subtractions from a series of vertical columns of stocks extending throughout the height of the cave. The sum of metal differences (extracted versus in situ) for each vertical column results in a residual metal map at any particular mining level. The metal maps show areas where the metal production has been greater than or less than expected. The maps also highlight areas in the cave where residual metal is located, areas where targeted overdraw can reduce cave stocks.

Jan 1, 2006

By Tiebao Yang

In high pressure die casting processes, a die plays a critical role in removing heat from the molten metal during the cavity filling and solidification stages. Proper control of die temperature is essential for producing superior quality components and yielding high production rates. This paper proposes a local temperature control scheme for die thermal management based on a computerized intelligent real-time monitoring and control system (IRMCS). In this scheme, cooling water lines are controlled by a pump and solenoid valves. A controller is designed according to the law of die temperature fluctuations. The results obtained from the experiments carried out on a laboratory die casting process simulator indicate that the controller can limit the local die insert temperatures in a given band. Hence, the desired thermal pattern of the die insert becomes achievable.

Jan 1, 2006

By F. A. Guo

Ultrafine-grained surface layers were obtained by surface mechanical attrition treatment (SMAT) in copper and titanium samples. The thermal properties of the deformed layers were characterized using a scanning thermal microscopy (SThM) that allows thermal conductivity to be mapped down to the submicrometer scale. A theoretical approach, based on this investigation, was used to calculate the heat flow from the probe tip to the sample and then estimate the thermal conductivities at different scanning positions. Experimental results and theoretical calculation demonstrate that SThM can be used as a powerful tool for the thermal property and microstructural analysis of ultrafine-grained microstructures.

Jan 1, 2006

By M. Ye. Melnikov

The report is about oceanic ferromanganese crusts ? covers of iron and manganese hydroxides developed over an opened rock of seamounts and rises. Ore bed parameters of crusts are understandable as their thickness and content of main economic components ? manganese, cobalt and nickel. All known results of research activity on ferromanganese manganese crusts point to that crust are characterized by notable variability of thicknesses and composition. It is possible to separate few levels of variability. The most evident is the first level of parameters variability, which is manifested in various regions of the Ocean, and connected first of all, with an age of submarine mountains, a host objects for a crusts. It was proved by many authors, that most powerful crusts are connected with submarine mountains of Cretaceous age. [1]. Crust thickness at the Magellan Seamounts reaches, for example 12-15 cm, sometimes exceeds 20-22 cm. Thicknesses of Hawaii Archipelago or Tuamotu crusts in 3-4 times less. Biostratigraphy studies of crustal sections at the Magellan Seamounts already show, that its main part started to form in the Late Paleocene. Four layers with well expressed features in structure and composition of a layer are separated in the section. From foot to top: Late Paleocene ? Early Eocene layer I-1, Middle-Late-Eocene layer I-2, Miocene layer II and Pliocene ? Quaternary layer III. Relics of more ancient Campanian ? Maastrichtian ore layer [2, 4] were discovered. It is evident for example, that Oligocene mountains could not be a host for two lower layers in the crust section.

Jan 1, 2010

By M. Ye. Melnikov

The report is about oceanic ferromanganese crusts ? covers of iron and manganese hydroxides developed over an opened rock of seamounts and rises. Ore bed parameters of crusts are understandable as their thickness and content of main economic components ? manganese, cobalt and nickel. All known results of research activity on ferromanganese manganese crusts point to that crust are characterized by notable variability of thicknesses and composition. It is possible to separate few levels of variability. The most evident is the first level of parameters variability, which is manifested in various regions of the Ocean, and connected first of all, with an age of submarine mountains, a host objects for a crusts. It was proved by many authors, that most powerful crusts are connected with submarine mountains of Cretaceous age. [1]. Crust thickness at the Magellan Seamounts reaches, for example 12-15 cm, sometimes exceeds 20-22 cm. Thicknesses of Hawaii Archipelago or Tuamotu crusts in 3-4 times less. Biostratigraphy studies of crustal sections at the Magellan Seamounts already show, that its main part started to form in the Late Paleocene. Four layers with well expressed features in structure and composition of a layer are separated in the section. From foot to top: Late Paleocene ? Early Eocene layer I-1, Middle-Late-Eocene layer I-2, Miocene layer II and Pliocene ? Quaternary layer III. Relics of more ancient Campanian ? Maastrichtian ore layer [2, 4] were discovered. It is evident for example, that Oligocene mountains could not be a host for two lower layers in the crust section.

Jan 1, 2010

By W Assibey-Bonsu

The paper provides a brief review of the multivariate uniform conditioning and the localised multivariate uniform conditioning techniques and presents a case study based on a porphyry copper gold deposit in Peru. Two other important scenarios have been investigated and will be particularly emphasised: The recovered selective mining unit (SMU)s depend on a combination of copper and gold content, which can be expressed by means of ænet smelter returnsÆ (NSR). Two approaches are compared. Firstly, the application of a composite cut-off on NSR on the joint distribution of each grade and the application of uniform conditioning to three variables is investigated, ie for the first approach NSR is used as the main variable. The second approach considers copper as the main variable. In the case of multiple domains the procedure used to apply the technique to process mixed panels is clarified and recommendations are made.

Sep 26, 2011

By James Boyd

REACTIVE metals are not only those sufficiently radioactive to be used as fuels, such as uranium and thorium, but all metals that will find application in power reactors. It is required of such metals that they be relatively inert or chemically unreactive, dimensionally stable at high temperatures and pressures, and either very absorbent of radioactivity or transparent to it. To gain the right perspective concerning these metals it is necessary at this point to explode some erroneous concepts propounded so often they have become accepted as fact. The first of these is that the great industrial nations, especially the U. S., have reached their pre-eminent position chiefly because they possess abundant mineral resources. Some U. S. mineral economists, echoed by the politicians, have taken this position so often that many of their theories and policies are based on the presence of developed mineral resources as a sine qua non to the country's greatness. Actually the reverse is true- under a social and political system granting free rein to the initiative and creativeness of its people, many hidden mineral resources that otherwise would have lain fallow have been developed into productive enterprises to the benefit of the national industrial economy. Again, once the proper incentive was furnished, other countries have also been able to establish valuable mineral enterprises in recent years; resources long dormant for lack of a proper economic environment suddenly have become valuable and productive. It is possible to name immediately several nations where such domestic economic developments have had favorable repercussions within the last decade. The absence of productive mines in any country is no indication that workable deposits do not exist within its territory.

Jan 11, 1957

By Walton J. Greer, System By John E. Owen

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By System By John E. Owen, Walton J. Greer

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By R. H. Winn

A method for the selection of the most suitable corrosion inhibitor for a particular system is given. The method involves the evaluation of surface passivity by means of copper ion displacement after the metal surface has been subjected to the corrosive atmosphere. The application of the method to the selection of suitable inhibitors for use in producing wells is described. Correlation with recognized laboratory tests has beet1 found to be good within the limitations of the test. The use of the test to evaluate inhibitor persistencc is described. INTRODUCTION Corrosion as it is associated with the industry shows wide variations in its qualitative as well as its quantitative aspects. This complicates the work of the corrosion engineer. In the past few years the efforts of the corrosion engineer have been further taxed by the large numbers of products being marketed as corrosion inhibitors by various manufacturers. These products are submitted to him together with a limited amount of data to support their use as inhibitors. The data are usually authentic and reliable yet all too often when these products are applied to an actual corrosive system the results are disappointing due to the ineffectiveness of the inhibitor and the corrosive system. The corrosion engineer must select a comparatively limited number of inhibitors for field trial from the large number available. The selection is usually made on the basis of a standardized laboratory test such as that adopted by the National Association of Corrosion Engineers or by field experience in an area; however, testing of this type is discouraging on large numbers of compounds, particularly in view of the specificity of environment. It has been an object of this work to devise a method which will allow the corrosion engineer to select the best inhibitor for a specific environment under field conditions. The test would of necessity be rapid and inexpensive. It would preferably eliminate the need for expensive and delicate instruments. STATEMENT OF THEORY The test as developed makes use of the fact that metal ions will be displaced from solution by metals having a more positive electrode potential. Thus, if an active iron surface is exposed to a solution of a copper salt, free copper will plate spontaneously on the iron surface as it is displaced from the salt solution by iron ions. If the iron surface is passified, as by coating with an insulating-type organic corrosion inhibitor, it is no longer capable of displacing the copper ions due to its own limited ionization. The result will be a change in the amount of copper plated upon exposure to a neutral copper salt solution. In practice it has been found possible to measure the magnitude of the alteration of the cell potential by determining the copper deposited on a standard iron surface under controlled conditions. This means that, as the film builds up, the resulting shift in the electrode potential tends to cause the iron surface to act more like a noble metal, resulting in a reduction in the cell potential to a point that copper will no longer plate spontaneously. Obviously, the salts of other metals such as silver, gold or platinum might be used for this operation; however, copper was selected because of the color difference of the plate, the comparatively low cost of copper salts and the ease of evaluation of the plated copper. Furthermore, its high cell potential provides a substantial driving energy. The determination of the copper is readily done colorimetrically by dissolving it in 5 per cent ammonium hydroxide solution containing 2 per cent potassium per-sulfate. The blue color of the copper ammonic complex ion so developed may be compared with standards prepared by dissolving known quantities of copper powder in the same reagent. In routine screening it is seldom desirable to determine the amount of copper plated. It is usually more important to determine the concentration of inhibitor required to prevent the plating of copper.

By P. Majani, F. P. Kokesh, M. Grosmangin

Determination of the quality of cementation of casing in oil wells in the past has involved inflow and circulation tests to insure that the producing zones were adequately sealed off from the adjacent zones. Existing logging methods, such as temperature and radioactivity surveys, may detect the presence of cement behind the casing. However, the qualities of the cement (i.e., its hardness and particularly its bond to the casing) are not indicated. The new logging method described in this paper operates on the principle that the attenuation of a sonic pulse transmitted by a casing is greatly increased when that casing is bonded to an outer annulus of hard material (such as set cement) which has an appreciably smaller sonic-wave velocity than that of the casing. The down-hole tool contains a source of recurrent sound pulses which are detected by a receiver spaced a few feet from the source The amplitude of the detected casing-borne pulse is measured, and the resulting signal is transmitted to the surface where it is recorded vs depth. Since amplitude is a function of attenuation, the log is readily interpreted. Laboratory studies have shown straightforward relationship between attenuation and such variables as source-detector spacing and per cent of circumference bonded. It is shown that cement not set or not bonded to the casing has compara- tively little attenuating effect. Field examples show not only the cement top, but also the variation in cementation quality below the top. Further, the increase of bonding with time and after squeeze cementation is depicted. The detection of poor cement jobs is confirmed by production tests and by formation-test results. It is anticipated that the method will have wide application in evaluating cementation quality prior to formation testing in completions and recompletions. The analysis it affords may aid in further improving cementation techniques. INTRODUCTION The main purpose of oilwell cementing is to isolate a production zone from other undesirable zones. To investigate whether this purpose has been accomplished, several logging methods have been used such as temperature logs, radioactive tracer logs, etc. While these logs all respond to the presence of cement behind the casing, they do not indicate the degree of bonding of the cement to the casing. Early in the application of sonic logging, it was noticed that considerable attenuation of sound signals takes place in cemented pipe and is often made evident on the standard Sonic log by cycle skipping.' The development of a circuit capable of continuously recording the amplitude of the casing-borne sound signal has made possible an extensive series of laboratory and field tests, which gave the following results. The amplitude of a sound signal after it has traveled in a firmly cemented pipe is only a small fraction of that recorded by the same device in free pipe. This provides a wide spectrum of energy levels; for given local conditions, empirical values of the amplitude can be correlated with the quality of cementation. Interpretations made in this manner generally have been confirmed by production tests, circulation tests and squeeze cementation. The purposes of this paper are to give a general description of the new logging method and to present some laboratory and field results. CYCLE SKIPPING Early attempts to study the quality of the cement behind the casing were performed with a standard Sonic log, which measures the transit time At, and were based on the well known phenomenon of cycle skipping.' Cycle skipping normally is interpreted as being a manifestation of weak signals at the receivers. The log of Fig. 1 was run with the recording instrumentation adjusted to enhance cycle skipping. A mirror-image presentation was used for better visual interpretation. The transit time of sound in steel is about 58 microseconds/ft (corresponding to a velocity of 17,000 ft/ sec), and the portions of the log where this value is recorded are interpreted as zones with no cement bond. Where cycle skipping produces a higher value of At, weak signals (or a high rate of attenuation) are indicated, and a good cement bond may be present. The occurrence of cycle skipping, however, depends too much on instrument adjustment to give a uni-

By S. E. Szasz, E. J. Moore, B. F. Whitney

An accurate value of formation water resistivity R, is essential in calculating formation porosity and fluid saturation from electrical well logs. In the cases where R, has not been measured directly, it must be obtained from other data, e.g., the SP curve. This paper deals with another approach: how to calculate R, from the chemical analysis of the formation water. INTRODUCTION It is known that the resistivity of aqueous solutions of pure salts depends on their concentration and on the temperature; the concentrations are given in MPL (mg of solute per liter of solution), or sometimes in ppm (mg of solute per kg of solution): MPL = ppm X specific gravity. Values for different pure salts are available in the literature, but not for solutions of mixtures which are of practical interest. The major component of the dissolved material in almost all formation waters being sodium chloride, it is customary to express the resistivity of formation waters in terms of equivalent sodium chloride concentration, i.e., the concentration of a solution of pure NaCl which has the same resistivity at a given temperature as that of the formation water under consideration. Thus, the problem of calculating R, from the chemical anaylsis can also be stated as how to convert the other constituents of the solute into equivalent NaCl concentration. Salts dissolved in water are at least partly dissociated into ions, and do not conserve their identity. If known amounts of several salts are dissolved in water, the solution does not necessarily contain the same salts in the original proportion, but perhaps some other combination of the ions, along with free ions in solution. This is why the chemical analysis of formation waters is often given in terms of ions, as if all dissolved salts were completely dissociated. Our problem then boils down to how to convert the concentrations of the various ions to equivalent concentrations of Na' and C1-. Dunlap and Hawthorne' have proposed to convert the concentration of all other ions to equivalent Na' and C1-concentrations by means of constant multipliers; e.g., 0.95 for Ca"; 2.0 for Mg"; 0.27 for HCO 3-; 0.5 for SO, -, etc. Their factors were based on measurements made at 68F on 26 formation water samples from the Texas Gulf Coast, ranging in concentration from 1,500 to 75,000 ppm. The Dunlap method is widely used in electric log interpretation, and is often extrapolated beyond its original concentration range. A comparison of R, values calculated by this method and values actually measured on formation water samples has shown large discrepancies, especially at higher concentrations. Therefore, two new methods were developed at Sinclair Oil Corp.'s Tulsa Research Center to calculate equivalent sodium chloride concentration from the chemical analysis of formation water samples. FUNDAMENTAL CONSIDERATIONS The resistivity of a solution, or its reciprocal the conductivity, at a given temperature is determined by the charge, concentration and mobility of the ions actually present. Monovalent ions such as Na' or C1- always carry the same charge. Compounds of polyvalent ions, however. may show incomplete dissociation, e.g., NaSO; + Na' instead of SO,-- + 2Na'. This happens especially in more concentrated solutions. Only very dilute solutions are completely dissociated, as assumed in the chemical analysis report. At higher concentration, the degree of dissociation depends not only on the nature and concentration of the particular salt under consideration but also on the nature and concentrations of the other solutes. Mobility of the ions depends on the viscosity of the solution. It also depends on the degree of hydration of the ions, which in turn is a function of the nature and the charge of the ions and also of the amount of free water available per ion, i.e., the total ionic concentration. The net effect is that the conductivity increases slower than proportional to the concentration, even if a solution contains only one salt such as NaC1, and is different for different salts (Fig. 1). Conductivity can even decline with a further increase in concentration, e.g., if additional salt is little dissociated but ties up some of the free water and/or causes an increase in viscosity. In solutions containing more than one salt, the contribution of one salt to the total conductivity depends not only on the fractional concentration of this same salt, but also on the concentration of all other solutes. A perfect method would give the conductivity or resistivity of a solution as a function of the concentrations of all solutes present. This is so complicated as to be impractical, and a simpler method must be found which is of acceptable accuracy. The Dunlap method, on the other hand. is too simple because it askmes that at any concentration the contrih-

Jan 1, 1967

By J. D. Milburn, H. J. Hill

In quantitative interpretation of electrical logs the presence of clay minerals introduces an additional variable which further complicates an already complex problern. Although recognizing the difficulties introduced as a result of the heterogeneity of natural sediments and despite the present incomplete state of knowledge regarding electrochemical behavior of shales, dissemirzated clay minerals and concentrated electrolytes, it was felt that useful empirical correlations might be obtained from experimental investigation. Six typical sandstone formations, having a wide variety of petrophysical properties, were selected for the study. Approximately 45 samples from each formation were selected to satisfactorily represent the range of pore size distribution within the particular formation, As a matter of general interest, four limestone formations were also included in the investigation. Previously proposed equations relating to resistivity, SP and interrelationship of the two phenomena have, where possible, been tested with data obtained in this investigation. These equations do not satisfactorily describe experimental behavior of samples through all degrees of shaliness or throughout the range of brine solution resistivities normally encountered in logging practice. An empirical equation has been developed which quantitatively relates formation resistivity factor to satirrnting solution resistivity, porosity, and "effective clay content." This relation is indicated to be uniformly applicable to clean or shaly reservoir rocks. It is shown that both the SP and resistivity phenomena of shaly samples are related to the sample cation exchange capacity per unit pore volume. The independent chemical determination of this parameter is thus a means of determining the "effective clay content" of samples. Some implications regarding theory and electric log interpretation of shaly sands are discussed. INTRODUCTION The use of electrical resistivity logs as a means for estimating formation porosity is based upon the original work of Archie1. It was shown by empirical methods that the resistivity of a rock, when 100 per cent saturated with brine solution, could be related to rock porosity through the equation, F = Ro/ RW = f-m.......(1) where F, the formation resistivity factor, is defined as the ratio of the resistivity of the 100 per cent water saturated rock, Ro, to the saturating solution resistivity, Rw; f is the ratio of pore volume to bulk volume; and m is the slope of the average line when the data are plotted on log-log paper. This relation was established for relatively shale-free formations containing water having high salt concentrations, and under these conditions F may be considered constant for a given rock sample. Applications of Eq. 1 to interpretation of logs of shale-free formations has been quite successful when satisfactory formation water resistivity data could be obtained. The most readily available means of estimating formation water resistivity is the self-potential log. Conventional methods of SP log interpretation involve correct.

Jan 1, 1957