Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen I. Verhalten gegenüber wäßrigen Medien

Investigations into the corrosion behaviour of zirconium alloys I. Behaviour in the presence of aqueous media Extensive corrosion research covering 5O Zr alloys have shown that the good corrosion resistance of pure Zr cannot be improved to any greater extent by alloying. Pur Zr as well as most of its alloys have a high corrosion resistance; even in boiling mineral acids (20% H₂SO₄, HNO₃, and HCl) the corrosion rate is below 0.5 g/m²·d and no attack can be recognized in neutral salt solutions. The metal also resists attack by boiling 2O% KOH. Strong attack, however, it caused bv Fe-III-chloride. The metals do not resist attack by HF, while neutral KF attacks but little, however produces pitting. The effect of alloying additions is due to the structure produces by them: pure grain boundaries or very fine heterogeneous structures show good corrosion resistance. Ti, Hf, Sn and small amounts of Nb have little influence, Mo, W, larger amounts Nb and small pt and Re additions give rise to Local cells, while Fe, Cr and Ni have practically no influence.     

Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen. III. Untersuchungen an Zirkonium-Titan-Legierungen

Investigations into the corrosion behaviour of zirconium alloys III. Investigations on zirconium titanium alloys Investigations on zirconium alloys containing up to 4OO% titanium and, eventually, up to 10% Nb or Mo and small amounts of Fe, Ni and Cr (together 1.5% maximum) have revealed that titanium increases the dissolution power of zirconium for other alloying elements without tending to form two-phase structures. As to corrosion behaviour the better alloys are somewhat superior to other alloys. While titanium impairs the corrosion resistance of pure zirconium with respect to boiling mineral acids (20% HCl, sulphuric or nitric acids) titanium additions up to 10% of improve the corrosion behaviour of ZrNb and ZrMo alloys; alloys of the type Zr10Nb10Ti or Zr10Ti10Ta are comparable, with respect to the corrosion resistance, to pure zirconium. The scaling resistance of zirconium passes through a minimum at a five to ten percent Ti and arrives at its maximum value with 40% Ti. Further improvements may be obtained by addition of 10% Nb.     

Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen II. Verhalten bei Wasserdampfkorrosion

Investigation into the corrosion behaviour of zirconium alloys. 11. Behaviour under steam corrosion conditions An investigation into the corrosion behaviour of about 50 Zr alloys in high pressure high temperature steam (240 atm, 400°C) and hot air (4OO°C) has revealed a clear correlation between the behaviour in the two media. Alloys characterized by lower scaling susceptibility are also less susceptible to corrosion in steam, while, on the other hand, thicker scale layers tend to reduce hydrogen embrittlement. From the alloying additions studied Sn, Fe, Cr and Ni have a clearly favourable influence and W may have a similar effect. Ti has an outspoken negative influence on the behaviour in steam (spalling off of the scale) and Si, too, is deleterious because the SiO₂ being formed is soluble in steam, so that the scale layers retain their penetrability. Mo cannot be recommended either, while Nb is favourable in particular because of its grain refining effect. The favourable effect of Cu additions has been confirmed. Alloys with Fe, Cr and Ni and single types with Mo, Nb and Cu are superior to pure Zr with respect to steam resistance and are in part superior to Zircaloy 2 with respect to their mechanical strength.     

Die Oxydation von intermetallischen Zirkoniumlegierungen in Sauerstoff und Wasserdampf bei 400 °C

The oxidation of intermetallic zirconium alloys in oxygen and steam at 400°C The author has studied the oxidation behaviour of some intermetallic zirconium alloys in oxygen and steam. Depending on their behaviour the alloys can be divided into three categories:

• 1 Selective oxidation of alloying elements in the case of the alloys ZrAl₃ et ZrSi
• 2 Selective oxidation of Zr produced by rearrangement and enrichment of alloying elements in the case of Zr₄Sn, ZrCU₃ ZrNi, ZrV₂ and ZrMo_2/
• 3 Oxidation control by mixed oxides in the case of ZrNb and ZrTa

The mechanism of the corrosion of ZrAl₃ and ZrSi₂ in steam is interpreted in terms of the selective attack of Al and Si respectively.     

Untersuchung verschiedener Einflußgrößen bei der Korrosion von Zirkonium-Vanadium-Legierungen in Wasser und Wasserdampf

A study of various factors influencing the corrosion of zirconium/vanadium alloys in water and steam Experimental investigations in water and steam at saturation (250 to 350°C) with Zr and Zr alloys (0.5 to 0.7 and 2.5 to 3.9% V) have revealed, that it is advisable to use grinding for the surface preparation of the specimens (good reproducibility). The increase in weight is linear at 250 and 350°C, the oxide scale is removed by disintegration after some time; increasing amounts of V give rise to increasing corrosion rates. Between Zr sponge and iodide Zr there is no difference as to oxidation behaviour. The rate increase with increasing V additions is attributed to the poor resistance of ZrV₂ precipitated at grain boundaries and being also responsible for the poor adhesion of the oxide layer. In pure Zr, too, higher rates of corrosion are found when two phase (α + β) are present.     

Electrochemical behaviour of amorphous and nanoquasicrystalline Zr-Pd and Zr-Pt alloys in different environments

The corrosion behaviour of melt spun amorphous and nanoquasicrystalline Zr₇₀Pd₃₀ and Zr₈₀Pt₂₀ alloy ribbons has been investigated using potentiodynamic polarization study in NaCl, H₂SO₄ and NaOH solutions at different concentrations. The amorphous and nanoquasicrystalline alloys show better corrosion resistance than Zr in all the solutions studied. Both the alloys are susceptible to chloride attack and pitting has been observed. Complete passivation has been observed in H₂SO₄, while gradual break down of passivating layer occurs in NaOH. In general, nanoquasicrystalline state in both the alloys shows better corrosion resistance than amorphous state in all the solutions studied.     

Corrosion property of copperized layer on Zr formed by double glow plasma surface alloying technique

Zr and its alloys have excellent mechanical properties as new structural material,but in specific application environment,its corrosion resistance still needs to be further explored.In this work,double glow plasma surface alloying technique was used for copperizing on pure Zr surface.Besides,X-ray diffraction(XRD),scanning electron microscope(SEM) and energy dispersion spectrum(EDS) were employed to characterize the samples.Furthermore,research was also conducted on the polarization curve of the samples in different solutions.Copperizing on surface can improve corrosion resistance of pure Zr in 3.5 % Na Cl and 0.5 moláL-1Na OH solutions.Especially in 0.5 moláL-1Na OH solution,the corrosion resistance can achieve significant improvement.However,copperizing has no influence on the improvement of corrosion resistance of pure Zr in 0.5 moláL-1H2SO4 solution.The results may provide new insight into way for improving the corrosion property of zirconium alloys.     

Betrachtung zur Verbesserung der Zunderbeständigkeit von Zirkonium und Zirkoniumlegierungen

Some considerations concerning the improvement of the scaling resistance of zirconium and zirconium alloys Improving the scaling resistance of Zr and its alloys requires a reduction of gas solubility in the metal and an improvement of scale adhesion to the base metal. For this reason only such alloy additions are eligible which are either incorporated in the scale layer or form a ductile or molten alloy phase between the base metal and the ZrO₂, layer being formed. In this way one would on the one side prevent the scale layer from becoming porous (thus also eliminating the possibility of hydrogen diffusion into the base metal) while on the other hand the scale layer would be prevented from spalling off under shearing stress. These possibilities are discussed in terms of probable mechanisms for the action of alloying additions such as Sn and Al.     

Corrosion behavior of Zr–Nb–Cr cladding alloys

Zr-Nb-Cr alloys were used to evaluate the effects of alloying elements Nb and Cr on corrosion behavior of zirconium alloys. The microstructures of both Zr substrates and oxide films formed on zirconium alloys were characterized. Corrosion tests reveal that the corro- sion resistance of ZrxNb0.1Cr （x = 0.2, 0.5, 0.8, 1.1; wt%） alloys is first improved and then decreased with the increase of the Nb content. The best corrosion resistance can be obtained when the Nb concentration in the Zr matrix is nearly at the equilibrium solution, which is closely responsible for the formation of columnar oxide grains with protective characteristics. The Cr addition degrades the corrosion resistance of the Zrl.lNb alloy, which is ascribed to Zr（Cr,Fe,Nb）2 precipitates with a much larger size than β-Nb.     

Preliminary electrochemical testing of some Zr–Ti alloys in 0.9% NaCl solution

The aim of this study is to investigate the corrosion behaviour of three ZrTi alloys (denoted with Zr5Ti, Zr25Ti, and Zr45Ti) in 0.9% NaCl solution. For comparison, cp‐Ti was also investigated. In order to study the localized corrosion resistance and corrosion behavior at open circuit potential versus time, the open circuit potential (E_OC) was recorded, and the cyclic potentiodynamic polarization (CPP) and electrochemical impedance spectroscopy (EIS) were performed. Scanning electron microscopy (SEM) observations were made following the CPP tests. The Zr5Ti alloy was the most susceptible to localized corrosion. The Zr25Ti alloy presents a dangerous breakdown potential but have a sufficiently negative zero corrosion potential that the difference between them is sufficiently to provide a higher localized corrosion resistance in comparison with Zr5Ti. Among ZrTi alloys subjected to investigation, the Zr45Ti alloy had a much larger passive range in the polarization curve and was the most resistant to localized corrosion. For used test conditions, the localized corrosion was not found for the cp‐Ti. The EIS tests show that both investigated ZrTi alloys and cp‐Ti exhibit passivity after 168 h immersion in 0.9% NaCl solution, at open circuit potential.     

Korrosionseigenschaften laserstrahlgeschweißter Aluminium- und Magnesium-Automobilwerkstoffe

Corrosion behaviour of laser beam welded aluminium and magnesium alloys in the automotive industry The pitting behaviour of unwelded and laser beam welded AlMgSi alloys and an AlMgMn alloy was investigated. Electrochemical investigations and the metallographic determination of the pit volume were used to characterize the susceptibility to pitting corrosion. Both investigation methods showed that, in the unwelded condition, the material AlMgMn was the most resistant. In the case of laser beam welded materials, the resistance to pitting corrosion is lower or also higher than that of the non-affected materials depending on the material combination selected. The material combination AlMgSi0.5/AlMgSi1 F21 proved to be the most suitable. Magnesium extruded alloys with approx. 3 to 8% Al and 0.5 to 0.8 % Zn are susceptible to filiform corrosion and pitting corrosion in aqueous chloride solutions depending on chloride concentration. The resistance of unwelded alloys increases with Al content. On welding of the alloys, the corrosion resistance is determined by the Al/Mg proportion at the surface of the non-affected material and the laser welding seam. The pits occur mainly in the heat affected zone of the welding seam. The laser beam welded material AZ61 HP was found to have the highest resistance.     

Effect of chloride ions on electrochemical properties of anodized <Emphasis Type="Italic">AV</Emphasis> and <Emphasis Type="Italic">D</Emphasis>16 aluminum alloys in aqueous and glycerin-containing aqueous sodium sulfate solutions

The effect of chloride ions (0.01 N NaCl) on the electrochemical properties of anodized (in chromic anhydride or sulfuric acid) AV and D16 aluminum alloys in aqueous sulfate (0.5% Na₂SO₄) and glycerin-containing aqueous sulfate (0.5% Na₂SO₄, 33% glycerin) solutions is studied. Depending on the conditions of anodizing and the composition of the alloy and environment, currents on the anodized alloys in the passive range are shown to be smaller by one to four orders of magnitude compared to those on nonanodized alloys. Anodizing increases the resistance of alloys against pitting corrosion. Alloys anodized in sulfuric acid and then treated in dichromate are not susceptible to pitting corrosion. Alloys anodized in chromic anhydride are less resistant against pitting.     

Microstructure and corrosion behaviour of ferritic steel–Zr-based metal waste form alloys in simulated ground water

ABSTRACT

The microstructure and corrosion behaviour of the metal waste form (MWF) alloys based on ferritic steel with Zr content in the range of 3–15?wt-% were investigated. The MWF alloys are composed of α-Fe and Fe-Zr phases and with the increase of Zr content, α-Fe phase gradually decreases and the relative content of Fe–Zr intermetallic phase also increases. TEM and XRD confirmed the presence of Fe₂Zr and Fe₂₃Zr₆ intermetallics. Potentiodynamic polarisation curves showed The MWF alloys exhibited passivation behaviour in the simulated Kalpakkam (KGW) and Rajasthan ground water (RGW) media. Electrochemical impedance spectra revealed improved passive film stability in RGW than in KGW which is related to the formation of more stable adherent insoluble passive film in RGW. Higher Zr containing MWF alloy exhibited higher corrosion resistance than lower Zr containing MWF alloys. The relative content of Fe–Zr intermetallics is attributed for the corrosion resistance of The MWF alloys.     

Die Lochkorrosionsbegrenzung bei hochlegierten Sonderedelstählen und NiCrMo‐Legierungen in Chloridlösung – Einflußfaktoren und Ausmaß

Limit of pitting corrosion at high‐alloyed special steels and NiCrMo alloys in chloride solution The phenomenon of the limit of pitting corrosion in direction to positive potentials is studied by potentiokinetic polarization after a jump in the transpassive range and by potentiostatic tests at technical wrought materials and at model alloys of the systems NiCrMo and NiMo in CaCl₂ solution in the concentration range 1 to 9 mol/l chloride at pH‐values of 1 to 9 at temperatures of 30 to 110°C. Surface‐analytical investigations gives in connection with knowledges from anodic polarization studies directions to the mechanism of the limit of pitting corrosion. Ranges of the limit of pitting corrosion are obtained at materials with a Mo content above 6.5% and contents of chloride of the media above 2 mol/l chloride. Increasing temperatures, increasing contents of chloride and sulfate shift the potential of the limit of pitting corrosion being always above 0.2 V (SCE) at potentiostatic determination to noble direction. There are indications that the mechanisms of limit of pitting corrosion is resulting from an inactivation of pitting nuclei by the formation of hardly soluble molybdenum chlorides in the potential range of limit of pitting corrosion.     

Untersuchungen zur Korrosion von metallischen Werkstoffen in hochkonzentrierten,siedenden Salzlösungen

Investigations into corrosion of metallic materials in highly concentrated boiling salt solutions Container for the disposal of radioactive waste in carnallite formations can be exposed to corrosion by highly concentrated hot salt solutions. Previous investigations of the corrosion resistance of candidate materials have been supplemented by measurements of the current density-potential curves of iron-silicon, cobalt-silicon, titanium-nickel and nickel-molybdenum alloys and of tantal. The electrolyte was a concentrated MgCl₂-NaCl-KCl-MgSO₄ solution at its boiling point of 170°C. The measurements give useful information on the stability of the corrosion resistance of these materials.     

Influence of nickel additions on the corrosion behaviour of low nitrogen 22% Cr series duplex stainless steels

Four 22% Cr duplex stainless steel alloys containing varying nickel contents of approximately 5%, 7%, 9% and 13% were melted in a vacuum induction furnace, hot rolled, solution annealed and water quenched. Their corrosion behaviour was investigated in sulphuric acid and sodium chloride solutions using potentiodynamic polarization and chronoamperometric techniques. Increasing nickel contents have an appreciable influence on the observed corrosion behaviour. Polarization curves show similarities in the uniform corrosion behaviour of the alloys in the various solutions, but significant differences in their pitting resistance in chloride environments. Alloy 2209 (22% Cr - 9% Ni) generally exhibited the highest resistance to uniform corrosion, while alloy 2213 (22% Cr - 13% Ni) displayed the best pitting corrosion resistance. X-ray diffraction analysis of the surfaces of the alloys after corrosion in the different media revealed different corrosion products. Scanning electron micrographs revealed that the alloys were differently attacked by chloride ions, with different pit depths and morphologies. The corrosion behaviour exhibited by the alloys was attributed to the influence of nickel on phase modification, microstructural refinement, and the types of films formed in different environments. Uniform corrosion behaviour of the alloys was concluded to be predominantly controlled by phase composition and ratio, while pitting resistance was chiefly controlled by an alloy’s nickel contents.     

An electrochemical study on the effect of pitting inhibition in weakly alkaline solution by copper addition in pure iron

The effects of copper on the corrosion rafe of steel have been investigated in order to propose the application of scraps as material of reinforcing steels in concrete structures. The corrosion behaviors of pure iron and several Fe−Cu alloys were examined by conducting potentio-dynamic and galvanostatic polarization in pH 10, 12.5 and 13.5 Ca(OH)₂ solutions added to several chloride concentrations. Values of the pitting potential (E _p) of pure iron were plotted at negative potential. In contrast to pure iron, theE _p values of Fe−Cu alloys showed much more positive values. The polarization curves in weakly alkaline solutions containing chloride ions indicated that the addition of copper up to 3 mass% significantly improved the corrosion resistance of steel.     

Corrosion Behavior of Novel Al-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Composites in Aerated 3.5% Chloride Solution

The corrosion behavior of novel Al-Al₂O₃ MMCs was evaluated in aerated 3.5% NaCl solution through potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). These materials corrode almost spontaneously by pitting in aerated 3.5% NaCl solution. Observations indicate that intermetallic particles in these composites appear to play an important role in this pitting corrosion behavior. Addition of Al₂O₃ particles to the base alloys did not appear to increase their corrosion resistance significantly, although corrosion rate was affected by these reinforcement particles. In cyclic polarization experiments, the small difference between the pitting potentials and the repassivation potentials for these MMCs indicated their low resistance to pitting corrosion. EIS measurements indicate adsorption/diffusion phenomena at the interface of the composites. Electrically equivalent circuits are proposed to describe and substantiate the corrosion processes occurring in these materials.     

Modelling the corrosion behaviour of Al2CuMg coarse particles in copper-rich aluminium alloys

The corrosion behaviour of 2024 aluminium alloy in sulphate solutions was studied; attention was focused on the influence of coarse intermetallic Al₂CuMg particles on the corrosion resistance of the alloy. Model alloys representative of the aluminium matrix and of Al₂CuMg coarse intermetallics were synthesized by magnetron sputtering. Open-circuit potential measurements, current-potential curve plotting and galvanic coupling tests were performed in sulphate solutions with or without chlorides. Further explanations were deduced from the study of the passive films grown on model alloys in sulphate solutions. The results showed that model alloys are a powerful tool to study the corrosion behaviour of aluminium alloys.     

Pitting,Crevice and stress corrosion resistance of high chromium und molybdenum alloy stainless steels

This paper presents new data on the resistance of recently developed high-alloy stainless steels to localised corrosion in chloride solutions. Pitting potential was determined in artificial sea water, and critical pitting temperature CPT in very aggressive FeCl₃ solution. Critical crevice corrosion temperature CCT was tested in the same FeCl₃ solution. Stress corrosion measurements, made in a more familiar NaCl solution by the drop evaporation method, demonstrate that alloy stainless steels with high chromium and molybdenum have very long failure times, comparable with those of nickel alloys found to be SCC-resistant under practical conditions. Stainless steels of 20 Cr 25 Ni 6 Mo type showed the best resistance to localised corrosion.