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 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).

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.

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.

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 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.

Two hot water reheat coil valves from a heating/ventilating/air-conditioning system failed in service. The values, a 353 copper alloy 19 mm (3/4 in.) valve and a 360 copper alloy 13 mm (1/2 in.) valve, had been failing at an increasing rate. The failures were confined to the stems and seats. Visual examination revealed severe localized metal loss in the form of deep grooves with smooth and wavy surfaces. Metallographic analysis of the grooved areas revealed uniform metal loss. No evidence of intergranular or selective attack indicating erosion-corrosion was observed, Recommendations included use of a higher-copper brass, cupronickel, or Monel for the valve seats and stems and operation of the valves in either the fully opened or closed position.

Electrical contact-finger retainers blanked and formed from annealed copper alloy C65500 (high-silicon bronze A) failed prematurely by cracking while in service in switchgear aboard seagoing vessels. In this service they were sheltered from the weather but subject to indirect exposure to the sea air. About 50% of the contact-finger retainers failed after five to eight months of service aboard ship. Investigation (visual inspection, 250x images etched with equal parts NH4OH and H2O2, emission spectrographic analysis, and stereoscopic views) supported the conclusion that the cracking was produced by stress corrosion as the combined result of: residual forming and service stresses; the concentration of tensile stress at outer square corners of the pierced slots; and preferential corrosive attack along the grain boundaries as a result of high humidity and occasional condensation of moisture containing a fairly high concentration of chlorides (seawater typically contains about 19,000 ppm of dissolved chlorides) and traces of ammonia. Recommendations included redesign of the slots, shot-blasting the formed retainers, and changing the material to a different type of silicon bronze-copper alloy C64700.