7xxx系铝合金晶界偏析研究进展

评述了7xxx系铝合金晶界偏析问题的国内外研究现状,讨论了晶界结构以及晶界偏析的实验研究.针对目前研究工作中尚未从理论上揭示晶界Mg偏析本质的突出问题,指出了今后7xxx系铝合金晶界偏析问题的研究方向,同时结合前期的研究工作,提出了相关的建议.     

Al—Zn—Mg三元合金的晶界偏析

使用俄歇电子光谱仪对合金添加剂在新淬火,未充分时效、峰值时效和过时效状态的三元Al—5.5％Zn—2.5％Mg合金晶界处的含量分布情况进行了测量。AES深度分布图示出了Mg和Zn在晶界处的明显偏析,它与以前对相同合金的测量结果完全不同。还发现,这种明显的矛盾,可通过AES光谱的等离子损失特点来阐明晶界偏析情况面得到解决。用AES等离子损耗测量方法,即可测定Mg和Zn在晶界处的偏析,又能测定合金添加剂周围的冶金环境。还指出,过时效的Al合金试样,仅有部分Mg(占晶界处总Mg含量的一部分)进入了MgZn_2沉淀相,余者则集中分布在界面处的几个原子层内。     

Mg在铸造镍基高温合金In100相界上的偏析

应用电子探针、Auger能谱仪、透射电镜能谱等微区成分分析技术研究了铸造镍基高温合金In100中微量Mg在第二相中的分布。结果表明,微量Mg偏析于MC和γ′相界面,而在其内部没有富集;Mg在MC相界面上的偏析厚度大于在γ′相界面的偏析厚度;试验结果及理论分析表明,Mg不仅是晶界偏析元素,更重要的是相界偏析元素。     

Al-Zn-Mg-Cu超高强铝合金晶界偏聚与腐蚀机制研究

采用自编软件建立Al-Zn-Mg-Cu合金中α-Al、η(MgZn2)相及晶界含η相的α-Al大角度晶界原子集团模型.用递归法计算合金中Zn、Mg、Cu的环境敏感镶嵌能、原子相互作用能,α-Al和η相结合能、费米能级等电子参数.并依据电子参数分析合金的腐蚀特性.结果显示:合金元素Mg、Cu容易在晶界偏析,Mg、Zn形成η相原子集团.因Mg在晶界偏析,晶界析出的η相较为粗大,晶内形成的η相比较细小.计算还表明:η相的费米能级最高,在腐蚀过程中作为阳极优先溶解.合金元素Zn具有增大晶界、晶内电位差的作用,降低合金的抗腐蚀性.Cu能减小晶界与晶内费米能级差,降低晶界与晶内的电位差,具有减缓合金腐蚀的作用.     

Al-Zn-Mg-Cu系铝合金中不同区域电子结构及应力腐蚀机理分析

利用计算机编程建立了Al--Zn--Mg--Cu合金 (7175铝合金) 中α--Al, η相及α--Al大角度晶界原子集团模型, 采用递归法计算 合金中Zn, Mg, Cu和H的环境敏感镶嵌能、原子间相互作用能、Fermi能级和态密度等电子结构参数, 分析了合金的应力腐蚀机理. 计算 结果表明: Mg, Cu和H容易在晶界偏析. Mg对H具有吸引作用, 促进H在晶界偏析, 引起晶界氢脆; Zn增大晶界与晶内的电位差, 降低合 金抗腐蚀性; Cu能减小晶界与晶内Fermi能级差, 降低晶界与晶内的电位差, 具有减缓合金腐蚀的作用. 计算结果还表明: η相的Fermi能 级最高, 腐蚀过程中作为阳极优先溶解. 由于η相俘获H, 当晶界析出断续η相时可减弱晶界H的偏析, 提高抗腐蚀性; 但晶界连续分布η相则形成腐蚀通道, 加速腐蚀进程.     

合金元素Mg对含RE铝阳极组织与性能的影响

采用恒电流方法,测定了Al-5Zn-0.05In-0.1Sn-0.3RE和Al-5Zn-0.05In-0.1Sn-Mg-0.3RE两种铝合金牺牲阳极材料电流效率、利用金相显微镜、扫描电镜和能谱分析,研究了它们的金相组织。结果表明：镁对含RE铝阳极性能有较大改善,镁的添加改变了铝合金晶界偏析相的组成;晶界析出物Mg相减轻了铝阳极的晶界腐蚀和晶粒脱落。     

ZL205A合金晶界偏析行为研究

利用SEM和XRD研究了ZL205A合金铸件Cu元素晶界偏析。结果表明:结晶过程中Cu元素自发往晶界偏聚,晶界偏析宏观形貌为弯曲条状,曲线条之间相互平行,偏析组织是Al2Cu共晶相,呈枝晶状、网状和散乱碎片状分布在粗化的晶界上;晶界偏析与热裂具有较大相关性。     

微量元素偏析对厚大断面球铁石墨形态的影响

分析了厚大断面球铁件石墨畸变的形成原因及影响因素,浇注了400mm×400mm×450mm的试块研究微量元素偏析对石墨形态的影响。结果表明：开花状石墨的中心部存在Mg、Al、La、Ca、S等元素的富集,这些元素的富集破坏了石墨生长的稳定性;而晶界上V、Ti的偏析和球化元素Mg或RE等氧化形成的氧化夹杂,破坏了奥氏体壳的稳定性,造成石墨畸变;在铁液中添加微量Sb,凝固过程中Sb偏析于石墨—奥氏体界面上,可有效抑制或减缓C向石墨球扩散,限制石墨球生长,抑制石墨球畸变。     

GH698合金塑性的研究

本文研究了我厂试制的GH698合金个别试样中温塑性偏低的原因。对试样的组织、大γ′相不均匀性、元素偏析、夹杂物及晶界状态等与实物进行了对比。研究结果表明,大γ′相分布不均匀是合金中Al、Ti偏析所致。夹杂物多且沿轧向呈条带分布,大颗粒呈网状或骨架状,个别Nb(C,N)夹杂中含有氧,还存在有高Zn、S、Mg的夹杂。这些都影响了合金的中温塑性。本文也对加入微量Mg后,合金的组织、Mg的分布,对断口形貌的改善进行了详细对比分析。     

7050铝合金晶界偏析与应力腐蚀,腐蚀疲劳行为的研究

研究了不同时效状态的７０５０铝合金晶界偏析与应力腐蚀开裂及湿空气环境下疲劳裂纹扩展的关系，并采用修正的化学方法计算了晶界偏析对断裂应力的影响。结果表明：随着时效程度的增加，晶界上Ｍｇ偏析浓度减小，捕获Ｈ的能力减弱，晶界断裂应力的百分数随之下降，因而合金的抗应力腐蚀和腐蚀疲劳性能提高。     

Deformation of nanocrystalline binary aluminum alloys with segregation of Mg,Co and Ti at grain boundaries

The influence of the temperature and sort of alloying element on the deformation of the nanocrystalline (NC) binary Al alloys with segregation of 10.2 at % Ti, Co, or Mg over grain boundaries has been studied using the molecular dynamics. The deformation behavior of the materials has been studied in detail by the simulation of the shear deformation of various Al bicrystals with the grain-boundary segregation of impurity atoms, namely, Ti, Co, or Mg. The deformation of bicrystals with different grain orientation has been studied. It has been found that Co introduction into grain boundaries of NC Al has a strengthening effect due to the deceleration of the grain-boundary migration (GBM) and difficulty in the grain-boundary sliding (GBS). The Mg segregation at the boundaries greatly impedes the GBM, but stimulates the development of the GBS. In the NC alloy of Al–Ti, the GBM occurs actively, and the flow-stress values are close to the values characteristic of pure Al.     

Effect of Zn and Y Additions on Grain Boundary Movement of Mg Binary Alloys During Static Recrystallization

Texture evolution in rolled Mg–1 wt% Zn and Mg–1 wt% Y binary alloys was analyzed by quasi-in situ electron backscatter diffraction (EBSD) during static recrystallization. Mg–1 wt% Zn and Mg–1 wt% Y alloys exhibited strong basal texture at the initial recrystallization state. After grain growth annealing, the basal texture component {0001} < $11\overline{2}0$ > was increased in Mg–1 wt% Zn alloy and that of Mg–1 wt% Y alloy was decreased to be a random texture. Zn and Y atoms segregated strongly to the recrystallized grain boundaries in Mg–1 wt% Zn alloy and Mg–1 wt% Y alloy, respectively. Thus, Zn and Y elements facilitated the grain boundary movements along contrary directions during grain growth. In Mg–1 wt% Zn alloy, due to the Zn element segregation on grain boundaries, the grains consisted of a strong texture grew more easily because the grain boundary migration tended to move from the orientation close to normal direction to the orientation near to transverse direction or rolling direction. Therefore, after grain growth, the volume fraction of texture component {0001} < $11\overline{2}0$ > was increased by consuming the neighboring grains, leading to a stronger basal texture. On the contrary, in the Mg–1 wt% Y alloy, the Y element segregation caused the opposite direction of grain boundary migration, resulting in a random texture.     

Effects of solute Mg on grain boundary and dislocation dynamics during nanoindentation of Al–Mg thin films

Using in situ nanoindentation in a transmission electron microscope (TEM) the indentation-induced plasticity in ultrafine-grained Al and Al–Mg thin films has been studied, together with conventional quantitative ex situ nanoindentations. Extensive grain boundary motion has been observed in pure Al, whereas Mg solutes effectively pin high-angle grain boundaries in the Al–Mg alloy films. The proposed mechanism for this pinning is a change in the atomic structure of the boundaries, possibly aided by solute drag on extrinsic grain boundary dislocations. The mobility of low-angle boundaries is not affected by the presence of Mg. Based on the direct observations of incipient plasticity in Al and Al–Mg, it was concluded that solute drag accounts for the absence of discrete strain bursts in indentation of Al–Mg.     

Zn对Mg-9Al合金凝固行为的影响

研究了Zn元素对Mg-9Akl合金的凝固行为，尤其是对热裂倾向性的影响。通过热分析手段考察合金的凝固特征。用热裂环法评价合金的热裂倾向性，引入了热裂倾向性（HSC）因子的概念。并通过金相观察、扫描电镜和电子探针对合金的凝固、热裂行为进行了研究。研究发现，在凝固过程中An,Al元素由于晶间偏析而在晶界富集。Zn元素的加入，增加了晶界低熔点相的量，并降低了其熔点，从而明显增加了合金的热裂倾向性。Mg-9Al-xZn合金的热凝产生于凝固后期，呈沿晶断裂。加入Zn元素对Mg-9Al合金的晶粒有细化作用。     

均匀化处理对含钪Al-Zn-Mg-Zr合金组织的影响

采用金相分析、扫描电镜、能谱分析、DSC等手段研究含钪Al-Zn-Mg-Zr合金均匀化态显微组织的演变。结果表明：在合金铸态组织中存在大量的枝晶偏析,在晶界处存在很多低熔点共晶相,主要元素在枝晶内部区域呈周期性变化;合金中元素Zn、Mg和Cu在晶内及晶界分布不均匀;在均匀化过程中,随着均匀化温度的升高或时间的延长,残留相逐渐溶入基体,元素分布逐渐均匀。合金的过烧温度为476.7°C。当均匀化温度升高到480°C时,合金中开始出现复熔球和三角晶界。综合考虑：合金的最佳均匀化制度为470°C,24 h。     

Gd对Mg9AlZnY镁合金消失模组织和性能的影响

在Mg9AlZnY合金基础上添加不同含量Gd元素,采用消失模铸造成形,研究其组织性能变化。结果发现,随着Gd含量的增加,Mg9AlZnY合金中的β-Mg17Al12相形成数量显著减少,并由连续网状结构转变为断续状和颗粒状结构。含Gd的Mg9AlZnY合金组织主要由α-Mg固溶体、β-Mg17Al12相和分布在α-Mg晶界的少量棒状Al2Y相和块状Al2Gd相组成。Al2Y和Al2Gd相热稳定性好,在高温下对晶界具有钉扎作用,防止晶界滑移,提高了晶界的高温强度。当Gd含量在0.9%(质量分数)左右时,经T6热处理后室温的抗拉强度为235MPa,200℃高温抗拉强度为156MPa,分别比Mg9AlZnY合金提高了11.9%和28.9%。     

Sc,La对Al-Mg焊料中杂质元素偏聚的调控作用

采用金相显微镜、扫描电镜、能谱分析和X射线衍射仪,研究了添加微量钪、镧对铝镁焊料中杂质元素偏聚的调控作用. 结果表明,在铝镁焊料合金凝固过程中,铁、硅等杂质元素在晶界有偏聚效应,添加微量钪、镧可以降低铁、硅杂质在晶界的偏聚浓度. 钪与镧减轻杂质元素在晶界偏聚的效果存在差别,添加钪的合金比添加镧的合金晶界处杂质元素偏聚强度明显减弱. 造成这种差别的原因是,钪、镧对杂质元素偏聚的调控机制不同.     

Intergranular fracture caused by trace impurities in an Al–5.5 mol% Mg alloy

A coarse-grained Al–5% Mg alloy, which does not show high temperature embrittlement, is successfully prepared using high purity raw materials and a graphite crucible. By preventing the contamination of sodium and hydrogen, it becomes possible to examine separately the effects of various trace elements on hot ductility in the Al–5% Mg alloy. Sodium, calcium, or strontium of 2 mol ppm brings about the high temperature embrittlement based on intergranular fracture, while lithium of 4 mol ppm does not. Sodium is the most highly embrittling among such detrimental elements. The detrimental effect of such impurity is due to its segregation to grain boundaries. Further, the embrittlement caused by sodium or strontium of 2 mol ppm is greatly suppressed by an addition of more than 1000 mol ppm of silicon which scavenges those detrimental elements from grain boundaries.     

热矫正次数对7N01铝合金应力腐蚀开裂的影响

采用慢应变速率拉伸试验(SSRT)和透射电镜(TEM)测试分析方法研究了热矫正次数对7N01-T5铝合金应力腐蚀敏感性的影响。结果表明:随着热矫正次数的增加,7N01-T5铝合金应力腐蚀敏感性增加。原因主要在于晶界析出相的转变以及溶质元素Zn和Mg从基体向晶界的不断扩散。基于非平衡偏聚理论可知,三次热矫正的等效恒温时间小于临界时间t_c。因此,随着热矫正次数的增加,晶界处Zn和Mg元素含量逐渐增加,增大了晶界与基体间的腐蚀电位差,使7N01-T5铝合金应力腐蚀敏感性增加。     

The effect of scandium on the microstructure,mechanical properties and weldability of a cast Al–Mg alloy

The microstructure, mechanical properties and weld hot cracking behaviour of a cast Al–Mg–Sc alloy containing 0.17 wt.% Sc were compared with those of a Sc-free alloy of similar chemical composition. Although this level of Sc addition did not cause grain refinement, the dendritic substructure appeared to be finer. There was a significant increase in the yield and tensile strength and the microhardness of the Al–Mg–Sc alloy relative to its Sc-free counterpart. A discontinuous precipitation reaction was observed at the dendritic cell boundaries. Microchemical analysis revealed segregation of Mg and Sc at these interdendritic regions. No improvement was observed in the resistance of the alloy to weld solidification cracking or heat affected zone (HAZ) liquation cracking. This is explained in terms of the inability of this level of Sc addition to refine the solidification structure and to influence the liquation of solute-enriched dendritic cell boundaries of the cast material.