FGH95合金长期时效过程中二次γ′相的“反粗化”分裂行为

利用场发射扫描电镜研究了FGH95粉末冶金高温合金在750℃/5000h时效过程中二次γ′相的尺寸、分布和形貌变化,为其在新型航空发动机中的应用提供理论依据。结果表明,随着时效时间增加,二次γ′相形态不稳定,其尺寸变化不符合体扩散控制的LSW规律。二次γ′相在0~500h发生"反粗化"的分裂,由碟状分裂为块状。在500~1000h阶段分裂的细小γ′相发生粗化,在1000h粗化到一定程度后又开始分裂,2000h后随着时效时间延长又逐渐粗化,椭球状二次γ′相逐渐增多。研究证明,γ′相粒子之间的弹性交互作用是导致其形态变化的主要原因,它属于降低界面能与弹性交互作用能总量的形貌转变机制。     

FGH95合金长期时效过程中二次γ'相的“反粗化”分裂行为

利用场发射扫描电镜研究了FGH95粉末冶金高温合金在750℃/5000 h时效过程中二次γ'相的尺寸、分布和形貌变化,为其在新型航空发动机中的应用提供理论依据.结果表明,随着时效时间增加,二次γ'相形态不稳定,其尺寸变化不符合体扩散控制的LSW规律.二次γ'相在0～500 h发生“反粗化”的分裂,由碟状分裂为块状.在500～1000 h阶段分裂的细小γ'相发生粗化,在1000 h粗化到一定程度后又开始分裂,2000 h后随着时效时间延长又逐渐粗化,椭球状二次γ'相逐渐增多.研究证明,γ'相粒子之间的弹性交互作用是导致其形态变化的主要原因,它属于降低界面能与弹性交互作用能总量的形貌转变机制.     

微量元素Hf对镍基粉末高温合金FGH97显微组织的影响

利用SEM和物理化学相分析方法研究了5种Hf含量的FGH97粉末高温合金中γ'相和MC型碳化物形貌、化学组成及含量.结果表明:Hf促进γ'相和MC相析出,改变γ'相和MC相的化学组成,对MC相的尺寸和形貌影响不大,显著影响γ'相的尺寸和形貌,促使γ'相的形态失稳,导致立方状γ'相发生分裂,使γ'相更快地进入稳定的立方状择优形态.在FGH97合金中添加Hf,可通过改变错配度d,从而改变γ'相发生分裂的临界尺寸Dc.建立了Dc与Hf含量w(Hf)的关系式:Dc=315.4+640.2w(Hf)-358.2[w(Hf)]2.随着Hf含量的增加,|d|逐渐变小,Dc增大.γ'相长大到临界尺寸时,γ'相由立方状分裂为八重小立方体状.     

镍基粉末高温合金中微量元素Hf的作用

利用FEG-SEM,TEM,AES和EDS分析技术以及物理化学相分析等方法,系统地研究了微量元素Hf在镍基粉末高温合金中的作用.结果表明:Hf以固溶态分布在枝晶间γ固溶体内,有助于减少原始粉末颗粒边界组织.Hf促进γ′相形态失稳,导致大尺寸立方状γ′相发生分裂,更快地进入γ′相低能稳定的择优形态.Hf主要分布在γ′相和MC型碳化物中,改变γ′相和MC型碳化物及γ固溶体相间合金元素的再分配,有利于消除合金的缺口敏感性,改善合金综合力学性能.     

FGH95合金中γ′相稳定性研究

利用扫描电镜和透射电镜观察分析了热等静压HIP FGH95高温合金经热处理后,基体中γ′相的形貌、分布和稳定性。结果表明:合金经热处理后基体为再结晶晶粒与原始枝晶的混晶组织。基体中除了晶界上分布的固溶处理未溶的棒状γ′相颗粒外,在再结晶晶粒内部还存在有大、中、小3种尺寸的γ′颗粒,其中大的方形γ′相颗粒尺寸约为0.5～0.8μm,并呈8个一组排列,此8个一组排列的γ′相颗粒是由合金在1160℃固溶冷却过程中所形成的单个高温γ′相分裂而形成。进一步观察发现,分裂后的方形γ′相颗粒在后续热处理过程中又发生了不稳定分解,在其颗粒内部有细小γ′相的重新析出,并且随着新析出γ′相的长大原来的方形γ′相颗粒逐渐消失。     

FGH95粉末镍基合金组织结构对蠕变机制的影响

通过对热等静压态FGH95合金进行完全热处理、组织形貌观察、点阵常数测定和蠕变曲线测定,研究了FGH95镍基合金的组织结构和蠕变机制.结果表明:合金经热等静压成型后,粗大γ′相沿原始颗粒边界不连续分布,经高温固溶和时效处理后,晶粒尺寸无明显变化,粗大γ′相数量减少,且细小γ′相和MC碳化物在合金中弥散析出,可提高合金蠕变抗力,同时由于γ′相形成元素A1、Ti溶入基体,经XRD谱线测定,γ′相的平均点阵常数减小,而γ体相平均点阵常数增加,致使γ/γ′两相晶格错配度减小;在实验温度和应力范围内,测得合金的蠕变激活能为630.4 kJ/mol.在蠕变期间,FGH95合金的蠕变机制是位错在基体中运动或剪切γ′相,其中,蠕变位错以Orowan机制绕过γ′相,而＜110＞超位错切过y′相发生分解形成(1/3)＜112＞超肖可莱不全位错+层错的位错组态.     

镍基粉末高温合金FGH4096中γ′相完全溶解温度的测定

通过JmatPro软件测试了镍基粉末高温合金FGH4096平衡相图,并根据γ′相平衡态溶解温度采用OM和SEM等方法研究了不同固溶温度下的γ′相溶解结果。结果表明,热力学软件JmatPro计算的FGH4096合金中的γ′相在930~1100 ℃大量溶解,完全溶解温度在1100 ℃以上。从1110 ℃到1130 ℃晶粒尺寸从16.1 μm长大至18.2 μm,变化不明显,从1130 ℃到1160 ℃,晶粒迅速从18.2 μm长大到28.6 μm。镍基粉末高温合金FGH4096中的γ′相起到强化作用的同时,对晶粒长大具有阻碍作用,随着固溶温度从1110 ℃升至1130 ℃,γ′相含量减少,其对晶粒的钉扎作用降低,导致晶粒有所长大。1130 ℃以上时,γ′相完全溶解,γ′相钉扎作用消失,晶粒迅速长大。最终确定FGH4096合金中γ′相实际的完全溶解温度为1130~1140 ℃。     

Hf含量对镍基粉末高温合金中γ′相形态的影响

研究了含Hf镍基粉末高温合金在长期时效处理过程中γ′相形态的演化过程.结果表明:合金在高温长期处理过程中立方状γ′相发生分裂、呈现出二重平行状和八重小立方体组态.八重小立方体组态作为择优形态不再发生分裂,处于低能稳定状态.不同Hf含量合金的错配度发生明显变化,γ′相的长大或粗化过程可以粗略地分为"界面控制"和"应变控制"2个阶段,γ′相间弹性相互作用能对合金中析出相的形态变化起着重要作用.     

挤压工艺参数对FGH96合金棒材显微组织的影响

对FGH96合金进行了不同挤压工艺参数的热挤压变形,研究了挤压温度、挤压比、挤压速度对FGH96合金热挤压棒材的晶粒组织和γ′相的影响,以及γ′相对再结晶晶粒长大的影响。结果表明:在实验选定的挤压工艺参数范围内,FGH96合金均发生了动态再结晶,随着挤压温度的升高,再结晶晶粒尺寸增大;在FGH96合金棒材的显微组织中,大尺寸γ′相呈链状分布于晶界,小尺寸的γ′相弥散分布在晶粒内部;随着挤压温度的升高,晶界处的大尺寸γ′相逐渐溶解,晶界迁移、阻力减小,再结晶晶粒长大,挤压温度为1100℃时,晶界处的大尺寸γ′相开始快速溶解,再结晶晶粒开始明显长大;挤压比和挤压速度的影响主要体现在单位时间内等效应变量和变形潜热对再结晶形核和长大的双重作用上,挤压比或者挤压速度过大或过小均会出现不均匀组织。     

Hf含量对FGH97合金γ/γ′晶格错配度的影响

采用X射线衍射(XRD)方法测算镍基粉末冶金高温合金FGH97中γ和γ′相的晶格常数,计算出γ/γ′晶格错配度。结果表明:γ′相的晶格常数比γ相的小,错配度为负值。Hf 主要存在于γ′相中,随着合金中 Hf 加入量的增加,进入γ′相中 Hf 的数量增加,使γ′相的晶格常数逐渐增大,错配度的绝对值逐渐减小。     

Effect of rapid cold stamping on fracture behavior of long strip S′ phase in Al−Cu−Mg alloy

High-angle annular dark-field scanning transmission electron microscopy and selected area electron diffraction techniques were used to study the mechanism that underlies the influence of rapid cold-stamping deformation on the fracture behavior of the elongated nanoprecipitated phase in extruded Al−Cu−Mg alloy. Results show that the interface between the long strip-shaped S′ phase and the aluminum matrix in the extruded Al−Cu−Mg alloy is flat and breaks during rapid cold-stamping deformation. The breaking mechanisms are distortion and brittle failure, redissolution, and necking. The breakage of the long strip S′ phase increases the contact surface between the S′ phase and the aluminum matrix and improves the interfacial distortion energy. This effect accounts for the higher free energy of the S′ phase than that of the matrix and creates conditions for the redissolution of solute atoms back into the aluminum matrix. The brittle S′ phase produces a resolved step during rapid cold-stamping deformation. This step further accelerates the diffusion of solute atoms and promotes the redissolution of the S′ phase. Thus, the S′ phase necks and separates, and the long strip-shaped S′ phase in the extruded Al−Cu−Mg alloy is broken into a short and thin S′ phase.     

铜模内径对亚快速凝固K424合金析出相的影响

采用阶梯铜模喷铸制备了不同内径的亚快速凝固K424合金,采用时效处理研究了原始非平衡组织状态对快冷合金γ′析出相析出的影响。结果表明:铜模内径的降低可以减弱合金凝固过程中的溶质偏析程度,缩短相变时间,抑制共晶相及析出相形成,有利于获得高固溶组织。经700℃时效30 min处理后,Ф2合金由于形核驱动力高,临界形核半径小,相比Ф6合金优先析出γ′相。当时效温度提高到800℃,低内径铜模基体中可形成均匀分布的析出相,同时形核密度得到显著提高。随时效时间延长,γ′相先快速长大随后缓慢生长,其中Ф2合金由于γ′相过早析出导致其尺寸比相应的Ф6合金更大。析出相析出可以有效增加合金的显微硬度,经800℃时效180 min后Ф2合金硬度高达494 HV0.2,相比原始快冷合金提高13.8%。     

Atom probe tomography analysis of the distribution of rhenium in nickel alloys

Atom probe tomography (APT) is used to characterise the distributions of rhenium in a binary Ni–Re alloy and the nickel-based single-crystal CMSX-4 superalloy. A purpose-built algorithm is developed to quantify the size distribution of solute clusters, and applied to the APT datasets to critique the hypothesis that rhenium is prone to the formation of clusters in these systems. No evidence is found to indicate that rhenium forms solute clusters above the level expected from random fluctuations. In CMSX-4, enrichment of Re is detected in the matrix phase close to the matrix/precipitate (γ/γ′) phase boundaries. Phase field modelling indicates that this is due to the migration of the γ/γ′ interface during cooling from the temperature of operation. Thus, neither clustering of rhenium nor interface enrichments can be the cause of the enhancement in high temperature mechanical properties conferred by rhenium alloying.     

Effect of Interactions Among Elements on Diffusion Process Associated with γ′ Coarsening in a Ni-Based Single-Crystal Superalloy

Coarsening of cuboidal γ' precipitates and relevant diffusion process in Ni-based single-crystal superalloy CMSX-4 were investigated at 1000,1020 and 1040℃ for specific times.The y' coarsening kinetics followed a cubic rate law with time and was presumably controlled by bulk diffusion of elements in y matrix.The associated diffusion activation energy was experimentally determined to be about 300 kJ/mol when it is considered the temperature-dependent thermo-physical parameters in modified Lifshitz-Slyozov-Wagner theory.The influence of temperature on γ/γ' microstructure is briefly discussed based on pseudo-binary [Ni]-[Al] phase diagram.Interactions among elements can effectively raise the local vacancy formation and vacancy-atom exchange barriers close to γ-and γ'-partitioning elements,respectively.Thus,it can significantly reduce the inter-coupling migrations of atoms during the macroscopic cross-diffusion process associated with γ' coarsening of Ni-based superalloys.     

Partitioning and site occupancy of Ta and Mo in Co-base γ/γ′ alloys studied by atom probe tomography

The detailed understanding of solute partitioning and site occupancies of these solutes within the ordered γ′ (L1₂) precipitates holds a key role in the development of cobalt-base γ/γ′ alloys with optimized properties. The present atom probe tomography study utilizes both structural and compositional information to determine the partitioning behavior of transition elements like Ta and Mo between γ matrix and γ′ precipitates and their site occupancy within the γ′ phase. The addition of Ta, which enhances the formation of γ′, to a ternary Co–Al–W alloy with stoichiometric Co₃(Al,W) precipitates, results in the substitution of only the W in the γ′ precipitates to form Co₃(Al, W, Ta) precipitates. Interestingly, Mo, typically considered a γ solid solution strengthener in nickel-base alloys, also partitions strongly to γ′ precipitates when added to the Co–Al–W alloy and displaces only the W atoms. The experimentally observed equal atomic substitution of W by both Ta and Mo, without any change in the Al content within the γ′ precipitates, gives insights into the energetics of relative site substitutions in this ordered compound.     

Re-recognition of the Effects of Phosphorus and Boron on the γ’’ and γ’ Phases in IN718 Alloy

The effects of P and B on the matrix strength and precipitations of γ’ and γ’’ phases in the grain interior were re-recognized in this study. The combination addition of P and B markedly accelerated the precipitations of γ’ and γ’’ phases and strengthened the matrix of IN718 alloy when air-cooled from high temperature, while made no difference when waterquenched from high temperature. The effect of single addition of P on the precipitations of γ’’ and γ’ phases was the same with that of the combination addition of P and B, while the single addition of B had no effect on the precipitations of the two phases. Therefore, it was P rather than B which accelerated the precipitations of γ’ and γ’’ phases. P could take part in the precipitations of γ’ and γ’’ phases, which was revealed by electrochemical extraction and quantitative analysis of chemical composition. It also revealed that P atoms were dissolved in the c matrix to a relatively high degree at the temperature that γ’ and γ’’ phases began to precipitate, and consequently the precipitations of γ’ and γ’’ phases were accelerated. The first-principle calculation indicated that P decreased the formation enthalpies of γ’ and γ’’ phases when it occupied the Ni lattice sites in the two phases, which explained the effect of P on the γ’ and γ’’ phases.     

Microstructural Instability of an Experimental Nickel-Based Single-Crystal Superalloy

Microstructural instability with the precipitation of topologically close-packed (TCP) phases of an experimental nickel-based single-crystal superalloy has been investigated. A significant amount of σ phases are distinguished in the interdendritic region of the as-cast samples after thermal exposure at 900 °C for 1000 h. The σ phases are preferentially precipitated at the periphery of coarse γ/γ′ eutectic, and their morphological evolution from needles to granules is observed. Microstructural analysis suggests that the local segregation of Cr and Ti at the periphery of coarse γ/γ′ eutectic accounts for the formation of σ phases in the as-cast samples. After heat treatment with low solution temperature and short holding time, the dendritic segregation of alloying elements (i.e., W, Re, Ti and Ta) and the volume fraction of γ′ phase in the interdendritic region are similar to that of the as-cast samples. However, no TCP phases are present in the interdendritic region of the heat-treated samples after thermal exposure, which is primarily ascribed to the elimination of local segregation of Cr and Ti near the coarse γ/γ′ eutectic. Moreover, small quantities of μ phases are precipitated in the secondary dendrite arm near the interdendritic region after thermal exposure, due to the increased volume fraction of γ′ phase and the concomitant enrichment of W and Re in the γ matrix.     

FGH95粉末冶金高温合金长期时效的组织稳定性

利用扫描电镜和透射电镜观察了FGH95镍基粉末冶金高温合金在650℃长期时效后的显微结构,评价了该合金在时效过程中的组织稳定性。结果表明,该合金在650℃具有较好的组织稳定性。经500～5000h时效后,合金的主要析出相为γ′相、MC型和M23C6型碳化物,在合金中没有发现TCP相。γ′相在不同热处理时期具有3种不同的尺寸及形貌:尺寸为1～3μm的γ′相,呈不规则块状在晶界析出;尺寸约为500nm的γ′相,呈蝶形均匀分布于基体中,随时效时间延长,其大小、形貌及在基体中的分布稍有变化;更小的γ′相在长期时效过程中经历不规则长大、分裂、再长大和再分裂的循环过程,尺寸在60～200nm范围内变化。合金时效3000h时发现晶界上生成M23C6型碳化物。