Causes and solutions of metal hydrogen embrittlement

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I. Hydrogen embrittlement 1. Phenomenon of hydrogen embrittlement Hydrogen embrittlement typically manifests as delayed fracture under stress. There were instances of galvanized parts such as car springs, washers, screws, and leaf springs that broke within a few hours after assembly, with a failure rate of 40% to 50%. Cadmium-plated components of a certain specialty product experienced batch failures due to cracking during use; a national-level research effort was launched to develop strict dehydrogenation processes. Furthermore, some cases of hydrogen embrittlement do not manifest as delayed fracture; for example, electroplating hangers (steel wires, copper wires) suffer from severe hydrogen infiltration due to repeated electroplating and acid washing processes, and often experience brittle fracture as soon as they are bent during use ； The mandrel used for precision forging of shotguns broke after falling to the ground, following multiple chromium plating processes ； Some quenched parts (with high internal stress) develop cracks during pickling. These parts suffer from severe hydrogen permeation; cracks form in them even without any applied stress, and it is no longer possible to restore their original toughness through dehydrogenation. 2. Hydrogen embrittlement mechanism: The occurrence of delayed fracture is due to the diffusion and accumulation of hydrogen within the part toward areas where stress is concentrated; these stress-concentrated areas contain numerous metal defects such as atomic lattice dislocations and voids. Hydrogen diffuses into these defects, where hydrogen atoms combine to form hydrogen molecules, generating significant pressure. This pressure, together with the residual stresses within the material and any external stresses applied to it, creates a combined force. When this combined force exceeds the material’s yield strength, fracture occurs. Since hydrogen embrittlement is related to the diffusion of hydrogen atoms, diffusion takes time, and its rate depends on the concentration gradient, temperature, and type of material. Therefore, hydrogen embrittlement usually manifests as delayed fracture. The hydrogen atom has the smallest atomic radius, allowing it to diffuse easily in metals such as steel and copper; however, hydrogen diffusion is more difficult in cadmium, tin, zinc, and their alloys. The cadmium plating layer is the most difficult to diffuse through. The hydrogen generated during cadmium plating remains initially within the plating layer and on the surface of the metal beneath it, making it very difficult for it to diffuse outward; degassing is particularly challenging. After some time, hydrogen diffuses into the interior of the metal; in particular, hydrogen that enters defects within the metal has great difficulty diffusing back out. At room temperature, the diffusion rate of hydrogen is quite slow, so immediate heating is required for dehydrogenation. As the temperature rises, the solubility of hydrogen in steel increases; excessively high temperatures can reduce the hardness of the material. Therefore, when selecting the temperature for stress relief before plating and hydrogen removal after plating, it is necessary to ensure that the material’s hardness is not reduced, that such temperatures do not fall within the range associated with brittle tempering of certain steels, and that the properties of the coating itself are not compromised. II. Measures to avoid and eliminate it: 1. Reduce the amount of hydrogen absorbed by metals. When removing rust and scale, sandblasting should be used as much as possible; if acid washing is employed, corrosion inhibitors such as ribonol should be added to the acid wash solution ； During oil removal, chemical degreasing, cleaning agents, or solvents are used, resulting in less hydrogen absorption; if electrochemical degreasing is employed, cathodic treatment is carried out first followed by anodic treatment ； During electroplating, alkaline plating baths or plating baths with high current efficiency absorb less hydrogen. 2. Use plating coatings with low hydrogen diffusivity and low hydrogen solubility. It is generally believed that when electroplating Cr, Zn, Cd, Ni, Sn, Pb, hydrogen that penetrates into the steel tends to remain there, whereas metal platings such as Cu, Mo, Al, Ag, Au, W have low hydrogen diffusivity and low hydrogen solubility, resulting in less hydrogen penetration. Where the product’s technical requirements are met, coatings that do not cause hydrogen infiltration can be used; for example, Dacromet coating can replace galvanizing. It prevents hydrogen embrittlement, increases corrosion resistance by 7 to 10 times, has good adhesion, and a film thickness of 6 to 8 um – which is equivalent to a relatively thin layer of galvanizing – without affecting assembly. 3. Pre-plating stress relief and post-plating dehydrogenation are necessary to eliminate the risk of hydrogen embrittlement. If significant residual stresses remain inside the parts after processes such as quenching and welding, tempering should be carried out before plating to reduce the risk of severe hydrogen absorption. In principle, parts that absorb a large amount of hydrogen during the electroplating process should be dehydrogenated as soon as possible, because the hydrogen in the coating and that in the surface base metal diffuse into the steel matrix, with their quantity increasing over time. The new draft international standard specifies that “dehydrogenation should be carried out within 1 hour after plating, but no later than 3 hours”. There are also corresponding domestic standards that specify the dehydrogenation treatment before and after electro-galvanizing. The dehydrogenation treatment after electroplating commonly employs heating in an oven; the typical baking temperature ranges from 150 to 300°C, with a holding time of 2 to 24 hours. The specific treatment temperature and time should be determined based on the size and strength of the parts, the properties of the coating, and the duration of the electroplating process. Dehydrogenation is often carried out in an oven. The dehydrogenation temperature for galvanized parts is 110–220°C, and the level of temperature control should be determined based on the base material. For elastic materials, thin-walled parts with a thickness of less than 0.5 mm, and steel parts with high mechanical strength requirements, dehydrogenation treatment must be carried out after galvanizing. To prevent \"cadmium embrittlement,\" the dehydrogenation temperature for cadmium-plated parts must not be too high; it is usually between 180 and 200°C. III. Issues to Note: The greater the strength of a material, the greater its susceptibility to hydrogen embrittlement; this is a fundamental concept that surface treatment technicians must keep in mind when formulating electroplating process specifications. International standards require that steel with a tensile strength of σb > 105 kg/mm2 undergo corresponding pre-plating stress relief and post-plating dehydrogenation treatments. The French aerospace industry requires corresponding dehydrogenation treatment for steel components with a yield strength of σs > 90 kg/mm2. Since there is a good correlation between the strength and hardness of steel, it is more intuitive and convenient to use material hardness to determine its susceptibility to hydrogen embrittlement than to use strength. Because both a complete product diagram and the machining process should specify the steel hardness. In electroplating, we find that the hardness of steel begins to present a risk of hydrogen embrittlement fracture at around HRC38. For parts with a hardness higher than HRC43, dehydrogenation treatment should be considered after plating. When the hardness is around HRC60, dehydrogenation treatment must be carried out immediately after surface treatment; otherwise, the steel parts will crack within a few hours. In addition to the hardness of the steel, the following factors should also be considered comprehensively: ① The safety factor of the parts during use: For parts where safety is of great importance, dehydrogenation measures should be strengthened ； ②Geometry of parts: For parts with notches prone to stress concentration, small radii, etc., dehydrogenation treatment should be intensified ； ③Cross-sectional area of the parts: Fine spring wires and thin leaf springs are highly susceptible to hydrogen saturation; therefore, dehydrogenation measures should be strengthened ； ④Degree of hydrogen permeation in parts: For parts that generate a lot of hydrogen during surface treatment and require a long treatment time, enhanced dehydrogenation measures should be taken ； ⑤Coating types: For example, a cadmium coating will severely prevent hydrogen from diffusing outward, so dehydrogenation needs to be enhanced ； ⑥Stress characteristics during part use: Dehydrogenation should be intensified when the part is subjected to high tensile stress; hydrogen embrittlement does not occur when only compressive stress is applied ； ⑦Surface treatment condition of parts: For parts with high internal residual stresses resulting from cold bending, drawing, cold roll forming, quenching, welding, etc., it is necessary to perform stress relief prior to plating; additionally, dehydrogenation must be carried out after plating ； ⑧History of the parts: Special attention should be paid to parts that have experienced hydrogen embrittlement during previous production, and relevant records should be kept. Hydrogen embrittlement is primarily caused by the \"hydrogenation\" of metals during the plating process. The substandard products you are using are not the result of an issue with the plating process itself; after all, plating (with the exception of vacuum plating) does cause metal hydrogenation. However, many metal surface treatment manufacturers omit the final step in this process – the \"dehydrogenation\" step – which is particularly fatal for elastic components. Under normal circumstances, metal parts that require high strength must undergo dehydrogenation before being delivered to customers. But in order to reduce production costs, and since customers may not be aware of this or have never requested or inspected it, skipping this step can save 5–15% in costs. Therefore, you notice that parts such as bolts and spring washers become “brittle” after being electroplated. Generally speaking, for metal parts that require certain strength levels, the dehydrogenation treatment involves maintaining the part at a temperature of 120 degrees to 220 degrees for 1 to 2 hours (after electroplating); the specific conditions must be determined according to the requirements of the particular part.