Search Documents

By D. K. Crampton

The object of this work was to obtain and correlate information on effect of internal stress in variously drawn tubes on several properties. Also, a simple approximate method of comparing types of stress distribution in such variously drawn tubes was sought. There is also included some work on comparison of single and polycrystalline materials and effect of different types of operation and preferred orientation. Preparation of Material A series of tubes was drawn to study the effect of the type and degree of final reduction on various physical properties and the approximate distribution of stress intensity across the tube wall. The material used all came from a single heat of 70-30 brass melted in a regular production Ajax-Wyatt induction furnace. The analysis of the metal as cast was: copper, 70.36 per cent; lead, 0.04; iron, 0.02; zinc, balance. The material was cast in "shells" with 4 in. outside diameter and in. wall thickness. It was drawn part way down according to the usual standard mill schedule and then by suitable individual schedules to finish by a variety of types and degrees of drawing to the same final cases in every instance; namely, 0.750 in. outside diameter by 0.080 in. wall thickness. The exact final draws, together with the percentage area reductions, diameter reductions and gage reductions are given in Table 1. In fabricating these tubes, rather unusual precautions were observed to insure the elimination of ail variables not under immediate study. All intermediate anneals were carried out at about 1200" F. down to the so-called "cut-in size"; namely, 17/16 by 3/16 in. From this point on, all anneals were made at from 1050' to 1100" F. The greatest care was used all through to have the tubes as free from minor surface defects as possible. When such defects were visible on intermediate sizes they were carefully filed out. On the final draw to 3/4-in diameter the die was aligned with the greatest possible precision in order to insure as straight a tube as possible

Jan 1, 1933

By John T. Eash, Clair Upthegrove

During recent years nickel has had an increasingly important role as an alloying element in the copper-tin bronzes. Nickel additions not only produce better casting alloys but also make alloys whose properties can be varied by precipitation hardening; thus leading to increased commercial application of copper-nickel-tin alloys. Recent investigations have indicated a decrease in the solubility of tin in the alpha phase as the annealing temperature is lowered and as the nickel content is increased within certain limits. A further change caused by the nickel additions is produced in the excess phase of the copper-tin bronzes. The alpha plus delta eutectoid is replaced by a clear precipitated constituent in the alloys containing up to 15 per cent tin and not less than 1 per cent nickel. This paper has a dual purpose. The first is to present a new determination of the alpha-phase boundary in alloys containing from 0 to 20 per cent nickel, together with the liquidus and solidus temperatures above that field. The second purpose is to give the equilibrium conditions existing in alloys exceeding the alpha phase containing up to 31 per cent tin and 5 per cent nickel, so that the disappearance of the alpha plus delta eutectoid constituent may be explained. After considering the earlier investigations of the related alloy systems and the experimental procedure used in this investigation, the alloys will be discussed in groups as separate quasibinary systems containing constant amounts of nickel. The systems considered contain 0, 1, 2, 3, 5, 10 and 20 per cent nickel. The straight copper-tin system was reinvesti-gated in order to establish a foundation on which to build the remaining material. The 1 per cent nickel alloys studied give the relations existing in the region of the eutectoid transformation between the copper-tin system and the 2 per cent nickel copper-tin system which has been investigated in detail. The thorough examination of the latter system was made since 2 per cent of nickel is representative of the commercial additions to the cast bronzes and also because it is sufficient to produce

Jan 1, 1933

By H. F. Moore

Jan 1, 1936

By H. F. Moore

Jan 1, 1936

By R. M. Brick

The etched mierostructures of cold-worked alpha brasses, after reductions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonymously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {ill), in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson6 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into symmetry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By R. M. Brick

The etched mierostructures of cold-worked alpha brasses, after reductions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonymously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {ill), in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson6 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into symmetry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By New kensington P. A, W. L. Fink, H. R. Freche

The investigation of aluminum alloy systems prior to 1923 was severely handicapped by the low purity of the best aluminum available. However, by that time, the electrolytic purification of aluminum had been developed by the Aluminum Company of America,(1)† and in May, 1923, there was initiated, under the direction of E. H. Dix, Jr.,(2) a program for the investigation of the aluminum-alloy systems using the purest electrolytically refined aluminum. Up to the present time 15 papers (3) have been published, most of which are on the binary aluminum systems. Work is now in progress on the ternary systems, and it seems probable that most of the future work will be on ternary systems. Therefore this survey of the binary aluminum systems investigatcd up to the present time (the sixteenth paper of the series) concludes the first phase of this program. Certain qualitative relations between corresponding portions of the various binary diagrams as well as between different parts of the same diagram were noted some time ago by R. S. Archer.(4) In the present paper these relations and others are considered quantitatively by the application of well-known thermodynamic equations or by newly discovered empirical relations. No attempt will be made here to present the history of the development of the thermodynamic equations defining equilibrium or their application to metallic systems, although a list of references is given at the end of this paper for those who are interested in this phase of the subject. Two thermodynamic equations, which will be employed extensively in this paper, are: loge x1 = - L/RT + C

Jan 1, 1934

By H. G. Landua, Leah L. Naugle, H. H. Lowry

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By Leah L. Naugle, H. H. Lowry, H. G. Landua

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By F. L. Wolf

The catenary system of line construction possesses so many desirable characteristics from the operating standpoint that it has wide application for all types of electric traction. Many steam roads are electrifying sections of their lines, and in most cases are operating both steam and electric locomotives over the same track. This means that the overhead catenary system is subjected to the severe corrosive action of locomotive smoke, and data concerning the resistance of various alloys to this form of corrosion are very desirable from every point of view. Reliable and specific information and data on the subject of corrosion due to steam and smoke from locomotives are extremely meager and, on this account, extensive service tests, together with accelerated tests, have been made on a number of commercial metals and alloys. The observations and data recorded in this paper are the result of a preliminary test which was started in 1923 and which has been carried on to the present time. The recognition of the need for even more detailed and accurate data has resulted in the undertaking of another test which has been in progress for about a year. The result of this test will be published in due course. Some years ago The Ohio Brass Co. was asked by one of the large steam railroad companies to furnish data on construction details for a catenary system which it was considering for one of its divisions. The selection of materials which would give the necessary physical characteristics as well as withstand the severe corrosive action of locomotive gases caused electrical railroad engineers considerable concern. At that time, there were available no specific or authentic data on these important questions: no systematic investigation of the problem appeared to have been made, even though it's importance was generally recognized. Such observations as had been made were crude in that they had been limited largely to visual inspection which too frequently is most misleading. However, the scattered information which was collected gave important clues as to how best to start an investigation. Technical literature was studied, metallurgical experts were consulted, and the problem was discussed with engineers who were in close contact

Jan 1, 1930

By D. J. McAdam

In 1917 Haighl presented evidence that under simultaneous corrosion and cyclic stress metals may fail at lower stresses than if the corrosion is prior to the cyclic stress. In 1926 the author, while investigating the cooling effect of water on the fatigue resistance of metals, found that under these conditions steel specimens fail at stresses far below the endurance limit.2 (By "endurance limit" is here meant the fatigue limit obtained with specimens as free as possible from stress concentration and corrosive influences.) This led to an investigation (at the Naval Engineering Experiment Station, Annapolis, Md.) of the influence of cyclic stress on corrosion. This investigation may be divided into three parts. The first part was a general survey of the conditions necessary to cause complete failure under corrosion and cyclic stress of relatively high frequency. The entire process by which metals fail under these conditions was called LLcorrosion-fatigue." Corrosion-fatigue limits" for a large number of metals were determined and the relationships of these limits to chemical composition, heat treatment and physical properties were established. The conclusion was reached that corrosion-fatigue is due to the accelerating influence of cyclic stress on corrosion. Results of this part of the investigation were presented in five papers.*-= The second part of the investigation was a preliminary study of the influence of cyclic stress on corrosion. Each experiment was conducted in two stages. The first was a corrosion stage in which the specimen was corroded under cyclic stress; the second was a fatigue stage, in which the previously corroded specimen was tested (without further corrosion) to determine its fatigue limit. The difference between this fatigue limit and the endurance limit was used as a criterion of the "damage" due to

Jan 1, 1932

By D. K. Crampton

Internal stress and season cracking in brass have been studied for many years and the technical literature contains many data on various phases of the subject. A resume of the literature shows certain fairly well established points upon which various authors are mostly agreed: 1. Season cracking is primarily caused by the presence of relatively high internal stresses, or possibly in some cases by external stresses, or both. 2. A specific corrosion is also essential to season cracking. Certain agents, particularly mercurous salts, mercuric salts and ammonia salts, have such a specific corrosive effect. 3. The tendency to season crack under given conditions increases with increasing zinc content, brass containing less than 20 per cent. zinc being relatively immune. 4. In alpha brass the season cracks are intercrystalline; in alpha-beta brass they lie between the two constituents; and in beta brass they are transcrystalline. 5. The ordinary impurities or added elements in special brasses have little or no effect on the tendency to season crack. 6. Internal stresses can be eliminated, or at least reduced to a safe limit by annealing treatments at temperatures that do not produce visible microstructural changes or appreciable softening of the worked brasses. There are, however, some points in connection with the phenomenon of season cracking which have not been thoroughly investigated, or wherein different authors and investigators are not entirely in agreement. The investigations described in this paper were undertaken to determine: 1. The correlation between mercurous nitrate tests and actual season cracking on long-time atmospheric exposure. 2. The quantitative effect of type and degree of drawing operations on the intensity of internal stress and on the tendency to season crack in brass tubes. 3. The possibility of drawing high-brass tubes in such a manner as to prevent the occurrence of harmful stresses rather than to find a remedy for such stresses once having obtained them.

Jan 1, 1930

By L. G. E. Bignell

Surveying what was done in 1929 in meeting problems of oil-field equipment corrosion, one is struck by the fact that fewer meetings were held for discussion of these problems and fewer papers written than in any year since the subject engaged the attention of petroleum engineers. This does not mean that progress has not been made, for a great deal actually has been accomplished. Recommendations that accompanied field reports have been put into actual trial and some results obtained are gratifying. The type of papers prepared also has undergone a change, for they now deal with things accomplished rather than recite damages and suggest possible remedies. Some of the most notable work pointing the way for future solution of many pipe line problems is that done for the U. S. Bureau of Standards by Dr. K. H. Logan and Dr. Gordon N. Scott, dealing with tests of pipe coatings and reports on soil conditions. Many facts of great importance have been isolated and defined by these two men, not only indicating what may be done in some instances to retard corrosion, but showing that things formerly considered of importance have little bearing apparently upon the practical results. All-aluminum Storage Tanks In April, 1928, an all-aluminum 500-bbl. field storage tank was put into actual field use in Crane County, Texas, together with another tank of the same capacity but made with steel bottom and lower section of side sheets and aluminum upper ring of side sheets and deck. In April, 1929, after a little over one year's use these tanks were opened and examined by a group of engineers and chemists. The results of the test were enlightening. Other tanks made entirely of steel and used in the same battery with the two test tanks had some of their side and bottom sheets destroyed by corrosion in six to nine months, but the all-aluminum tank was in actual use for 18 months before holes were found corroded through the bottom, when the tank was examined for a second time in September, 1929. This field test of the aluminum tank confirmed the already known

Jan 1, 1930

By Alan Morris

Impingement attack, as one of the types of corrosion suffered by condenser tubes, has been given a prominent place in corrosion literature of recent years. It has been reproduced and studied in carefully controlled laboratory tests. Much has been learned of its mechanism, and of the effects of variables such as temperature, amount of air, size of bubble and water velocity. Incidentally the technical public has been given comparisons between the behavior of some few metals under various conditions of impingement attack. The tests recorded here were undertaken in an effort to find at least some sort of qualitative answer to questions which arose occasionally as to the relative resistance of various alloys to impingement attack, and which could not be answered by reference to the literature. The final decision to start work on the problem was influenced in large measure by the nature of the water available in this particular place. The mill of the Bridgeport Brass Co. is located on the Pequonnock River at Bridgeport, Conn., within two miles of its mouth. The water is much like many other estuarine sources which are used in condensers, and which cause particularly severe corrosion. It seemed a most suitable water to use in such tests. As the work progressed an important seasonal variation was noted. The purpose of this note is to record this seasonal effect. The results of individual tests are given only incidentally. Impingement Tests Early in 1929 the apparatus was built. The samples were disks of 1-in. dia., cut from sheet metal. They were eleaned with fine emery cloth and set in holders, as shown in Fig. 1. A stream of water pumped directly from the river impinged on the surface of the sample. Compressed air was injected into the water stream through an air duct. Water pressure was maintained at about 35 Ib. per sq. in. and air was controlled by a needle valve. Velocity of

Jan 1, 1932

By Alan Morris

Season cracking of brass has received wide attention and there is a wealth of technical literature on the subject. Its causes arc fairly well understood and means for its prevention are inexpensive and effective, so that the frequency of failures from this source has diminished of recent years. But its sister phenomenon, the failure of annealed brass by reason of applied tensile stress plus a certain type of corrosion, has received less attention, though it has been responsible for occasional more or less troublesome cases of cracking of brass in service. The work described in the following pages was undertaken about two years ago to determine the relative resistance of various commercial brass mixtures to stress-corrosion cracking, and to learn something of the controlling factors. By stress-corrosion cracking we mean the cracking of brass free from internal stresses by reason of applied tensile stress and simultaneous attack by certain corrosive agents. Rogers,' in discussing a paper by Hatfield and Thirkell, says: " He had also applied a solution of mercuric salt to tensile test pieces of brass whilst they were under stress in the testing machine. At very moderate stresses such test pieces cracked, and very readily broke." Moore, Beckinsale and Mallinson2 subjected test pieces to simultaneous corrosion and tensile stress. In order to determine the minimum stress detectable in brass by the mercurous nitrate test, tensile samples were placed under stress and treated with mercurous nitrate solution. They found that brass stressed below a minimum did not crack. Dr. McAdam3 has investigated the effect of corrosion on the fatigue limit of brasses, among other materials. He directed a stream of either fresh or salt water against the specimen while it was undergoing fatigue test. The corrosion-fatigue limits thus determined may be considerably lower than the endurance limit without coincident corrosion. The exact

Jan 1, 1930

By John Wulff, J. H. Hollomon

The opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was re-deposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,a in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As2O3),

Jan 1, 1942

By John Wulff, J. H. Hollomon

The opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was re-deposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,a in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As2O3),

Jan 1, 1942

By John Wulff, J. H. Hollomon

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

Jan 1, 1941

By John Wulff, J. H. Hollomon

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

Jan 1, 1941

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942