Hydrogen embrittlement is the brittleness affecting copper and copper alloys containing oxygen which develops during heat treatment at temperatures of about 400 deg C (752 deg F) and above in an atmosphere containing hydrogen. The phenomenon of hydrogen embrittlement of copper and its alloys is illustrated by examples from practice and reference is made to data from recent publications on the subject. Embrittlement due to this cause can only be identified by microscopic examination because other modes of failure in copper; e.g., from heat cracking, mechanical overload, the formation of low melting point eutectics or corrosion; show a similar appearance when investigated on a macroscopic scale.

A steel bolt had been used to join the copper connecting strips between the poles of a 10-pole, series-connected, rotating field rotor of a synchronous motor. The exciting current was 155 amps. Failure of the bolt resulted in severe damage to the stator windings by the loosened ends of the strips. The bolt had fractured near the head, a location which probably coincided with the junction of the strips. A portion of the fracture surface was covered with copper that had been deposited in the molten state, while some was also present along the shank of the bolt, having apparently run in between the bolt and the hole in the strip. The bolt end adjacent to the fracture had been subjected to intense local heating. The extent of the grain-growth indicating that the temperature had been in the region of 1200 deg C (2192 deg F). When the temperature reached the melting-point of copper, 1083 deg C (1981 deg F), molten metal came into contact with the bolt, into which it penetrated along the grain boundaries, culminating in rupture.

A 25 mm (1 in.) copper coupling had been uniformly degraded around most of the circumference of the bell and partially on the spigot end. One penetration finally occurred through the thinned area on the spigot end of the pipe. Investigation supported the conclusion that although the pipe was buried in noncorrosive sandy soil, it was found to incur stray currents at 2 Vdc in relation to a Cu/CuSO4 half cell. Recommendations included eliminating, moving, or shielding the source of stray current.

An eddy current survey of the copper evaporator (chiller) tubes in an absorption air-conditioning unit revealed two tubes in the evaporator bundle with indications typical of longitudinal cracks. Significant necking down and grain distortion at the fracture surfaces was revealed by metallographic examination. The fracture features were found to be characteristic of an overload failure in a ductile material. The ruptured tubes were concluded as a result of examination to have failed as a result of excessive internal pressure. The source of the excessive internal pressure was assumed to be a freeze-up of the tube side water that occurred during interruption of the tube side flow or misoperation of the unit.

Eddy-current inspection was performed on a leaking absorber bundle in an absorption air-conditioning unit. The inspection revealed crack-like indications in approximately 50% of the tubes. The tube material was phosphorus-deoxidized copper. Investigation (visual inspection, chemical analysis, 0.75x images, 2x macrographs after light acid cleaning to remove corrosion product, and 75x micrographs) supported the conclusion that the absorber tubes failed by SCC initiated by ammonia contamination in the lithium bromide solution. No recommendations were made.

A T-piece from a copper hot water system failed. Microscopic examination of a polished section revealed a main crack and branching transcrystalline cracks running from the outer surface of the pipe into the pipe wall. The crack appearance indicated disintegration by stress-corrosion cracking. Although copper is not susceptible in the pure state, it is prone to stress-corrosion cracking under tensile stress in the presence of other elements in a damp ammoniacal atmosphere. The material was not defective, but a phosphorus-deoxidized copper type. The residual phosphorus combined with oxygen to form phosphorus pentoxide. Hard soldering in turn prevented the formation of cuprous oxide, and hydrogen embrittlement occurred.

Corrosion in potable and nonpotable water systems has been well documented in the past, and new research discusses innovations in water treatment and materials that are designed to enhance the quality of a water system, whether commercial or residential. This paper is a collection of five case histories on the failure of copper and steels as used in potable and non-potable water systems. The case histories cover a range of applications in which copper and steel products have been used. Copper and steel pipes are the two most commonly used materials in residential, commercial and industrial applications. The projects that are discussed cover these three important applications. The purpose of presenting this information is to allow the reader to gain an understanding of real life corrosion issues that affect plumbing materials, how they should have been addressed during the design of the water system, and how a water system should be maintained during service. We share this information in the hope that the reader will gain some limited knowledge of the problems that exist, and apply that knowledge in designing or using water systems in day-to day life.

Examination of a connecting-rod shell bearing from a six-cylinder gasoline engine was done after it was returned to the factory. Copper-lead alloy SAE 485 bonded to a low-carbon steel backing was used to make the bearing and the oil used in the engine was the recommended one. Measurable material loss was visible over most of the bearing halves particularly in a wide region at the centerline. A brittle waxlike substance identified to be a mixture of copper and lead sulfides covered the visible shallow pits and the darkened region. Change of oil with greater frequency to prevent the buildup of sulfur compounds or bearing halves that have corrosion-resistant overlay materials were recommended as best solutions.

A 12.7 mm (0.5 in.) diam tube was removed from a potable water supply due to leaks. The tube wall thickness was 0.711 mm (0.028 in.) with a thin layer of chromium plate on the OD surface. The tube had been in service for approximately 33 years. Investigation (visual inspection, EDS deposit analysis, metallurgical examination, and unetched magnified images) supported the conclusion that failure occurred due to porous material typical of plug-type dezincification initiating from the inside surface. Where the dezincification had progressed through the tube wall, the chromium plate had exfoliated from the base material and cracked. Recommendations included replacing the piping with a more corrosion-resistant material such as red brass (UNS C23000), inhibited Admiralty brass (UNS C44300), or arsenical aluminum brass (UNS C68700).

Tubes in heat exchangers, made of copper alloy C44300 and used for cooling air failed after 5 to six years of service. Air passed over the shell-side surface of the tubes and was cooled by water flowing through the tubes. Water vapor in the air was condensed (pH 4.5) on the tube surfaces during the cooling process. Air flow over the tubes reversed direction every 585 mm as a result of baffling placed in the heat exchangers. An uneven ridgelike thinning and perforation of the tube wall on the leeward side of the tube was revealed by visual examination. Undercut pits on the outer surface of the tube were revealed by metallographic examination of a cross section of the failed area. Impingement attack which led to perforation was revealed by both the ridgelike appearance of the damaged area and the undercut pitting. The heat exchanger was retubed with tubes made of aluminum bronze (copper alloy C61400).

After about 17 years in service, copper alloy C27000 (yellow brass, 65% Cu) innercooler tubes in an air compressor began leaking cooling water, causing failure and requiring replacement. The tubes were 19 mm in diam and had a wall thickness of 1.3 mm (0.050 in.). The cooling water that flowed through the tubes was generally sanitary (chlorinated) well water; however, treated recirculating water was sometimes used. Analysis (visual inspection, 9x and 75x unetched micrographs, and spectrochemical analysis) showed a thick uniform layer of porous, brittle copper on the inner surface of the tube, extending to a depth of about 0.25 mm (0.010 in.) into the metal, plug-type dezincification extending somewhat deeper into the metal. This supported the conclusion that failure of the tubes was the result of the use of an uninhibited brass that has a high zinc content and therefore is readily susceptible to dezincification. Recommendations included replacing the material with copper alloy C68700 (arsenical aluminum brass), which contains 0.02 to 0.06% As and is highly resistant to dezincification. Copper alloy C44300 (inhibited admiralty metal) could be an alternative selection for this application; however, this alloy is not as resistant to impingement attack as copper alloy C68700.

Penetration by molten copper occurred in the economizer of a large water-tube boiler. A cross section through a weld and the crack in the tube revealed a crack was an intergranular fissure. Small fissures of the same type also extended from its flanks. The main fissure was filled with an oxide scale in which were embedded particles having the appearance of metallic copper. It was concluded that the cracking that occurred at the time of re-welding was due to intergranular penetration by copper present in the deposit within the tubes, which had not been completely removed prior to welding. Subsequently, it was ascertained that trouble had been experienced with the centrifugal feed pumps, resulting in scuffing of some bronze rings. The presumption is that bronze particles had been carried in mechanical suspension in the feed water and deposited in the economizer tubes.

After 14 months of service, cracks were discovered in castings and bolts used to fasten together braces, posts, and other structural members of a cooling tower, where they were subjected to externally applied stresses. The castings were made of copper alloys C86200 and C86300 (manganese bronze). The bolts and nuts were made of copper alloy C46400 (naval brass, uninhibited). The water that was circulated through the tower had high concentrations of oxygen, carbon dioxide, and chloramines. Analysis (visual inspection, bend tests, fractographs, 50x unetched micrographs, 100x micrographs etched with H4OH, and 500x micrographs) supported the conclusions that the castings and bolts failed by SCC caused by the combined effects of dezincification damage and applied stresses. Recommendations included replacing the castings with copper alloy C87200 (cast silicon bronze) castings. Replacement bolts and nuts should be made from copper alloy C65100 or C65500 (wrought silicon bronze).

A straight-tube cooler type heat exchanger had been in service for about ten years serving a coal pulverizer in Georgia. Non-potable cooling water from a local lake passed through the inner surfaces of the copper tubing and was cooling the hot oil that surrounded the outer diametral surfaces. Several of the heat exchangers used in the same application at the plant had experienced a severe reduction in efficiency in the past few years. One heat exchanger reportedly experienced some form of leakage following discovery of oil contaminating the cooling water. This heat exchanger was the subject of a failure investigation to determine the cause and location of the leaks. Corrosion products primarily contained copper oxide, as would be expected from a copper tubing. The product also exhibited the presence of a significant amount of iron oxides. Metallographic cross sectioning of the tubes and microscopic analysis revealed several large and small well rounded corrosion pits present at the inner diametral surfaces. The cause of corrosion was attributed to corrosive waters that were not only corroding the copper, but were corroding steel pipes upstream from the tubing.

Tube sheets (found to be copper alloy C46400, or naval brass, and 5 cm (2 in.) thick) of an air compressor aftercooler were found to be cracked and leaking approximately 12 to 14 months after they had been retubed. Most of the tube sheets had been retubed several times previously because of unrelated tube failures. Sanitary (chlorinated) well water was generally used in the system, although filtered process make-up water (river water) containing ammonia was occasionally used. Investigation (visual inspection, chemical analysis, mercurous nitrate testing, unetched 5X micrographs, and 250X micrographs etched in 10% ammonium persulfate solution) supported the conclusion that the tube sheets failed by SCC as a result of the combined action of internal stresses and a corrosive environment. The internal stresses had been induced by retubing operations, and the environment had become corrosive when ammonia was introduced into the system by the occasional use of process make-up water. Recommendations included making a standard procedure to stress relieve tube sheets before each retubing operation. The stress relieving should be done by heating at 275 deg C (525 deg F) for 30 min and slowly cooling for 3 h to room temperature.

A welded joint between lengths of 4 in. OD x 13 SWG copper pipe which formed part of a cold-water main failed by cracking over one-third of the circumference. Microscopic examination of the filler metal showed that it had a structure corresponding to a brass of the 60:40 type commonly used for bronze welding. Failure resulted from dezincification of the joint material from the internal side of the tube. Also, a selective attack on the beta phase had occurred. It was evident that the loss in mechanical strength arising from the corrosion had resulted in the development of cracking in service. The filler metal used was not resistant to the conditions to which it was exposed. Copper welding rods as per BS 1077 or a Cu-Ag-P brazing alloy as recommended in BS 699, would have been preferable.

A substantial number of copper alloy C27000 (yellow brass, 65Cu-35Zn) ferrules for electrical fuses cracked while in storage and while in service in paper mills and other chemical processing plants. The ferrules, made by three different manufacturers, were of several sizes. One commonly used ferrule was 3.5 cm long by 7.5 cm in diam and was drawn from 0.5 mm (0.020 in.) thick strip. Investigation (visual inspection, metallographic examination, and a mercurous nitrate test, which is an accelerated test used to detect residual stress in copper and copper alloys) of both ferrules from fuses in service and storage in different types of plants, and ferrules from newly manufactured fuses, supported the conclusion that the ferrules failed by SCC resulting from residual stresses induced during forming and the ambient atmospheres in the chemical plants. The atmosphere in the paper mills was the most detrimental, and the higher incidence of cracking of ferrules there was apparently related to a higher concentration of ammonia in conjunction with high humidity. Recommendations included specifying that the fuses meet the requirements of ASTM B 154.

Copper piping in a closed-loop water heater system was found to be corroded with MIC and erosion of the weak oxide layer. Investigation (visual inspection, bacterial corrosion cultures, and 20x/400x micrographs) supported the conclusion that the corrosion was caused by microbiological attack, specifically sulfur-reducing bacteria. No recommendations were made.

Copper shortening has been found to occur in the rotor windings of turbo alternators and takes the form of a progressive reduction in the length of the coils leading to distortion of the end windings. The trouble results from the high loading which develops between successive layers of the strip conductor due to centrifugal force. This leads to a high frictional binding force between turns and prevents axial expansion under normal heating in service. Rotor trouble which proved to be due to copper shortening was found in a set rated at 27.5 MW. It was manufactured in 1934 at which time silver-bearing copper was not available. The use of hard-drawn silver-bearing copper for a rewind, in conjunction with special attention to blocking up the end windings, is confidently expected to effect a complete cure.

A residential subdivision near Tampa, FL was constructed in 1984 through 1985. Several sections of copper pipe were removed from one residence that had reported severe leaking. Visual examination revealed extensive pitting corrosion throughout the ID surfaces of the sample. Microscopic evaluation of a cross section of a copper pipe revealed extensive pitting corrosion throughout the inner diametral surfaces of the pipe. Some pits had penetrated through the wall thickness, causing the pin hole leaks. Analysis of a sample of water obtained from the subdivision revealed relatively high hardness levels (210 mg/l), high levels of sulfate ions (55 mg/l), a pH of 7.6 and a sulfate-to-chloride ratio of 3:1. Analysis of corrosion product removed from the ID surfaces of the pipe section revealed that an environment rich in carbonates existed inside the pipe, a result of the hard water supply. It was concluded that pitting corrosion was a result of the corrosive waters supplied by the local water utility. Waters could be rendered non-pitting by increasing their pH to 8 or higher and neutralizing the free carbon dioxide.