Evaluation of hydrogen absorption properties of Ti–0.2 mass% Pd alloy in fluoride solutions

The hydrogen absorption properties of Ti–0.2 mass% Pd (Ti–0.2Pd) alloy in 2.0% and 0.2% acidulated phosphate fluoride (APF) and neutral 2.0% NaF solutions (25 °C) has been evaluated by hydrogen thermal desorption analysis. During the early stage of immersion (120 h) in the 2.0% APF solution, the amount of absorbed hydrogen was lower than 500 mass ppm. A thermal desorption of hydrogen primary appearing with a peak at 500–600 °C and a broad desorption ranging from 100 to 400 °C were observed. In the 0.2% APF solution, the amount of absorbed hydrogen saturated at 100–200 mass ppm; the thermal desorption of hydrogen appeared with a single peak at 550 °C. In the 2.0% NaF solution, hydrogen absorption was negligible even after 1000 h of immersion, although corrosion pits were observed. The results of the present study suggest that the hydrogen absorption of Ti–0.2Pd alloy, as compared with commercial pure titanium, is suppressed in fluoride solutions.     

Corrosion and hydrogen absorption of commercially pure zirconium in acid fluoride solutions

The corrosion and hydrogen absorption of commercially pure zirconium have been investigated in acidulated phosphate fluoride (APF) solutions. Upon immersion in 2.0% APF solution of pH 5.0 at 25 °C, a granular corrosion product (Na₃ZrF₇) deposits over the entire side surface of the specimen, thereby inhibiting further corrosion. In 0.2% APF solution, marked corrosion is observed from the early stage of immersion; no deposition of the corrosion product is observed by scanning electron microscopy. A substantial amount of hydrogen absorption is confirmed in both APF solutions by hydrogen thermal desorption analysis. The amount of absorbed hydrogen of the specimen immersed in the 2.0% APF solution is smaller than that in the 0.2% APF solution in the early stage of immersion. The hydrogen absorption behavior is not always consistent with the corrosion behavior. Hydrogen thermal desorption occurs in the temperature range of 300–700 °C for the specimen without the corrosion product. Under the same immersion conditions, the amount of absorbed hydrogen in commercially pure zirconium is smaller than that in commercially pure titanium as reported previously. The present results suggest that commercially pure zirconium, compared with commercially pure titanium, is highly resistant to hydrogen absorption, although corrosion occurs in fluoride solutions.     

Effects of acid type on corrosion and fracture behavior of Ni-Ti superelastic alloy under sustained tensile load in physiological saline solution containing hydrogen peroxide

The effects of acid on the corrosion and fracture behavior of Ni-Ti superelastic alloy have been examined by sustained tensile-loading test in physiological saline solution containing hydrogen peroxide. For immersion test without applied stress at the same solution pH, although corrosion is enhanced markedly irrespective of the type of acid added, corrosion morphology depends on the type of acid added. The amount of dissolved nickel ions increases in the order of the solutions with lactic acid > phosphoric acid > acetic acid. The amount of dissolved nickel ions increases with decreasing solution pH. In contrast, under applied stress, the time to fracture in the solution with phosphoric acid becomes longer than that in the solution without acid, although the time to fracture does not increase in the solution with acetic acid or lactic acid. The time to fracture is only slightly affected by solution pH for the same type of acid added. Fractographic features change in the solution with phosphoric acid. The present study suggests that the fracture behavior of Ni-Ti superelastic alloy in physiological saline solution containing hydrogen peroxide depends on acid type rather than on solution pH; the fracture behavior is not necessarily consistent with the corrosion behavior in the case without applied stress.     

Effects of nonhalide anions on the stress corrosion cracking behaviour of alloy 7475 in the tempers T651 and T7351

The stress corrosion cracking behaviour of 7475 plate material in the tempers T651 and T7351 was investigated performing constant load tests. Short transverse specimens were permanently immersed in aerated aqueous 0.6 M sodium chloride solutions with additions of 0.03 M sodium sulphate, 0.03 M sodium nitrate and 0.1 M sodium bicarbonate. Chloride solutions containing sulphate, nitrate or/and bicarbonate promoted environment‐induced cracking. A short transverse threshold stress below 50 MPa was found for 7475‐T651 plate material. Neutral 0.6 M NaCl solution was less conducive to stress corrosion cracking. Specimens of alloy 7475 in the overaged temper T7351 failed at applied stresses above 300 MPa. This failure resulted from overload fracture caused by a reduction of cross‐sectional area due to pitting corrosion, as confirmed by fractography showing severe pitting attack. Fractographic examinations of 7475‐T7351 specimens failed during immersion in chloride‐nitrate‐bicarbonate containing solutions with or without addition of sulphate after long exposure time periods revealed slight transgranular stress corrosion cracking, too. Pronounced transgranular environment‐induced cracking was observed on the fracture surfaces of specimens which were exposed to an aqueous solution containing chloride, sulphate, nitrate, and bicarbonate for 30 days at applied stress and were subsequently tensile tested in an inert environment.     

固溶冷却方式对TB15钛合金组织和力学性能的影响

采用扫描电镜观察、拉伸和断裂韧性测试研究了不同固溶冷却方式下TB15钛合金经900 ℃×2 h固溶+530 ℃×8 h时效后的力学性能、断口形貌和显微组织。结果表明,固溶冷却方式对TB15钛合金强度和塑性的影响较大,对断裂韧性的影响较小。固溶后回充0.1 MPa氩气真空气冷时,合金的综合力学性能最好,抗拉强度为1391 MPa,伸长率为7.0%,断面收缩率为13.6%,断裂韧度为70.3 MPa·m^1/2。随着固溶冷却速率的增加,TB15钛合金的断裂韧度逐渐减小,但变化幅度不大。不同固溶冷却方式下,TB15钛合金经固溶时效后的次生α相数量、厚度及片层间距有所不同。与空冷相比,回充0.1 MPa氩气真空气冷的片层状次生α相数量增多,厚度略有增加,片层间距有所增大。     

环境湿度及氢气压力对U-2.5%Nb合金拉伸性能的影响

研究了U-2.5%Nb合金(质量分数,下同)在相对湿度分别为3.5%、50%、100%、水浸、热水和水蒸气环境,氢气压力分别在0.4,1.0,2.0MPa条件下的拉伸性能及断口形貌。结果表明:拉伸速率在3×10-5/s时,随环境湿度及氢气压力的增加,U-2.5%Nb合金的抗拉强度降低,规定非比例延伸强度增加,塑性急剧下降。同样在水浸环境,3×10-5/s与1×10-4/s的拉伸速率相比,U-2.5%Nb合金断后伸长率下降约84%,断面收缩率下降约79%。拉伸速率在3×10-5/s时,合金在2.0与0.4MPa的氢气压力相比,断后伸长率下降约20%,断面收缩率下降约13%。在相对湿度3.5%的环境下,U-2.5%Nb合金试样断口边缘呈韧窝状,有一定的韧性特征。在水浸环境下,试样断口边缘韧窝明显减少,有一定的脆断特征。在水蒸气环境中,试样断口边缘有明显的解理脆断特征。在氢气环境中,试样断口的脆断特征随氢气压力的增加而增强。     

氟化处理对植入材料Mg-Ca二元合金腐蚀行为的影响(英文)

在室温下,将Mg-0.5Ca合金在不同浓度的氢氧化钠和HF溶液浸渍不同的时间,研究HF处理对合金腐蚀行为的影响。采用原子力显微镜、X射线衍射、场发射扫描电子显微镜表征样品的微观组织变化。通过动电位极化和Kokubo溶液浸泡试验测试样品的耐腐蚀性。结果表明,与35%HF处理的样品相比,经40%HF溶液处理的Mg-0.5Ca合金具有更均匀、更致密、更薄的涂层(12.6μm)。电化学测试表明,在Kokubo溶液中,经氟化物处理的Mg-0.5Ca合金样品的耐腐蚀性比未处理样品的高35倍;前者的体外降解速率远远低于后者的。在40%HF溶液处理过的样品表面只出现了一些腐蚀点,而未经处理的样品完全被腐蚀产物覆盖且出现了分层现象。40%HF处理的Mg-0.5Ca合金,具有低的降解速率和良好的生物相容性,是一种有潜力的植入材料。     

Hydrogen induced stress corrosion cracking in low and high strength ferritic steels of different phosphorus content in acid media

Hydrogen induced stress corrosion cracking (HSCC) resistance and mode of fracture in various low and high strength steels (yield strength 120 to 960 MPa) and containing different levels of phosphorus content were studied using constant extension rate test method in various acid media viz. sulphuric acid solutions under cathodic polarisation, hydrogen sulphide saturated solutions of sodium chloride + acetic acid (NACE solution) and synthetic sea water (BP solution). In case of low strength steels (yield strength 120–265 MPa), the HSCC susceptibility in sulphuric acid increased with phosphorus content and became very high irrespective of phosphorus content in hydrogen sulphide saturated solutions. The susceptibility was directly related to different hydrogen activities measured in these solutions. No significant dependence of HSCC susceptibility on the phosphorus segregation as high as 20 atom % at the grain boundaries was found and the fracture mode was always transgranular. In contrast, a similar segregation of phosphorus in high strength steels (yield strength 875–960 MPa) caused a reduction in HSCC resistance and changed the fracture mode to intergranular.     

Stress corrosion crack propagation in a TiO alloy in aqueous and methanolic solutions

Stress corrosion crack propagation in a TiO alloy in aqueous NaCl and MeOH/HCl solutions has been examined in dynamic straining experiments. Crack velocity is determined by the value of the applied strain-rate. In aqueous solutions repassivation and crack arrest occur if the strain-rate falls below a certain value, designated s,. Embrittlement tests under either open circuit conditions or with applied anodic currents in Me0H/HCl solution result in 3-zone fractures: intergranular, caused by dissolution, transgranular cleavage, caused by absorbed hydrogen, and ductile fracture. The intermediate cleavage zone disappears if specimens are aged before fracture or if the intergranular dissolution rate is raised until it becomes comparable to the rate of hydrogen diffusion. Interrupted dynamic straining tests with periodic removal of solution indicated that an embrittling process occurs in stressed specimens after removal of the solution. Additions to the solutions that promote hydrogen entry into the metal increased the crack velocity while the addition of species that inhibit hydrogen entry lowered the crack velocity. Increasing the corrosion rate was shown to result either in a reduced crack velocity or an increased crack velocity, depending upon the presence in the solution of a species inhibiting hydrogen entry. It is concluded that intergranular cracking in McOH/HCl solutions occurs as a result of anodic dissolution while the transgranular cleavage observed in both aqueous and methanolic solutions is a form of slow strain-rate hydrogen embrittlement.     

固溶处理对Al-8.8Zn-2.0Mg-2.1Cu-0.1Zr-0.1Ce合金组织性能的影响

采用拉伸性能和导电率测试、光学显微镜(OM)、扫描电镜(SEM)、差热分析(DSC)、透射电镜(TEM)研究了固溶温度和时间对Al-8.8Zn-2.0Mg-2.1Cu-0.1Zr-0.1Ce合金板材微观组织、拉伸性能及断口形貌的影响。结果表明,试验合金适宜的固溶工艺为470 ℃×60 min,使冷轧态金属间化合物充分固溶。在此工艺下合金时效后的抗拉强度、屈服强度(以R_p0.2计)以及伸长率分别为646 MPa、581 MPa和14.5%。TEM观察发现合金板材固溶时效后晶内强化相η′仅为2~5 nm,并且晶界析出相η呈现断续分布。此外,合金拉伸断面韧窝中大量弥散分布的AlCuCeZn粒子有利于合金塑性的明显提升。     

Evaluation of susceptibility of high strength steels to delayed fracture by using cyclic corrosion test and slow strain rate test

To evaluate susceptibilities of high strength steels to delayed fracture, slow strain rate tests (SSRT) of notched bar specimens of AISI 4135 with tensile strengths of 1300 and 1500 MPa and boron-bearing steel with 1300 MPa have been performed after cyclic corrosion test (CCT). During SSRT the humidity around the specimen was kept high to keep absorbed diffusible hydrogen. The fracture stresses of AISI 4135 steels decreased with increment of diffusible hydrogen content which increased with CCT cycles. Their delayed fracture susceptibilities could be successfully evaluated in consideration of both influence of hydrogen content on mechanical property and hydrogen entry.     

稀土Y元素对铸态镁合金组织与力学性能的影响

采用熔炼工艺制备了Mg-2.0Zn-0.2Ca与Mg-2.0Zn-0.2Ca-2Y合金,研究了两种合金的铸态组织及力学性能。结果表明,Y元素的添加细化了Mg-2.0Zn-0.2C合金的铸态组织。Mg-2.0Zn-0.2Ca合金主要由α-Mg与少量Mg₇Zn₃相组成,添加2wt%的Y后,改变了Zn在Mg基体中的固溶度,降低了其固溶强化效果,同时组织中形成了I相和W相。添加Y元素后,合金的规定塑性延伸强度升高,从41.0 MPa升高到50.6 MPa;伸长率降低,从12.6%降低到4.0%。     

TiNi形状记忆合金的氢致滞后断裂

用单边缺口拉伸试样研究了TiNi形状记忆合金在恒载荷下动态充氢时的滞后断裂过程，以及原子氢、氢致马氏体和氢化物在氢致滞后断裂中所起的作用，结果表明，TiNi合金能发生氢致滞后断裂，归一化门槛应力强度因子随总氢浓度对数的增加而线性下降，即KIH/KIC=2.01-0.25lnCT。在恒载荷动态充氢时氢化物含量不断升高，材料的断裂韧性不断下降，这是氢致滞后断裂的主要原因；而原子氢和氢致马氏体在氢致滞后断裂中所起的作用则极小。     

Wasserstoffinduzierte Spannungsrißkorrosion an unverzinkten und verzinkten Baustählen

Hydrogen induced stress corrosion cracking of non galvanized and galvanized construction steels The processes of atmospheric corrosion and corrosion in collected water which may lead to hydrogen induced stress corrosion cracking of high-strength reinforcing steels in casing tubes before injection with concrete are discussed. Hydrogen uptake during corrosion occurs in weakly acid solutions as well as in neutral or alkaline aqueous solutions. The hydrogen uptake by proton discharge in acid solutions decreases with increasing pH of the electrolyte. Hydrogen can also be absorbed in neutral to weakly alkaline solutions if steels are plastically deformed and water reacts with the fresh iron surface. In alkaline solutions, hydrogen uptake is possible if, at the generally passivated steel surface, localized corrosion (pitting or crevice corrosion), local galvanic cells and a sufficient decrease in the pH of the pit electrolyte occurs. In the case of galvanized steels with damaged zinc layers, hydrogen uptake may result from the cathodic polarization of the free steel surface by zinc dissolution. The absorbed hydrogen interacts with the microstructure of the steels and weakens the bonds between the iron atoms. The influence of the microstructure of high-strength steels on the fracture behaviour is discussed on the basic of the so-called decohesion theory.     

纳米晶Mg2-xTixNi0.8Cr0.2四元合金的气态储氢性能

纳米晶Mg2-xTixNi0.8Cr0.2(x=0.05,0.10,0.15,0.20)四元合金由纯Mg,Ti,Ni,Cr粉在773 K经4h烧结后机械球磨而成.该合金具有良好的活化性能和吸氢动力学性能.合金在393 K,4.0 MPa氢压条件下,2min内便可以完成总吸氢量的75%(质量分数)以上,Mg1.95Ti0.05Ni0.8C0.2最大吸氢量可达到3.35%.在493 K,0.1 MPa条件下可快速放氢,Mg1.80Ti0.20Ni0.8Cr0.2在18 min内便可完成放氢过程,总放氢量为2.17%.所有合金具有良好的低温吸氢性能,353 K时Mg1.85Ti0.15Ni0.8Cr0.2合金最大吸氢量可达到2.08%.XRD分析结果显示,Ti替代Mg后,合金中主要存在Mg2Ni与Ni两相,另外,还有微量的Mg与TiNi相,TiNi相弥散分布在合金中,对合金的吸放氢性能有一定的催化作用.     

固溶处理对TC11钛合金组织与性能的影响

通过光学显微镜、扫描电镜、X射线衍射仪以及室温拉伸性能测试,研究TC11钛合金分别在955、975、995和1015℃固溶处理后的微观组织与力学性能的对应关系。结果表明,合金原始锻态显微组织为α+β两相区锻造形成的双态组织,以α_p相和β转变组织为主。经固溶处理后,原始锻态组织中被扭转和拉长的α_p相随着固溶温度升高逐渐变小、变圆,同时体积较小的α_p相逐渐消失。固溶温度为995℃时,合金强度达到最大值,抗拉强度(R_m)为1403 MPa,屈服强度(R_p0.2)为1158 MPa;固溶温度为955℃时,合金塑性最佳,断后伸长率(A)为9.5%,断面收缩率(Z)为32%。当固溶温度位于两相区时,其拉伸断口微观形貌相似,均以韧窝为主;当固溶温度位于单相区时,断口形貌结晶状明显,且有较大的撕裂棱,在岩石状表面有大量撕裂状小韧窝。     

Anion effects on the stress corrosion cracking behaviour of aluminium alloys

The stress corrosion cracking behaviour of plate material of the aluminium alloys 2024‐T351, 8090‐T8171, 7475‐T651, and 7075‐T7351 was investigated performing constant load tests. Short transverse tensile specimens were permanently immersed in aerated aqueous 0.6 M Na₂Cl solutions with additions of Na₂SO₄, NaNO₃, NaHCO₃, NH₄HCO₃, Na₂HPO₄, Na₂SO₃ or Na₂CO₃. The concentration of the added salts was 0.06 M. The applied stress was 100 MPa, except with 7075‐T7351 specimens, which were loaded at 300 MPa. Environment induced failure was not observed in neutral 0.6 M NaCl solution. The various salts added promoted intergranular stress corrosion cracking with the alloys 2024‐T351, 8090‐T8171, and 7475‐T651. Threshold stresses were generally below 100 MPa. For 8090‐T8171 exposed to chloride containing electrolytes with additions of sulfate, hydrogen phosphate, or sulfite, threshold stresses were approximately 100 MPa or higher. Similar results were obtained for 7475‐T651 plate when immersed in chloride‐hydrogen phosphate and chloride‐carbonate solutions. Alloy 7075‐T7351 was resistant against intergranular stress corrosion cracking. Specimens suffered pitting corrosion during immersion in the corrosive environments. Failure observed with 7075‐T7351, in particular when exposed to the chloride‐nitrate solution, was associated with reduction of cross‐sectional area due to pitting and transgranular stress corrosion cracking.     

氢致TA10钛合金焊接接头拉伸性能演变

钛合金焊接件低氢浓度下常发生氢脆失效,文中研究了充氢量对钛合金焊接接头拉伸性能的影响规律及其作用机制. 结果表明,随充氢量增加,室温强度明显提升,而塑性指标显著恶化. 充氢0.05% (质量分数)时,固溶氢对组织强化效果有限,抗拉强度略有增加;固溶氢降低了溶质原子对位错运动“钉扎”作用,屈服强度下降;固溶氢仅依靠扩散聚集,致局部微区氢浓度增加,其对塑性影响不大. 充氢0.12%后,氢化物“钉扎”作用加强,氢致位错交叉滑移更为困难,室温强度显著增加;脆性氢化物自身断裂、析出特征或加速与基体分离,致塑性显著下降. 未充氢或0.05% H时,焊接接头发生韧性断裂;充氢0.12%后,以脆性断裂为主;固溶氢、氢化物对断裂方式转变产生直接影响.     

镁合金阳极氧化膜在NaCl溶液中的腐蚀行为

利用盐水浸泡实验研究了AZ91D镁合金阳极氧化膜层在3．5％NaCl溶液中的腐蚀行为。结果表明：AZ91D镁合金阳极氧化膜层不论封闭与否,在中性NaCl溶液中浸泡出现第一个腐蚀点后,膜层表面均很少再出现新的腐蚀点,而是原有的腐蚀点向纵、横两个方向扩展形成腐蚀坑,表面呈“树枝”状腐蚀形貌;浸泡溶液的pH值对阳极氧化膜层的耐蚀性影响很大,酸性溶液中的腐蚀速率明显大于中、碱性溶液的;随浸泡溶液温度的升高阳极氧化膜层的腐蚀速率加快。据此,提出了AZ91D镁合金阳极氧化膜层在NaCl溶液中腐蚀过程的模型。     

Mechanical properties and corrosion behaviors of Mg−4Zn−0.2Mn−0.2Ca alloy after long term in vitro degradation

An extruded Mg−4Zn−0.2Mn−0.2Ca alloy was developed as potential biodegradable bone-plate due to its excellent biocompatibility. Long term in vitro immersion in Hank's solution and bending test were used to evaluate the degradability and the mechanical integrity of the alloy. The results revealed that the degradation rate of the bone-plate increased in the first 7 days and then decreased with the prolonged immersion time before it finally reached a steady stage (about 0.84 mm/a) after immersion for 90 days. The bending strength after immersion for 60 days was 67.6 MPa, indicating that the bone-plate could support certain mechanical load after long term degradation. The formation of corrosion pits after degradation stemmed from the separation of the continuously distributed second phases from Mg matrix under the action of micro-galvanic couples. As a result, the mechanical performance of Mg−4Zn−0.2Mn−0.2Ca alloy was aggravated owing to the corrosion holes on its surface.