The IGSCC, sensitization, and microstructure study of Alloys 600 and 690

Both Alloys 600 and 690 were studied to understand the effect of heat treatment on the sensitization and SCC behavior of these alloys. The microstructural evolution and chromium depletion near the grain boundaries were carefully studied using analytical electron microscopy. The majority of the precipitates formed in Alloy 600 was found to be M₇C₃ with a hexagonal structure (a₀ = 1.398 nm, c₀ = 0.45 nm); whereas the carbides found in Alloy 690 were identified as M₂₃C₆ with an fcc structure (a₀ = 1.06 nm). Modified Huey test performed in boiling 40% HNO₃ was used to study the effect of heat treatment and degree of sensitization. Constant load tests and constant extension rate tests were performed in the solution containing sodium thiosulfate to study the SCC resistance of these alloys. The results of the constant load tests for Alloy 600 indicated that the susceptibility to SCC is sensitive to the chromium depletion depth at grain boundary, and the minimum value to prevent SCC failure is approximately 8 wt%. No SCC was observed for Alloy 690 tested using constand load and CERT in the same environments. All tests showed that Alloy 690 has a far better resistance to intergranular attack and SCC than Alloy 600, which is believed due to its high chromium content. It is therefore anticipated that Alloy 690 now a better substitute to Alloy 600 as a steam generator tubing material for pressurized water reactor will also offer a superior corrosion resistance when “sensitized” and in particular if exposed to sulfur containing media such as thiosulfate solutions.     

Corrosion aspects of Ni-Cr-Fe based and Ni-Cu based steam generator tube materials

This paper reviews corrosion related issues of Ni-Cr-Fe based (in a general sense) and Ni-Cu based steam generator tube materials for nuclear power plants those have been dealt with for last more than four decades along with some updated information on corrosion research. The materials include austenitic stainless steels (SSs), Alloy 600, Monel 400, Alloy 800 and Alloy 690. Compatibility related issues of these alloys are briefly discussed along with the alloy chemistry and microstructure. For austenitic SSs, stress corrosion cracking (SCC) behaviour in high temperature aqueous environments is discussed. For Alloy 600, intergranular cracking in high temperature water including hydrogen-induced intergranular cracking is highlighted along with the interactions of material in various environments. In case of Monel 400, intergranular corrosion and pitting corrosion at ambient temperature and SCC behaviour at elevated temperature are briefly described. For Alloy 800, the discussion covers SCC behaviour, surface characterization and microstructural aspects of pitting, whereas hydrogen-related issues are also highlighted for Alloy 690.     

低浓去污预氧化过程中因科镍690合金我因科镍600合金的电化学 …

介绍了低浓去污预氧化过程中两种蒸汽发生器材料因科镍６９０合金及因科镍６００合金（下面简称６９０合金及６００合金）在不同邓氧化剂中脱膜效果（以铬的释放曲线表征）实验、腐蚀电位迁移测试和极化曲线测试。结果表明,６００合金在碱性高锰酸钾（ＡＰ）中的脱膜效果好于酸性高锰酸钾（ＮＰ）中,而６９０合金则在（ＮＰ）中的脱膜效果好于ＡＰ中。并且在ＮＰ中,随着硝酸浓度的增加,６００合金的腐蚀电位向正方向移动,６９０     

Effect of pH on corrosion behavior of CuCrZr in solution without and with NaCl

CuCrZr is a high copper alloy widely used as electrical and thermal conducting material, especially in heat exchangers in nuclear reactors. In this respect, the physical and fatigue properties of CuCrZr have been extensively studied. The electrochemical behavior of CuCrZr, on the other hand, has not been adequately investigated. In the present study, the effect of pH on the corrosion behavior of CuCrZr in aqueous solutions without and with chloride (0.6 M NaCl) was studied. The pH of the solutions is found to exert significant influence on the corrosion behavior of CuCrZr. In acidic solutions without chloride, the corrosion of CuCrZr is ascribed to active dissolution with soluble products. In neutral and alkaline solutions without NaCl, the presence of oxides on the surface of CuCrZr leads to a noble shift in corrosion potential and passivation results in increased corrosion resistance. In chloride solutions at various pH values, the chloride ions influence the formation of the surface layers and the anodic dissolution process during polarization. At high pH, CuCrZr shows significant passivity and high corrosion resistance due to the growth of Cu₂O/Cu(OH) film which hinders further dissolution whereas at low pH the corrosion resistance is lowered due to active dissolution of Cu.     

Decomposition pressures in the (α + β) fields of the Li-LiH,Li-LiD,and Li-LiT systems

Decomposition (“plateau”) pressures of H₂, D₂, and T₂ over Li-LiH, Li-LiD, and Li-LiT alloys were determined between 600 and 850°C, for pressures ranging from 3 to 460 Torr, and for alloy compositions falling within the (α + β) miscibility gaps. The measurements were carried out separately for each hydrogen isotope using the same lithium sample and experimental procedures. For each system the ln P vs. 1/T data form a pair of linear segments, the intersection of which represents the monotectic temperature (694°C for Li-LiH, 690°C for Li-LiD, and 688°C for Li-LiT). For a given temperature plateau pressures were in the order P_T2 >P_D2 >P_H2. The $\text{D}\text{H}$ and $\text{T}\text{H}$ isotope effects in pressures varied from 1.48 and 1.74 at 600°C to 1.34 and 1.45 at 850°C. The results were used to calculate the standard free energies of formation of solid LiH, LiD, and LiT. The tritium gas used in this study had significant amounts of hydrogen and deuterium. A method for correcting the plateau pressures of this mixture to those of pure tritium is presented.     

Effects of Hydrogen Peroxide on Intergranular Stress Corrosion Cracking of Stainless Steel in High Temperature Water, (III)

The stress corrosion cracking (SCC) of structural materials used in boiling water reactors has been studied at relatively low hydrogen peroxide (H₂O₂) concentrations, around lOppb, which was assumed to be representative of the corrosion environment formed in hydrogen water chemistry (HWC). The 1/4T compact tension specimen was used for measurement of crack growth rates (CGRs) of sensitized type 304 stainless steel in high temperature and high purity water. Crack length was monitored by a reversing direct current potential drop method. Since H2O2 is easily decomposed thermally, a polytetrafluoroethylene-lined autoclave was used to minimize its decomposition on the autoclave surface. The CGR in the H₂O₂ environment differed from that in the O₂ environment even though the electrochemical corrosion potential (ECP) for both conditions was the same. The data implied that the ECP could not be used as a common environmental deterministic parameter for SCC behavior at higher potentials for different oxidant conditions. The corrosion current density was found to play an important role as an environmental index for SCC, which was given as just the current density at the ECP at a specific oxidant concentration. The CGRs were found to be written as CGR = (3.8±0.6)xl0^-3 _icor +(l-5±1.6) x 10^-8mm/s using the calculated corrosion current density i_corbelow 10^-4 A-cm^-2.     

Microstructural Characterization of SCC Crack Tip and Oxide Film for SUS 316 Stainless Steel in Simulated PWR Primary Water at 320°C

Recent studies on stress corrosion cracking (SCC) behaviors of austenitic stainless steels in hydrogenated high-temperature water show that low potential SCC (LPSCC) can occur on cold-worked SUS 316 stainless steel (hereinafter, 316SS). In this study, oxide films and crack tips on cold-worked 316SS exposed to hydrogenated high-temperature water were characterized using analytical transmission electron microscopy (ATEM), grazing incidence X-ray diffraction (GIXRD) and Auger electron spectroscopy (AES) in order to study the corrosion and SCC behaviors of these films and crack tips. A double layer structure was identified for the oxide film after a constant extension rate tensile (CERT) test. The outer layer was composed of large particles (0.2–3 μm) of Fe₃O₄ and the inner layer consisted mainly of fine particles (~10 nm) of FeCr₂O₄. In addition, nickel enrichment was identified at the metal/oxide interface. Particles of Fe₃O₄ were also identified on the crack walls. These results indicate that the same electrochemical reactions had occurred inside and outside the crack. The crack tip area was filled with corrosion products of a chromium-rich oxide. In addition, nickel enrichment was observed at the crack tip. The formation of the nickel-enriched phase indicates that a selective dissolution reaction of iron and chromium occurred at the front of the LPSCC crack.     

Range profiles of medium and heavy ions implanted into SiO2

As, Cs, Xe, Eu and Yb have been implanted into SiO₂ in a typically 10–200 keV energy range. The implanted profiles were analysed using the Rutherford backscattering technique. The obtained projected ranges (R)_p) and projected range stragglings (ΔR_p) are compared with recent predictions due to Ziegler, Biersack and Littmark. While good agreement is obtained between the theoretical and experimental values of R_p, significant deviations are found for ΔR_p.     

The inhibiting effects of hydrogen on the corrosion of uranium dioxide under nuclear waste disposal conditions

A number of electrochemical experiments were employed to investigate the effects of hydrogen on the corrosion of UO₂ under nuclear waste disposal conditions. A combination of corrosion potential (E_CORR) measurements and cyclic voltammetry have indicated that dissolved hydrogen can polarize the UO₂ surface to reducing potentials; i.e., to E_CORR values more negative then those observed under anoxic (argon-purged) conditions. A comparison of the behaviours of SIMFUEL specimens with and without incorporated noble metal ε-particles indicates that these particles may act as catalytic electrodes for H₂ oxidation, H₂ ↔ 2e⁻ + 2H⁺. It is the galvanic coupling of these particles to the UO₂ matrix which suppresses the fuel corrosion potential.     

321-52M-690异种金属焊接接头的应力腐蚀开裂行为研究

采用慢应变速率拉伸(SSRT)和高温电化学相结合的方法,研究了外加电位对321-52M-690异种金属焊接接头在含Cl-高温高压水中应力腐蚀开裂(SCC)倾向的影响规律。结果表明,在300℃、50ppm Cl-环境下,焊接接头的SCC敏感性随电极电位(-700~+100mV)的升高而增大,且存在一个介于0~+50mV(vs.SHE)之间的临界电位Ecrit。当电极电位低于Ecrit时,焊接接头的SCC敏感性较小,SCC敏感性指数ISSRT基本在40%左右,断裂形式为外力主导的塑性开裂;当电极电位高于Ecrit时,ISSRT急剧增加至70%以上,断裂形式为腐蚀主导的脆性开裂。试样断裂位置均位于硬度最低的321母材处,表明在321/690异种金属焊接接头中321母材对SCC最为敏感,故进一步探讨了321不锈钢的应力腐蚀开裂行为和机理。     

Surface characteristics and electrochemical corrosion behavior of fluorinated diamond-like carbon (F-DLC) films on the NiTi alloys

Fluorinated diamond-like carbon (F-DLC) films with different CF₄ flux were deposited on polished NiTi alloys by plasma immersion ion implantation and deposition (PIIID). The results show CF_x bond is formed in the F-DLC films. With the increase of the CF₄ flux, the fluorine content and surface hydrophilicity of the F-DLC films are increased, while their sp³/sp² ratio and surface roughness are decreased. The F-DLC films improve the surface corrosion resistance of NiTi alloys, and the corrosion resistance of the F-DLC films on the NiTi alloys first increase and then decrease with increasing the CF₄ flux. Moreover, the relationship between the corrosion resistance and its structure and surface hydrophilicity of the F-DLC films is also clarified.     

Single electron capture in slow He2+-Li collisions

Optical measurements of single electron capture in He²⁺ -Li collisions are reported in the energy range 0.55–10keV/amu. These low energies were inaccessible in our earlier work on the same system [1].Cross sections for emission of the 1s?np (n = 2, 3, 4) Lyman series of He II have been measured with a VUV grazing incidence spectrometer. From these we have deduced the total capture cross section σ_t, and the subshell-selective capture cross sections σ_3p and σ_4p.Correction factors connected with the polarisation of the emitted radiation were applied to our data, using theoretical results of Fritsch and Lin [2], who calculated capture cross sections for nlm?states.Our results for σ_t, are in excellent agreement with very recent charge state selection measurements by Varghese et al. [3]. Both the total and the partial cross sections agree very well with theoretical results by Fritsch and Lin [2]. Comparison with other experimental and theoretical results is also made.     

Time-dependent corrosion product activity in a typical PWR due to changes in coolant chemistry for long-term fuel cycles

Extended fuel cycles with 18–24-month duration have complicated effects on primary coolant chemistry and finding optimum pH concentration range is difficult. For extended burnup cycles, study of changes in coolant activity due to corrosion products have been carried out for a typical pressurized water reactor (PWR) under pH and boric acid variations for linearly as well as nonlinearly accelerating corrosion rates. The computer program CPAIR-P (Deeba et al., 1999) has been modified to accommodate for time-dependent corrosion coupled with the effects of coolant chemistry. Results for ²⁴Na, ⁵⁶Mn, ⁵⁹Fe, ⁶⁰Co and ⁹⁹Mo show that the specific activity in primary loop approaches equilibrium value under normal operating conditions fairly rapidly. During reactor operation, predominant corrosion product activity is due to ⁵⁶Mn and after shutdown cobalt activity dominates. These simulations suggest that the effect of increase in pH value for an extended 24-month cycle on specific activity in the form of a decrease in the activity smeared by a linearly rising corrosion. The new saturation values for activity at the end of cycle are lower (∼50%) than a reactor operated at constant low pH/natural boric acid in coolant. For linearly accelerated corrosion and an increase in pH value, the coolant activity shows an initial rise and then it falls to a lower saturation level at the end of cycle when pH becomes large and the activity follows the slope of corrosion rate. For nonlinear rise in corrosion rate coupled with the pH rise from 6.9 to 7.4 and use of enriched boric acid (20%–40%) results in coolant activity peak during the cycle and it also approaches much smaller saturation values at the end of cycle when compared with the activity for the system having constant low pH value (6.9) in the coolant. In this paper we show that the use of enriched boric acid as chemical shim actually lowers the primary coolant activity when higher pH values are employed in coolant rather than natural boric acid. For multiple long-term fuel cycles the corrosion product activity shows an initial rise to a maximum value and then it fall back to low saturation values due to high pH concentration for enriched boric acid (40%) as chemical shim. If the removal rates of ion-exchanger are low (ε_IQ_I ∼100–300), then the activity builds up. However, when ion-exchanger performs well (ε_IQ_I ∼600–900) then the overall cobalt activity remains low and saturation value does not grow much with cycles.     

Compatibility between several heat resistant alloys and sintered Li2O in static helium gas environment

The reaction of sintered Li₂O discs with several commercial heat resistant alloys has been investigated under the conditions of 3.3 × 10⁴Pa ($\text{1}\text{3}\text{atm}$) static He gas atmosphere in the temperature range of 500 and 750° C. Reaction products were identified by X-ray diffraction analysis to be two phases of Li₅FeO₄ and LiCrO₂. The former was dominant below 650° C and the latter was dominant above 650° C. The activation energies of the reaction were determined by the Arrhenius plots for weight changes and sub-scale thickness measurements. The reactivity of the four Fe-Ni-Cr alloys decreased according to the order of Incoloy 800, 316 SS, Hastelloy X-R and Inconel 600. Grain boundary penetration was observed above 500° C for Incoloy 800, 550° C for 316 SS and 600° C for Inconel 600. There was no grain boundary penetration in Hastelloy X-R.     

热处理对690合金抗腐蚀性能影响综述

研究了热处理工艺对６９０使 为微组织及其抗腐蚀和应务腐蚀性能的影响。将国产６９０合金样品与国外同类产品作了对比分析。结果显示，国产样品显微组织已与国外同类产品基本相同；对应不同热处理工艺，合金的显微结构有很大区别沿晶界析出的碳化物大小、形貌也不同，抗腐蚀和应力腐蚀的性能存在明显差异。     

Corrosion characteristics of reduced activation ferritic steel, JLF-1 (8.92Cr–2W) in molten salts Flibe and Flinak

Static corrosion tests were performed in molten salts, LiF–BeF₂ (Flibe) and LiF–NaF–KF (Flinak), at 500 °C and 600 °C for 1000 h. The purpose is to investigate the corrosion characteristics of reduced activation ferritic steels, JLF-1 (8.92Cr–2W) in the fluids. The concentration of hydrogen fluoride (HF) in the fluids was measured by slurry pH titration method before and after the exposure. The HF concentration determined the fluoridation potential. The corrosion was mainly caused by dissolution of Fe and Cr into the fluids due to fluoridation and/or electrochemical corrosion. Carbon on the surface might be dissolved into the fluids due to the corrosion, and this resulted to the decrease of carbide on the surface. The corrosion depth of the JLF-1 specimen, which was obtained from the weight losses, was 0.637 μm in Flibe at 600 °C and 6.73 μm in Flinak at 600 °C.     

Inconel690在ETA/NH_3水化学环境中的均匀腐蚀行为研究

本文在模拟压水堆二回路的高温高压水化学环境下,研究了蒸汽发生器传热管材料镍基合金Inconel690试样在乙醇胺(ETA)和氨(NH3)水化学环境中的均匀腐蚀行为。结果显示:在5 000h均匀腐蚀试验后,ETA水化学环境下试样的均匀腐蚀速率为0.21mg/(m2·h),NH3水化学环境下试样的均匀腐蚀速率为0.50mg/(m2·h);在ETA水化学环境下试样表面形成的氧化膜中铬含量更高,氧化膜的保护性更好。以上结果表明,Inconel690在ETA水化学环境下的耐蚀性强于NH3水化学环境。     

热处理工艺对冷旋U-6.5Nb合金电化学腐蚀行为的影响

采用冷旋方法制备了管状U-6.5Nb合金零件,分别在400、600和700℃下对合金零件进行1h退火处理,考察了不同状态的U-6.5Nb合金在含50μg/gCl-的氯化钾水溶液中的电化学腐蚀行为,采用扫描电镜表征了腐蚀前后的形貌特征。结果表明：所有状态的合金均未发生钝化,冷旋态和700℃退火态合金为单相组织,具有较高的腐蚀电位和较小的腐蚀电流,400℃退火和600℃退火态合金为双相组织,具有较低的腐蚀电位和较大的腐蚀电流。单相合金比双相合金具有更好的抗腐蚀能力,但更易发生点蚀。双相合金表面Nb成分不均是其抗腐蚀性不佳的主要原因。     

Heat capacity of hydrogenated Zircaloy-2 and high Fe Zircaloy

Heat capacities (C_p) of non-hydrogenated and hydrogenated Zircaloy-2 and high Fe Zircaloy were measured in the temperature range from 350 to 873 K, using a differential scanning calorimeter. The hydrogen concentrations in the two types of alloys ranged from 26 to 1004 ppm. The C_p values of the as-received alloys with 26-29 ppm hydrogen were in good agreement with literature data for low hydrogen Zircaloys. From this finding and observation of almost the same enthalpy changes for hydride dissolution for both alloys, it was concluded that there was no difference in C_p values between the two types of hydrogenated Zircaloys. The dissolution enthalpy of hydrides calculated from C_p data was 41.0 kJ/g-atom H. For Zircaloy-2 samples with higher hydrogen concentrations than 700 ppm, the phase transition from α+δ to α+β was observed at the eutectoid temperature of 824-827 K. Two types of models describing an additional heat capacity due to the hydride dissolution were presented based on the present C_p data and previously derived terminal solid solubility of hydrogen.     

Range profiles of Ar implanted into C films

⁴⁰Ar implants with energies ranging from 10–200 keV into C films were profiled using the Rutherford backscattering technique. The obtained projected range (R_p) and projected range stragglings (σ_p) are compared with recent range-energy calculations. The analysis shows that the experimental R_p and σ_p values are respectively on average 20% and 25% larger than the predicted ones.