容错事故燃料包壳用FeCrAl合金的研究进展EI北大核心CSCD

福岛事故后,人们迫切需要开发相应的燃料包壳材料以忍受严重事故发生时的极端工况,从而提高核电站的事故承受能力。尽管FeCrAl合金的宏观中子吸收截面要远远高于锆合金,但其在严重事故下良好的耐腐蚀性、优越的高温力学性能及抗辐照损伤能力,使其被列为事故容错燃料包壳的候选材料之一。然而,现有FeCrAl合金难以满足核电站用材料的要求,因此需对其进行优化,以获得更佳的性能。本文系统总结了近年来关于优化后FeCrAl合金的腐蚀行为、力学性能、辐照后的微观结构及力学性能变化、焊接性及加工性等方面的研究进展,分析了FeCrAl合金的高温腐蚀机理以及引起FeCrAl合金微观结构及力学性能变化的主要原因,提出了FeCrAl合金在高温腐蚀、焊接性以及加工性等过程中存在的主要问题以及未来的研究方向。     

轻水反应堆（LWR）用包壳材料研究进展

轻水反应堆（LWR）是国际上多数核电站采用的堆型。锆具有良好的加工性能,优良的机械性能,较高的熔点、优异的耐蚀性能及核性能,被用作燃料包壳和堆芯结构材料,是发展核电及核动力舰船不可替代的关键结构材料和功能材料。随着核电技术的发展,对堆芯包壳材料性能提出了更高的要求,综述了核用锆合金包壳材料的国内外研究和使用现状以及新型SiC包壳材料的研发现状。总体来说,锆合金在未来几十年内仍是核反应堆包壳材料的主要用材,开展新合金的研发,不断提升锆合金的性能是世界各国研究者共同的目标;适时加大投入力度,强化条件建设,就能加快具有国内自主知识产权锆合金的产业化步伐,可最终实现核电及核动力用锆合金材料的自主化;SiC材料具有更高的熔点、更好的耐腐蚀性能,是一种极具应用潜力的材料,有可能成为第4代核反应堆的包壳材料,但还需投入大量研究。     

Mo含量对CoCrFeNiMo高熵合金组织及耐蚀性能的影响

高熵合金由于具有优异的机械性能及耐蚀性能在涂层工业领域备受关注。采用同步送粉激光熔覆技术在Q235钢表面制备了CoCrFeNiMo_x高熵合金涂层,研究了涂层的组织结构和耐蚀性能,并结合第一性原理计算分析了涂层耐蚀机理。研究结果表明：CoCrFeNiMo_0.1、CoCrFeNiMo_0.2高熵合金涂层是由fcc相组成,而CoCrFeNiMo_0.3高熵合金涂层则由fcc相和σ相组成。合金的晶粒主要呈树枝晶,枝晶间富集Cr、Mo元素,枝晶内富集Co、Fe元素。在3.5%(质量分数)NaCl溶液中,CoCrFeNiMo_x高熵合金涂层具有优良的综合耐蚀性能;并且随着Mo元素含量的增加,涂层的腐蚀电位正移,腐蚀电流密度减少,钝化区间变长,阻抗弧半径增大,电极反应阻力增强。通过第一性原理计算证明,涂层较高的耐蚀性能与表面致密的钝化膜形成密切相关。     

Microstructure and corrosion behaviour of FeCoNiCuSnx high entropy alloys

Abstract

The FeCoNiCuSn_x alloys with different Sn contents are prepared, the microstructure and the corrosion behaviour of the alloys are investigated. When Sn content is lower than 0.09, FeCoNiCuSn_x alloys consist of a single FCC phase. While Sn content of the alloy is 0.09, a small quantity of BCC structure is present. The FeCoNiCuSn_x alloys have a wider passive region in the NaOH solution. FeCoNiCuSn_x alloys exhibit a better corrosion resistance in NaCl solution than 304 stainless steel, the corrosion resistance of FeCoNiCuSn_0.04 alloy is best among all the alloys. The corrosion resistance of FeCoNiCuSn_x alloys in NaOH solution is lower than that of 304 stainless steel, the corrosion resistance of FeCoNiCuSn_0.03 alloy is best among all FeCoNiCuSn_x alloys.     

B_4C加入量对氩弧熔覆Ni-Cr-W合金涂层组织及耐蚀性能的影响

为改善Ni基合金涂层的组织及耐蚀性,采用氩弧熔覆技术在40Cr钢基体表面制备Ni-Cr-W基/B_4C复合涂层,主要研究了B_4C加入量对涂层显微组织、显微硬度以及耐蚀性能的影响。结果表明:合金涂层显微组织由平面晶、柱状晶和树枝状晶等组成;当B_4C含量为5%时,涂层熔覆层的组织明显发生细化;当B_4C含量超过5%时,熔覆涂层表面出现气孔和裂纹等缺陷,内部夹杂增多,涂层质量下降;B_4C的加入提高了合金涂层的硬度,当B_4C含量达到5%时表面硬度较高,达到1 027.4 HV_(0.5N),B_4C含量继续升高,硬度变化不大;B_4C的加入降低了熔覆层耐蚀性,当B_4C含量为5%时耐蚀性相比未加B_4C时的下降不多,耐蚀性较好。     

铜导线表面热浸镀PbSn合金镀层的组织与性能

为了改善铜导线的可焊性和耐蚀性,采用热浸镀技术在铜导线表面制备Pb40Sn60和Pb37Sn63两种成分的低熔点合金镀层,利用扫描电镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)等分析手段和电阻率检测实验、拉伸实验、中性盐雾实验等方法,系统研究其微观组织、相成分、电阻率、力学性能及耐蚀性。结果表明:Pb40Sn60和Pb37Sn63两种成分的合金镀层均由α相和β相两相组成,镀层的电阻率分别约为2.6832×10^-3,2.5929×10^-3Ω·m,均高于铜基体。铜导线热浸镀Pb40Sn60和Pb37Sn63两种成分合金镀层后的表面硬度分别为13.4,12.6HV0.2;抗拉强度分别为193,180 MPa;伸长率分别为35%和37%,与铜基体相比均降低。铜导线表面热浸镀PbSn合金镀层具有良好的导电性、力学性能及耐腐蚀性等综合性能。随着Pb含量的降低或Sn含量的增加,PbSn合金镀层中α相的相对量减少、β相的相对量增大,其电阻率、硬度和强度降低,塑性略有增大,耐蚀性增强。Pb40Sn60比Pb37Sn63合金镀层的腐蚀速率较高,分别为2.44×10^-2,3.65×10^-3 g·cm^-2·a^-1,耐腐蚀性较差。PbSn合金镀层中α相比β相的腐蚀程度更为严重,α相比β相的耐蚀性要差。     

Cr含量对CrMnFeNi系高熵合金腐蚀行为的影响EI北大核心CSCD

利用XRD,SEM/EDS,EBSD,电化学测试等表征手段研究Cr含量对Cr_(x)MnFeNi(x=0.8,1.0,1.2,1.5)高熵合金微观组织与耐蚀性能的影响。结果表明:Cr_(0.8)MnFeNi高熵合金为单相FCC结构,Cr_(x)MnFeNi(x=1.0,1.2,1.5)高熵合金为FCC+BCC双相结构,且BCC相比例随着Cr含量升高而增加。在0.5 mol/L H_(2)SO_(4)溶液中,高熵合金的耐蚀性能随着Cr含量降低而增强,其中,Cr_(0.8)MnFeNi单相高熵合金的耐蚀性能最好,这是因为Cr_(0.8)MnFeNi高熵合金的成分更为均匀。此外,Cr_(x)MnFeNi高熵合金在0.5 mol/L H_(2)SO_(4)溶液中均具有宽泛的钝化区域以及明显的伪钝化区域,表明合金在耐蚀性能上具有较大的研究价值和开发潜力。     

1Cr12Ni2W1Mo1V不锈钢表面等离子堆焊司太立熔覆层的组织及性能

为提高1Cr12Ni2W1Mo1V不锈钢的耐水蚀性能,采用等离子堆焊方法在其表面制备司太立熔覆层。研究了涂层的显微组织和显微硬度分布,分析了涂层的抗微粒冲蚀性能和耐水蚀性能。结果表明:司太立熔覆层与基体材料冶金结合良好,熔覆层组织细小、分布均匀,基体为枝晶状Co-Cr固溶体,枝晶间较均匀地分布着黑色碳化物,主要为M7C3和少量WC颗粒;司太立熔覆层的平均显微硬度(382.38 HV4.9 N)约为基材平均硬度(195.29HV4.9 N)的1.96倍,最高硬度值达到了421.00 HV4.9 N;堆焊第2层的硬度明显高于第1层的;司太立熔覆层合金的抗微粒冲蚀性能优于基材,其水蚀速度比基材小,在基材1Cr12Ni2W1Mo1V上堆焊司太立合金能有效提高其耐水蚀性能。     

Preparation and characterization of as-extruded Mg–Sn alloys for orthopedic applications

In this study, as-extruded Mg–Sn alloys with various Sn content were prepared and characterized for orthopedic applications. The results of microstructure observations and X-ray diffraction analysis showed that as-extruded Mg–Sn alloys were composed of α-Mg and Mg₂Sn phases, and the content of Mg₂Sn phase increased with increasing Sn content. The microstructure of as-extruded Mg–Sn alloy with 1 wt.% Sn was equiaxed grain, while the one with a higher Sn content was inhomogeneous microstructure and the grain size of the long elongated grains decreased with increasing Sn content. Tensile test revealed that the yield strength and ultimate tensile strength of as-extruded Mg–Sn alloys increased while the elongation decreased with increasing Sn content. Immersion and electrochemical tests indicated that the microstructure of as-extruded Mg–Sn alloys affected their corrosion properties, and the increase of Mg₂Sn phase resulted from the increase of the Sn content led to a higher corrosion rate. The cytotoxicity test showed that as-extruded Mg–1Sn and Mg–3Sn alloys met the requirement of cell toxicity for orthopedic applications. Our analyses showed that as-extruded Mg–1Sn and Mg–3Sn alloys were promising to be used as biodegradable orthopedic implants.     

Novel insight into dry sliding behavior of Cu-Pb-Sn in-situ composite with secondary phase in different morphology

The Cu-24 Pb-x Sn(wt%)(x = 0, 2, 4, 6) alloys with Pb-rich second-phase particles(SPPs) in different shapes show obviously differently mechanical and self-lubricating properties. The influence of the SPPs' shape difference on the alloys' mechanical and self-lubricating properties was revealed. Cu-24 Pb alloy with continuously netty SPPs shows much more intensive stick-slip phenomenon during dry sliding than the other three alloys with independently rodlike SPPs. That is mainly due to insufficient lubrication resulted by the netty SPPs' splitting matrix. With the SPPs transforming from netty to rodlike shape under the addition of Sn, the stick-slip phenomenon was notably weakened, which was proven to be related to the higher self-lubricating property of alloys with rodlike SPPs. Simultaneously, the simultaneous increase of ductility and tensile strength was observed in the Cu-24 Pb-x Sn alloys with increasing Sn content, which is because the netty SPPs' splitting behavior will be weakened with them replaced by the rodlike SPPs.     

激光熔覆CoCrFeMnNiMox高熵合金的组织和耐蚀性研究

目的 为了增强钢制结构表面的耐蚀性,研究Mo含量对CoCrFeMnNiMox高熵合金组织与耐蚀性的影响。方法 采用激光熔覆的方式在N80钢上制备CoCrFeMnNiMox（x=0.1、0.2、0.3、0.4、0.5）高熵合金熔覆层,研究Mo含量变化对高熵合金组织、物相与耐蚀性的影响。结果 CoCrFeMnNiMox熔覆试样均由单一的FCC固溶体相组成,随着Mo含量的增加,晶格畸变增大;当Mo的摩尔比超过0.3后,晶粒有长大倾向;Mo的摩尔比为0.5时,表面择优生长晶面由（111）密排晶面转变为（200）非密排晶面。熔覆试样在氯化钠溶液和稀硫酸溶液中的耐蚀性相较N80钢提升明显,其中,CoCrMnFeNiMo0.3的耐蚀性最好,在质量分数为3.5%的氯化钠溶液中其自腐蚀电流密度是N80钢的5%,自腐蚀电位比N80钢提高了1倍;在0.5 mol/L硫酸溶液中,其自腐蚀电流密度是N80钢的31%,钝化区电流密度比N80钢降低了1个数量级。结论 在该高熵合金体系中,随着Mo含量的增加,晶格畸变增大。CoCrMnFeNiMox高熵合金熔覆层可以有效地阻止基体腐蚀的发生。Mo元素在溶液中能够形成MoO3附着在金属表面,从而形成稳定致密的保护层,减少点蚀的发生。CoCrMnFeNiMo0.3熔覆层的耐蚀性最好。     

Microstructural evolution,mechanical properties and corrosion behavior of as-cast Mg-5Li-3Al-2Zn alloy with different Sn and Y addition

Influences of Sn and Y on the microstructure,mechanical properties,and corrosion behavior of as-cast Mg-5Li-3Al-2Zn (LAZ532) alloy were investigated.The addition of Sn and Y refines grains and results in the formation of Mg2Sn and Al2Y phases,thus improving the mechanical properties of alloy by second phase strengthening and grain refinement strengthening.As-cast LAZ532 alloy shows typical filiform corrosion morphology,and the addition of Sn and Y does not change the corrosion mode of alloy.Ascast LAZ532-0.8Sn-1.2Y alloy shows excellent mechanical properties with yield strength of 166.2 MPa,ultimate tensile strength of 228.6 MPa and elongation of 14.8 ％,and exhibits the best corrosion resistance with the smallest corrosion current density and the lowest anodic dissolution rate.     

添加钼对锆合金性能的影响研究

添加合金元素来提高锆合金的力学性能和耐腐蚀性能,近年来受到研究学者的广泛关注。概述了加钼锆合金的国内外研究现状和发展趋势,着重介绍了添加钼元素对锆合金力学性能、耐腐蚀性能、微观组织、形变织构、第二相等方面的影响。在锆-铌合金中添加适量的钼,再通过适当的热机械处理,可以得到高强度、耐腐蚀、晶粒细小的锆合金。     

锆合金涂层包壳专利申请态势全景分析

事故容错燃料(ATF)是日本福岛核事故之后提出的新一代核燃料概念,主要是为了提高反应堆在事故工况下的容错性能,从根本上提高核电厂对严重事故的抵御能力,从而有效地提高核电的安全性和经济性.针对传统核燃料使用的锆合金包壳,通过外表面涂层改性的方法提高其在事故工况下的抗高温氧化性能是事故容错燃料的主要研究方向.为了对锆合金涂...     

Laser cladding of Zr-based coating on AZ91D magnesium alloy for improvement of wear and corrosion resistance

To improve the wear and corrosion resistance of AZ91D magnesium alloy, Zr-based coating made of Zr powder was fabricated on AZ91D magnesium alloy by laser cladding. The microstructure of the coating was characterized by XRD, SEM and TEM techniques. The wear resistance of the coating was evaluated under dry sliding wear test condition at room temperature. The corrosion resistance of the coating was tested in simulated body fluid. The results show that the coating mainly consists of Zr, zirconium oxides and Zr aluminides. The coating exhibits excellent wear resistance due to the high microhardness of the coating. The main wear mechanism of the coating and the AZ91D sample are different, the former is abrasive wear and the latter is adhesive wear. The coating compared to AZ91D magnesium alloy exhibits good corrosion resistance because of the good corrosion resistance of Zr, zirconium oxides and Zr aluminides in the coating.     

事故容错燃料包壳候选材料的研究现状及展望

2011年福岛核电站事故中,反应堆堆芯燃料中的锆合金包壳在事故工况下与高温水蒸汽发生剧烈氧化反应继而产生大量的氢气和热量,最终导致反应堆堆芯熔化和氢气爆炸,对社会和环境造成极大负面影响。自此之后,国内外纷纷展开对事故容错燃料的研究开发。相较于传统的UO2-Zr合金燃料体系,事故容错燃料能够在反应堆正常运行工况下维持或提高燃料性能,并在事故发生后相当长的一段时间内维持堆芯完整性,提供足够的时间裕量来采取事故应对措施。反应堆堆芯环境非常极端,包壳长期处于高温高压腐蚀介质中,同时还受到中子辐照的影响,因此新型包壳材料需要较好的耐腐蚀性和辐照稳定性。经不同研究者的研究评估,目前能够替代Zr合金的事故容错燃料包壳材料可分为陶瓷材料和金属材料两类:陶瓷材料主要以SiC/SiC复合材料为代表;金属材料主要有以FeCrAl为代表的Fe基合金和以Mo为代表的难熔金属及其合金。上述三种替代Zr包壳的材料各有其利弊,均未达到工程应用水平,并且都存在待解决的关键性问题。其中,FeCrAl合金的研发进展最快,目前在热学性能、力学性能、抗腐蚀性能、抗辐照性能等方面表现较好,但在工业加工和焊接等方面仍有待进一步改善。就SiC/SiC复合材料而言,由于SiC自身的高脆性而导致力学强度不足,不同的研究者提出了不同的结构设计思路试图降低包壳管失效概率,但包壳最终的结构设计仍未确定,而辐照引起的热导率急剧降低及连接密封和加工制造等方面还在不断研究中。Mo及Mo合金的力学性能和抗辐照性能较好,但自身抗腐蚀性较差,解决思路主要集中在提高钼纯度、调整合金的元素成分、进行表面涂层等方面。目前,对后两种材料包壳管的加工能力均未达到薄壁长管的工业制造水平。对于这几种候选包壳材料,需要建立属性数据库和一套完善的标准来衡量材料的质量。此外,还需开发相应的程序来评估包壳在堆内的行为。本文主要综述了SiC/SiC复合材料、FeCrAl合金、Mo及Mo合金三种候选包壳材料的研究进展,包括候选包壳材料的物理性质、耐腐蚀性能、力学性能、抗辐照性能、芯块-包壳力学与化学相互作用、在事故工况下的行为和工程应用等,综合分析了事故容错燃料包壳材料当前的研究现状,指出了各事故容错燃料包壳未来需集中解决的关键性问题。     

Al-Zn-Mg-Cu系超高强度铝合金的研究现状与发展趋势

分析了近年来超高强度Al-Zn-Mg-Cu系铝合金的成分设计、工艺优化、显微组织分析、力学性能测试及微量元素的作用，对今后的发展动向提出了一些新的看法：采用传统铸造技术得到的铝合金，Zn含量的最大值在8wt％左右，抗拉强度低于700MPa；采用喷射成形技术，Zn含量最大值能够超过12wt％，同时抗拉强度可达800MPa以上，大大提高了铝合金的强度；超高强度铝合金的固溶强化相主要为MgZn2相；经回归时效处理(RRA)后，合金同时具有T6的强度和T7X的抗应力腐蚀性能；微量元素对超高强度铝合金的组织和性能具有显著的影响。     

Observation of crack microstructure in oxides and its correlation to oxidation and hydrogen-uptake by 3D FIB Tomography – case of Zr-ZrO2 in reactor

Abstract

Zirconium based alloys are used as fuel claddings in Light Water Reactors due to their good resistance to degradation and low neutron absorption cross section. However, life limiting processes occur during the service of the cladding such as oxidation and hydrogen-uptake. During the oxidation of the material, hydrogen enters the metal and it precipitates as brittle hydrides. In this study the 3D microstructure of a high burn-up and a low-burnup LK3/L Zircaloy-2 cladding is characterized and compared using FIB Tomography. 3D reconstruction of the oxides of the claddings shows that the crack volume fraction increases with the number of cycles in the reactor, reducing its protectiveness against further corrosion and H-uptake. The visualization of the metal-oxide interface revealed that the oxidation of the hydrides in the metal could induce crack formation in the oxide and therefore it could be one of the causes of the increasing oxidation and H-uptake in this material.     

Effect of Zr on the microstructure, mechanical properties and corrosion resistance of Mg–10Gd–3Y magnesium alloy

The influence of Zr on the microstructure, mechanical properties and corrosion resistance of Mg–10Gd–3Y (wt.%) magnesium alloy was investigated. The grain size of alloys decreased with Zr content from 0% to 0.93% (wt.%). The addition of Zr greatly improved the ultimate tensile strength (UTS) and the elongation (EL), while slightly improved the tensile yield strength (TYS). The UTS and the EL of the alloy containing 0.93% Zr increased by 125.8 MPa and 6.96% compared with base alloy, respectively. The corrosion resistances were found to decrease with Zr content from 0% to 0.42% and then increase from 0.42% to 0.93%. The differences in the sizes and distributions of the Zr-rich particles have significant effects on the corrosion behaviors. The alloy with 0.42% Zr addition revealed the optimum combination of mechanical properties and corrosion resistance.     

Microstructure and mechanical properties of Mg–6Sn and Mg–6Zn alloys prepared by different processing techniques: a comparative study

The microstructure and mechanical properties of Mg–6Sn and Mg–6Zn are investigated and compared in cast/heat treated, rolled and extruded conditions. Compared to the heat treated alloys, the grain size of both alloys decreases while the volume fraction of precipitates increases by rolling and extrusion in Mg–6Sn alloy at 350 ºC due to dynamic recrystallization and dynamic precipitation of intermetallic phases. Zinc has a stronger grain refining effect than tin in the heat treated alloys while the opposite effect is found in the rolled and extruded alloys. For the heat treated alloys the Mg–6Sn the strength reached 158.7 MPa with elongation 5.2% while Mg–6Zn exhibited a higher strength of 183.7 MPa and 8.4% elongation. In rolled condition the strength of Mg–6Sn reached 224 MPa with 1.6% elongation while Mg–6Zn exhibited a lower strength of 124 MPa and a lower ductility of 0.5% elongation due to susceptibility to hot shortness. Extrusion of Mg–6Sn alloy resulted in the maximum attained strength of 281 MPa and an elongation of 6.1% while Mg–6Zn cracked during extrusion due to hot shortness. The results obtained are discussed with respect to microstructure evolution in both alloys.