Permeation measurements to study hydrogen uptake by steel electroplated with zinc-cobalt alloys

Hydrogen permeation measurements were performed to investigate hydrogen uptake by a steel substrate when electroplated with zinc-cobalt alloys. The influence of plating bath composition and pH were studied and the effect of absorbed hydrogen on embrittlement of high strength steel was measured in slow strain rate tests. It was shown that the majority of the hydrogen generated during electroplating was either evolved from the surface or trapped in the coating. Only a very small proportion, equivalent to 0.1-0.6% of the total charged passed, was absorbed by the steel and was responsible for causing embrittlement. The average amount of hydrogen required to cause hydrogen embrittlement failure of quenched and tempered AISI 4340 steel was 1.5 × 10⁻⁷ g H atoms cm⁻². There was a linear relationship between the rates of hydrogen uptake from the different coatings and the extent of hydrogen embrittlement produced in the high strength steel. In certain conditions, a cobalt-rich layer formed at the steel/coating interface and this layer was shown to be beneficial in restricting hydrogen uptake and embrittlement.     

Evaluation of WC–17Co and WC–10Co–4Cr thermal spray coatings by HVOF on the fatigue and corrosion strength of AISI 4340 steel

It is known that chromium electroplating is related to the reduction in the fatigue strength of base metal. However, chromium results in protection against wear and corrosion combined with chemical resistance and good lubricity. Environmental requirements are an important point to be considered in the search for possible alternatives to hard chrome plating. Aircraft landing gear manufactures are considering WC thermal spray coating applied by the high-velocity oxygen-fuel (HVOF) process an alternative candidate, which shows performance at least comparable to results, obtained for hard chrome plating. The aim of this study is to compare the influence of WC–17Co and WC–10Co–4Cr coatings applied by HVOF process and hard chromium electroplating on the fatigue strength of AISI 4340 steel, with and without shot peening. S–N curves were obtained in axial fatigue test for base material, chromium plated and tungsten carbide coated specimens. Tungsten carbide thermal spray coating results in higher fatigue strength when compared to hard chromium electroplated. Shot peening prior to thermal spraying showed to be an excellent alternative to increase fatigue strength of AISI 4340 steel. Experimental data showed higher axial fatigue and corrosion resistance in salt fog exposure for samples WC–10Co–4Cr HVOF coated when compared with WC–17Co. Fracture surface analysis by scanning electron microscopy (SEM) indicated the existence of a uniform coverage of nearly all substrates.     

Hydrogen embrittlement of high strength steel electroplated with zinc-cobalt alloys

Slow strain rate tests were performed on quenched and tempered AISI 4340 steel to measure the extent of hydrogen embrittlement caused by electroplating with zinc-cobalt alloys. The effects of bath composition and pH were studied and compared with results for electrodeposited cadmium and zinc-10%nickel. It was found that zinc-1%cobalt alloy coatings caused serious hydrogen embrittlement (EI 0.63); almost as severe as that of cadmium (EI 0.78). Baking cadmium plated steel for 24 h at 200 °C gave full recovery of mechanical properties but specimens plated with zinc-1%cobalt and then baked still failed in 89% of the time of unplated controls. It was shown that hydrogen uptake and embrittlement could be controlled by depositing thin layers of cobalt or nickel at the steel/coating interface. For example, the least embrittlement was caused by zinc-10%nickel (EI 0.037) due to a nickel rich layer with very low hydrogen diffusion coefficient that formed during the initial stages of electroplating. Similarly, a 0.5 μm nickel layer was effective in lowering the embrittlement caused by zinc-1%cobalt to that of zinc-10%nickel. Furthermore, a 0.5 μm cobalt layer deposited before a zinc-1%cobalt coating gave virtually 100% recovery of mechanical properties after baking.     

Effect of pulsed DC CFUBM sputtered TiN coating on performance of nickel electroplated monolayer cBN wheel in grinding steel

The present research involves the deposition of pulsed DC CFUBM sputtered TiN on nickel plated steel discs and electroplated monolayer cBN wheels at seven different target frequencies and ten different bias voltages separately. The coating microstructures and the interaction between TiN and nickel were studied using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and electron probe micro analysis (EPMA). Phase detection was carried out using grazing incidence X-ray diffraction (GIXRD) technique. The cohesive and adhesive strengths of nickel layer were assessed by scratch test. After grinding of low carbon steel (AISI 1020) and hardened bearing steel (AISI 52100), the conditions of the uncoated and coated cBN wheels were observed under Stereo Zoom Microscope and SEM.Average column size of TiN was found to decrease with increase in both target frequency and negative bias voltage. The structure of the coating gradually transformed from porous and open columnar (at 0 V bias) to very compact, dense and featureless (at − 80 V bias). EDX line scan and EPMA confirmed the cross-diffusion between TiN and nickel and GIXRD indicated the formation of nickel-titanium intermetallic phases at their interface. The cohesive strength of nickel layer was not effectively enhanced with increase in target frequency, whereas the same was significantly improved with increase in negative bias voltage. Seemingly, TiN coated wheel could not perform better than the uncoated wheel in grinding AISI 1020 steel due to high wheel loading. However, the uncoated wheel was found to undergo fracture wear, which was remarkably absent in the coated wheels. On the other hand, many fractured grits and some grit pull-out were observed in the uncoated wheel when grinding AISI 52100 steel, whereas almost no pull-out along with much less fractured grits were observed in the wheels coated at bias voltages like − 60 V and − 90 V.     

Effects of electroplated zinc-nickel alloy coatings on the fatigue strength of AISI 4340 high-strength steel

Recovered substrates have been extensively used in the aerospace field. Cadmium electroplating has been widely applied to promote protective coatings in aeronautical components, resulting in excellent corrosion protection combined with a good performance in cyclic loading. Ecological considerations allied to the increasing demands for corrosion resistance have resulted in the search for possible alternatives. Zinc-nickel (Zn-Ni) alloys have received considerable interest recently, because these coatings show advantages such as a good resistance to white and red rust, high plating rates, and acceptance in the market. In this study, the effect of electroplated Zn-Ni coatings on AISI 4340 high-strength steel was analyzed for rotating bending fatigue strength, corrosion, and adhesion resistance. The compressive residual stress field was measured by x-ray diffraction prior to fatigue tests. Optical microscopy documented coating thickness, adhesion characteristics, and coverage extent for nearly all substrates. Fractured fatigue specimens were investigated using scanning electron microscopy (SEM). Three different Zn-Ni coating thicknesses were tested, and comparisons with the rotating bending fatigue data from electroplated Cd specimens were performed. Experimental results differentiated the effects of the various coatings on the AISI 4340 steel behavior when submitted to fatigue testing and the influence of coating thickness on the fatigue strength.     

塑性形变对4340钢中氢的富集及传输行为影响

采用渗氢试验和数值计算两种方法研究．了塑性形变对金属中氢的扩散和富集的影响，讨论了４３４０钢中的氢浓度与塑性形变大小、氢扩散时间及边界条件之间的关系．     

塑性形变对4340钢中氢的富集及传输行为影响

采用渗氢试验和数值计算两种方法研究.了塑性形变对金属中氢的扩散和富集的影响,讨论了4340钢中的氢浓度与塑性形变大小、氢扩散时间及边界条件之间的关系.     

Rapid Hydrogen Transportation Along Grain Boundary in Nickel

The permeability and diffusivity of hydrogen in directionally solidified polycrystalline and single crystal nickel foils were measured by gas permeation method.The results showed that both hydrogen diffusivity and permeability were higher in directionally solidified nickel specimen than those in single crystal one at the temperature ranging from 300 to480 °C,and confirmed the existence of short-circuit diffusion along the grain boundaries(GBs) in the directionally solidified nickel.The results suggested that the rapid diffusion along GBs was more obviously characterized in terms of higher permeability rather than higher diffusivity.The contribution of grain boundary to hydrogen transportation was represented by the differences of diffusivity(and permeability) in single crystal nickel and directionally solidified nickel.By modifying the Fick's first diffusion law and counting the grain boundary density,the hydrogen diffusivity and permeability of rapid diffusion along GBs were calculated.The results suggested both the diffusivity and permeability fit the Arrhenius relationship well at different temperature.     

Characteristics of Diffusion Annealing Between Martensitic Stainless Steel and Nickel in the Form of Coating and Foil

Characteristics of interaction between martensitic stainless steel type AISI 410 with nickel in the form of coating layer and foil were investigated. Nickel was coated on AISI 410 substrate by electroplating in various thicknesses (6-16 μm). The 300-μm-nickel with purity of 99.9% was employed as a foil layer. All specimens were annealed in the temperature range of 700-900 °C for 5, 10, 15, and 60 min. Optical microscopy, SEM and EPMA analyzer were carried out in order to characterize the interdiffusion behavior differences between nickel and AISI 410 while using nickel layer in different form. It was observed that the thickness of nickel coating had a minor effect during annealing on the interaction between Ni and substrate at faying surface. However, the results show that the interaction of nickel coating layer with base material is much faster than foil layer during annealing process. This study suggests that the coating layer diffused faster to the substrate than foil layer; moreover, in the former case, heavy outer load was omitted. The concentration profiles were plotted for two cases. Although in case of using layer in the form of coating the annealing time was relatively short (5-15 min), it was observed that the concentration profiles for main elements had shapes close to the theoretical curve. For various thicknesses (6-16 μm) of Ni coating, the experimental results show that the interaction at faying surface caused the thickness of nickel coating growth. The diffusion zone width was plotted against the annealing temperature and time for both cases and the growth of the diffusion zones was compared.     

Quantitative evaluation of detection efficiency of the hydrogen microprint technique applied to steel

The detection efficiency of a hydrogen microprint technique (HMT) applied to steel specimens was examined experimentally. Amounts of hydrogen released from the specimen surface were measured by an electrochemical hydrogen permeation method, and the amounts were also evaluated by means of HMT under the same charging conditions as employed for the permeation test. Detection efficiency of conventional HMT was found to be as low as about 1%, but nickel plating of the steel surface was found to increase this efficiency remarkably. This high efficiency by nickel plating was achieved only when the relative humidity of an experimental atmosphere was controlled to 80% or higher. The thus-modified HMT showed a detection efficiency of about 40%.     

Al2O3/Au Composite Coating on Stainless Steel Prepared by Electro-deposition

Tritium permeation barriers on stainless steels are required in fusion technology in order to reduce the tritium permeation rate through the structural material into the cooling water system.Preparation of tritium permeation barrier Al2O3 is an important way to solve the problem of leakage of tritium permeation.It is worth to note that the noble Au is an excellent barrier of hydrogen dissolution.Al2O3/Au composite coating was designed for potential tritium permeation barrier on stainless steel.The alternation coatings have been prepared by electrochemical deposition method.The processing parameters and subsequent sinter temperature for composite coatings were optimized.The oxidation resistance of the coating has been tested.A hydrogen diffusion test simulating tritium permeation has been conducted to compare the sample with and without coating.Microstructure was examined by scanning electron microcopy(SEM).The results showed Al2O3/Au multi-alternation coatings can be prepared on the surface of stainless steel at the case of controlling processing well.The coatings have the characteristic of high temperature oxidation resistance and good hydrogen permeability barrier.The tritium permeation should be study further.     

Vermeidung der Wasserstoffversprödung vergüteter Stähle bei galvanotechnischen Prozessen durch thermische Legierungsbildung

Avoidance of hydrogen embrittlement of high strength steels during electroplating processes by thermal alloying Low alloyed high strength steels are often electroplated by metal layers protecting against corrosion. For ultra high strength, quenched and tempered steels with yield strengths > 1000 Nmm^?2 embrittlement by hydrogen being envolved during the electrochemical pretreatment as well as metal deposition has to be avoided. More over the corrosion protecting layers should form a diffusion barrier for hydrogen which can be formed during corrosion processes under special circumstances. In this paper two problem solutions including thermal alloying processes will be discussed. Plating the steel substrate with a nickel layer subsequently annealed at a temperature above 800°C in an inert gas atmosphere an austenitic iron-nickel-alloy at the boundary is formed, being a high efficient diffusion barrier for hydrogen. Further zinc plating is improving the corrosion resistance avoiding at the same time pitting corrosion problems. Plating the steel substrate with a copper and a following nickel layer on top and annealing it at the temperature of 800°C a highly corrosion resistant copper-nickel-alloy is formed showing excellent barrier behaviour for hydrogen diffusion. In both cases hydrogen being formed during the plating process itself and penetrating into the base metal does not lead to embrittlement as it is effusing during the annealing procedure.     

Einfluß der plastischen Verformung auf das Diffusions- und Löslichkeitsverhalten von Wasserstoff in Austenitischen Fe- und Ni-Basislegierungen

Influence of plastic deformation on the hydrogen diffusivity and solubility in austenitic Fe- and Ni-basic alloys The measurements of diffusivity and solubility were performed on as received and up to 50% cold worked high alloyed austenitic materials Inconel 600, Inconel 690, Incoloy 800 and AISI 321 by means of an electrochemical permeation method and a hydrogen determination technique (LECO RH 402). With increasing nickel content of the materials the hydrogen diffusivity increases whereas the activation energy of diffusion and the hydrogen solubility decrease. A marked change of the diffusion behaviour is observed in the case of cold worked samples depending on the alloy composition. An increase of diffusivity by about two orders of magnitudes was measured for AISI 321 as a result of α-martensite transformation. The cold working of the other alloys results in a decrease of the diffusivity by a factor of 2.7 maximally and a higher hydrogen content after effusion of the solved hydrogen. This refers to a higher hydrogen trapping. It is assumed that hydrogen atoms are trapped at the cores of dislocations and at microcracks formed during charging.     

Hydrogen embrittlement susceptibility and permeability of two ultra-high strength steels

Slow displacement rate tensile tests were carried out in a saturated H₂S solution to investigate the effect of hydrogen embrittlement on notched tensile strength (NTS) and fracture characteristics of two ultra-high strength steels (PH 13-8 Mo stainless steel and T-200 maraging steel). Hydrogen permeation properties were determined by an electrochemical permeation method. The results of permeation tests indicated that over-aged specimens showed a lower diffusivity/hydrogen flux and higher solubility than those solution-annealed. The great increase in reverted austenite (irreversible hydrogen traps) together with numerous precipitates at the expense of dislocations (reversible) in the over-aged specimen led to such a change in permeability. Ordinary tensile tests indicated that four tested specimens had roughly the same yield strength level. Hence, the hydrogen embrittlement susceptibility of the material could be related to their permeation properties. The uniform distribution of strong hydrogen traps in over-aged specimens instead of weak traps in the solution-annealed impeded the hydrogen transport toward the strained region, thus, the resistance to sulfide stress corrosion cracking was improved in over-aged specimens.     

Untersuchungen über den Einfluß des Zinks auf das Korrosionsverhalten von Spannstählen

Investigations on the influence of zinc on the corrosion behavior of high strength steels Corrosion and fracture behavior of hot dip galvanized high strength steels with and without damaging zinc layer was studied in deionized water, in tap water, and in saturated calcium hydroxide solution through which nitrogen, air, and carbon dioxide were bubbled separately. Hydrogen permeation measurements have been carried out for steel specimens which were cathodically polarized by means of the zinc layer. It has been observed that the hydrogen activity reached to a maximum of 1-2 in neutral solutions and 4-10 in saturated calcium hydroxide solution or in dilute acid solutions containing carbon dioxide, before decreasing to low values. The decrease of hydrogen activity is due to the formation of surface layers. Constant load tests by application of a load amounting to 100-110% yield strength caused no hydrogen induced brittle fracture within 300-400 h neither with nor without damaging zinc layer. At a constant strain rate of 5· 10^?7/s only 8 mm cold drawn steel wires were found to be almost unsusceptible to hydrogen that was absorbed during the test. Under notched conditions, all the steels investigated showed macroscopic brittle fracture.     

Comparison of corrosion-resistance and hydrogen permeation properties of Zn-Ni, Zn-Ni-Cd and Cd coatings on low-carbon steel

Zn-Ni-Cd alloy was electroplated from an alkaline sulfate bath under potentiostatic conditions. The corrosion and hydrogen permeation characteristics of Zn-Ni-Cd alloy coatings electrodeposited from alkaline bath were studied and compared with those of Cd and Zn-Ni coatings obtained using commercial baths. Zn-Ni-Cd alloy was electroplated from an alkaline sulfate bath under potentiostatic conditions. The corrosion potential of this Zn-Ni-Cd coating was −0.62 V vs. SCE, which is still negative potential compared to iron. The corrosion rate of Zn-Ni-Cd coated steel was 0.073 mm y⁻¹, which is estimated in a solution at a pH of 7. This value is much lower than the corrosion rate of Zn-Ni alloy (0.502 mm y⁻¹) and Cd (0.306 mm y⁻¹) coatings deposited from commercial baths. Zn-Ni-Cd alloys are also demonstrated to have superior hydrogen permeation inhibition properties compared to Cd and Zn-Ni coatings. Kinetic parameters of hydrogen permeation such as the transfer coefficient, α, the modified exchange current density, i₀^′, thickness dependent adsorption-absorption rate constant, k^″, recombination rate constant, k₃, surface hydrogen coverage, θ_s, were evaluated by applying a mathematical model to analyze experimental results.     

CO2对Pd8Y0.23Ru合金膜氢渗透性能的影响

在300~450℃范围内,研究氢中加入CO2对Pd8Y0.23Ru合金膜氢渗透性能的影响。结果表明,CO2的加入会大大降低膜的氢渗透率,CO2浓度越高,氢渗透率降低越多;CO2对Pd8Y0.23Ru合金膜存在一定的毒化作用,使氢渗透率下降,450℃下的毒化作用明显强于300℃,但随着时间的延长,渗透率降低速率趋缓。CO2降低氢渗透率还有另外2个因素:当CO2浓度较高(>3%,摩尔分数)时,聚集在膜表面附近的CO2对氢气传质的阻塞作用是氢渗透率降低的主要因素;当CO2浓度较低(<1%)时,CO2在膜表面吸附,占据氢的活性点位,是氢渗透率降低的主要因素。     

Hydrogen transport in austenitic stainless steel

The permeability, diffusivity, and solubility of hydrogen in austenitic stainless steels were determined by analysing the time-temperature dependence of deuterium flux through foil specimens. For a variety of such steels, the temperature dependence of these transport properties is given by: .These equations lie within the range of reported values. Much of the scatter between the results of previous investigators probably resulted from surface control of permeation. Surface effects were minimized in the current study; therefore, the above equations should approximate diffusion-controlled hydrogen transport.     

Hydrogen permeation in high strength steel under load in aqueous environment

Abstract

The hydrogen assisted cracking problem is one of the major causes of the failure occurring in the high strength steel structures used in various industries. In aqueous environment, hydrogen is generated by the hydrogen reduction reaction on the steel surface. With depletion of the high quality resources in oil and gas industry, the hydrogen assisted cracking problem becomes severe in sour environment, which contains high amount of H₂S. Understanding on the hydrogen permeation behaviour is crucial to deal properly with the hydrogen related problems since they are primarily determined by the hydrogen uptake and transport in the steel. The Devanathan–Stachurski method is widely used to evaluate electrochemically the hydrogen permeation behaviour. This method has been successfully used for the steel with no load. Under loading condition, this electrochemical test method has been modified to accommodate the externally applied load. However, the data require careful examination to validate the technical importance because of the stability and homogeneity of palladium layer coated on the steel surface under load. In this paper, the hydrogen permeation test method under loading condition will be reviewed for the high strength steels used in oil and gas industry. The factors affecting the hydrogen permeation in the high strength steel will be discussed in terms of the applied stress level and the sulphide film forming on the steel surface in sour environment.     

Untersuchungen zum Einfluß des Stahlgefüges auf die instationäre Wasserstoffpermeation

Investigations on the influence of microstructure of steels on unsteady state hydrogen permeation The effect of microstructure of iron and a low alloyed steel on hydrogen permeation at room temperature is studied by means of the electrochemical permeation method. Hydrogen transport through these materials during charging or effusion processes is affected by microstructural heterogeneities and hydrogen content. The diffusivity as a function of the state of the materials ranges over about five orders of magnitude. In course of non-steady state diffusion dislocations and interfaces decrease the effective diffusivity to values between 10⁻⁷ and 10⁻⁹ cm²/s. At steady state permeation the diffusivity reaches the values of 10⁻⁵ to 10⁻⁴ cm²/s.