APT和萃取复型研究压力容器模拟钢中富Cu团簇的析出

用原子探针层析技术(APT)和萃取复型方法研究了核反应堆压力容器模拟钢中富Cu原子团簇的析出.提高了Cu含量的压力容器模拟钢经过880℃水淬,再经过660℃/10 h调质处理,随后在370℃进行不同时间的时效处理,利用APT对时效4500 h的样品分析结果显示,样品中富Cu原子团簇的数量密度达到3.1×1023m-3....     

Mn含量对Fe-Cu-Mn-Ni合金中富Cu相析出影响的相场法研究

通过耦合CALPHAD热力学数据库建立了一个模拟多元合金固态相变过程中微观组织演变的相场模型，并以Fe-Cu-Mn-Ni合金为例，从动力学角度揭示了Mn含量对富Cu相析出机制的影响。结果表明：随着富Cu相的析出，Mn和Ni原子在富Cu相的中心发生偏聚，导致在富Cu相界面形成B2环。Mn含量变化会改变富Cu相的形貌和析出机制。在Mn含量较低时，富Cu相仅发生Ostwald粗化，其形貌为球形；而在Mn含量较高时，富Cu相的粗化机制包括Ostwald粗化和合并长大，其形貌从球形转变为棒状。提高Mn含量会促进富Cu相的析出，其体积分数和半径也增大，但数量减少。     

利用APT对RPV模拟钢中富Cu原子团簇析出的研究

提高了Cu含量的核反应堆压力容器（RPV）模拟钢经过880℃水淬和660℃调质处理,在370℃时效不同时间后,利用原子探针层析技术（APT）进行分析.结果表明:样品经过1150 h时效后,富Cu团簇正处于析出过程的形核阶段;经过3000和13200 h时效后析出了富Cu团簇,团簇的平均等效直径分别为1.5和2.4 nm,团簇中Cu的平均浓度分别为45%和55%（原子分数）,团簇的数量密度约为4.2×10²²m^-3;样品经过13200 h时效后,α-Re基体中的Cu含量为（0.15±0.02）%,仍然高于Cu在α-Fe中平衡固溶度的理论计算值,说明这时富Cu团簇的析出过程还没有达到平衡.对渗碳体的分析结果表明,Ni,Si和P偏聚在渗碳体和α-Fe基体的相界面附近,Mn,Mo和S富集在渗碳体中;并没有观察到Cu在相界面上偏聚的现象.     

利用APT对RPV模拟钢中富Cu原子团簇析出的研究

提高了Cu含量的核反应堆压力容器（RPV）模拟钢经过880℃水淬和660℃调质处理,在370℃时效不同时间后,利用原子探针层析技术（APT）进行分析.结果表明:样品经过1150 h时效后,富Cu团簇正处于析出过程的形核阶段;经过3000和13200 h时效后析出了富Cu团簇,团簇的平均等效直径分别为1.5和2.4 nm,团簇中Cu的平均浓度分别为45%和55%（原子分数）,团簇的数量密度约为4.2×10²²m^-3;样品经过13200 h时效后,α-Fe基体中的Cu含量为（0.15±0.02）%,仍然高于Cu在α-Fe中平衡固溶度的理论计算值,说明这时富Cu团簇的析出过程还没有达到平衡.对渗碳体的分析结果表明,Ni,Si和P偏聚在渗碳体和α-Fe基体的相界面附近,Mn,Mo和S富集在渗碳体中;并没有观察到Cu在相界面上偏聚的现象.     

利用APT研究铁素体时效钢中富Cu相和碳化物的偏析行为

铁素体时效钢样品经过880℃水淬、660℃调质处理,然后400℃时效4000 h后,利用三维原子探针层析技术(APT)研究了时效钢中晶界和基体中富Cu析出相和碳化物的偏析行为。结果表明:分析区域中Mn、Ni、Mo、C和Cu元素更容易在晶界处偏聚,形成富Cu团簇和碳化物,晶界处的纳米富Cu相为短棒状,其尺寸大小约为6 nm,团簇中的Cu原子含量为40at%。基体中的纳米团簇近似为球状,其尺寸和团簇中的Cu原子的数量密度都比晶界处小。在晶界处析出的富Cu团簇在碳化物之间,形成一种"夹层结构"。此外,富Cu团簇内部有Mn和Ni原子的偏聚,促进富Cu相的析出。     

富Cu团簇的析出对RPV模拟钢韧-脆转变温度的影响

将Cu含量高于实际核反应堆压力容器（RPV）钢的模拟钢在880℃水淬后,在660℃进行调质处理,然后在370℃时效不同时间,采用TEM,原子探针层析法（APT）和冲击实验对其进行研究.结果表明,时效1150 h后,富Cu团簇的析出仍处于形核阶段,对韧-脆转变温度（DBTT）没有明显的影响;时效3000 h后,试样中析出了平均尺寸为1.5 nm的富Cu团簇,主要分布在位错线上,数量密度达到4.2×10²²m^-3,DBTT由调质处理后的-100℃升高至-60℃;时效13200 h后,富Cu团簇略有长大,平均尺寸达到2.4 nm,团簇的数量密度与时效3000 h的试样处于相同数量级,DBTT升高至-45℃.采用热时效方法使富Cu团簇析出后,DBTT只提高了55℃,没有中子辐照引起的那样显著,这不仅是因为富Cu团簇的数量密度低,基体中没有中子辐照产生的晶体缺陷也是重要的原因.     

RPV模拟钢中纳米富Cu相的析出和结构演化研究

提高了Cu含量的核反应堆压力容器(RPV)模拟钢经过880℃水淬和660℃调质处理后,在370℃时效6000 h,利用HRTEM,EDS和原子探针层析(APT)方法研究了纳米富Cu相的析出过程和晶体结构演化.观察到Cu原子在α-Fe基体的{110}晶面上以3层为周期发生偏聚,并产生了很大的内应力使晶格发生畸变,这是富Cu相析出时的形核过程;随着Cu含量的增加和富Cu区的扩大,内应力也随着增大,富Cu区沿着α-Fe基体的{110}晶面发生切变,形成了ABC/BCA/CAB/ABC排列的多孪晶9R结构;Cu含量继续增加,富Cu相最终转变为fcc结构.富Cu相的尺寸在1-8nm范围内,数量密度为0.71×10~(23)m~(-3).富Cu相中还含有3%- 8%(质量分数)的Ni和Mn.并且在相界面上发生偏聚,从而抑制了富Cu相的长大.     

Mn含量对Fe-Cu-Mn合金纳米富Cu析出相影响的相场法研究

采用相场法模拟了Fe-Cu-Mn合金在823 K时效时富Cu析出相的三维组织演化图像、体积分数、数量密度和平均颗粒半径随时效时间的变化等。相场模拟研究表明:相分离早期阶段通过失稳分解机制形成富Cu相;同时Mn原子也在富Cu相的中心发生偏聚,在富Cu相开始Ostwald粗化的过程中,Mn原子又从其核心处偏聚到富Cu相和基体的界面处,最终在富Cu相外部形成富Mn环。富Mn环的存在会抑制富Cu相的扩散长大和粗化;富Cu相在时效前期是球状的bcc结构,随着不断长大,转变为椭球形或棒状的fcc结构;提高Mn含量可以加快富Cu相的析出,有利于富Cu相的粗化。     

自然时效对Al-2.95Cu-1.55Li-0.57Mg-0.18Zr合金160℃人工时效的影响EI北大核心CSCD

针对Al-Cu-Li-Mg合金中自然时效对后续人工时效析出行为的影响机制问题,借助TEM、三维原子探针(3DAP)、三维重构(3DET)及力学性能测试等实验方法,系统研究了自然时效对Al-2.95Cu-1.55Li-0.57Mg-0.18Zr合金在160℃人工时效时微观组织及力学性能的影响。结果表明,自然时效形成的富Mg或Cu-Mg原子团簇及δ'相在人工时效早期溶解,导致硬度下降;随后大量的GPB区弥散均匀析出,硬度回升,随时效时间延长T1相析出,硬度进一步增加,在96 h出现第一个强化峰;随后,GPB区溶解,合金硬度降低;继续延长时效时间,T1相体积分数及板条状S相的数量增加,合金硬度再次升高,在192 h出现第二个强化峰。研究表明自然时效原子团簇可明显改变合金的人工时效析出行为及力学性能演变规律。     

低碳低合金钢中纳米富Cu相的析出特征

低碳低合金钢样品经880℃加热0.5 h后水淬,再进行660℃保温10 h的调质处理,最后分别在370℃和400℃等温时效3000 h和2000 h后,利用高分辨透射电镜(HRTEM)、能谱仪(EDS)以及三维原子探针(3DAP)相结合的方法,分析低碳低合金钢中析出的纳米富Cu相的晶体结构和Cu、Mn、Ni原子分布特征。在HRTEM图像中观察到长轴约9.3 nm,短轴约6.1 nm的短棒状纳米富Cu相,其结构为正交9R结构且互为孪生关系,其中9R结构与α-Fe基体存在一定位向关系,即:(011)_(bcc)//(114)_(9R),[111]_(bcc)//[110]_(9R)。说明Cu早期析出时可能由bcc结构优先转变孪晶正交9R结构,而不是直接转变为fcc结构。利用3DAP技术可以看出,在富Cu原子团簇形核长大过程中,Mn、Ni原子会偏聚在Cu与α-Fe基体的界面处,造成这种现象,除了富Cu原子团簇在富Ni、富Mn区域形核且在长大过程不断向外排挤Mn、Ni原子外,Cu与α-Fe基体界面存在较高的共格畸变能也会造成Mn、Ni原子的偏聚,进而阻碍富Cu原子团簇的长大。     

Synergistic effects of Cu and Ni on nanoscale precipitation and mechanical properties of high-strength steels

There is an increasing demand for ultrahigh-strength ferritic steels strengthened by nanoprecipitates. Improvement of the precipitation strengthening response requires an understanding of the nanoscale precipitation mechanisms. In this study, the synergistic effects of Cu and Ni on nanoscale precipitation and mechanical properties of ferritic steels were thoroughly investigated, and new steels with ultrahigh strength and high ductility have been developed. Our results indicate that Ni effectively increases the number density of Cu-rich nanoprecipitates by more than an order of magnitude, leading to a substantial increase in yield strength. It appears that Ni decreases both the strain energy for nucleation and the interfacial energy between the nucleus and the matrix, thereby decreasing the critical energy for nucleation of Cu-rich nanoprecipitates. Cu and Ni are also found to be beneficial to grain-size refinement, resulting from lowering the austenite-to-ferrite transformation temperature, as determined from thermodynamic calculations. In addition, the strengthening mechanisms of Cu and Ni were quantitatively evaluated in terms of precipitation strengthening, grain refinement strengthening and solid-solution strengthening. The current findings shed light on the composition–microstructure–property relationships in nanoprecipitate-strengthened ferritic steels.     

Compositional Variants of Cu-rich Precipitate in Thermally Aged Ferritic Steel

Atom probe tomography was utilized to investigate Cu precipitation in a high-strength low-alloy steel isothermally aged at 500℃ for 1, 4, 16, and 64 h after water-quenching from 900℃. With prolonged aging time, the Curich precipitates(CRPs) increased in size and decreased in number density, and gradually evolved from spheroidal to elliptical in morphology. The small CRPs were rich in a high amount of Fe and a certain amount of Ni and Mn at their early nucleation stage. The large CRPs with increased size due to extensive aging contained less Fe and more Cu at their later growth stage. Additionally, Ni and Mn were both readily to segregate at the CRP/matrix heterophase interfaces, and Mn was higher in content than Ni in the precipitate interior especially when the CRPs were large in size.     

Ni含量对0Cr17Ni4Cu4Nb不锈钢富铜相析出的影响

研究了不同Ni含量的0Cr17Ni4Cu4Nb不锈钢在1040℃固溶后油冷和炉冷(均进行480℃时效,分别表示为OC、FC试样)两种热处理工艺下的力学性能和微观组织变化规律,通过力学性能测试、SEM和TEM观察,探讨了Ni含量对力学性能和富铜相析出的影响.研究表明:FC试样的强度由于炉冷过程中析出了粗大的富铜相而显著低于OC试样的;随Ni含量的提高,两种试样的强度均增加,但差距在缩小,其原因是炉冷过程中析出的富铜相尺寸逐渐细小,表明Ni可以提高了Cu在γ相区的溶解度,延缓了固溶后炉冷过程中的富铜相析出;随时效温度的提高,不同Ni含量试验钢的强度降低,且Ni含量高的试验钢强度降低更显著;随Ni含量的提高,时效过程中富铜相的形核速率和长大速度增加,表明Ni降低了Cu在钢中的扩散激活能.     

Radiation-induced precipitation in a ferritic model alloy: An experimental and theoretical study

The radiation embrittlement of low-alloyed reactor pressure vessel steels is partly due to the formation of nanometer-sized solute clusters (Mn, Si, Ni, Cu and P). In order to determine if radiation-induced mechanisms can take part in the solute clustering, an under-saturated binary Fe–1 at.% Mn alloy was irradiated with Fe ions at 400 °C. After irradiation, atom probe tomography experiments revealed that a high density of Mn-rich clusters is formed. This observation clearly demonstrates that, under these irradiation conditions, Mn clustering in this model alloy is radiation-induced and not radiation-enhanced. Mn-rich clusters were not distributed homogeneously in the analyzed volume but were heterogeneously precipitated on a planar object, suggesting a grain boundary (GB) or a dislocation loop. In parallel, a rate theory model calibrated on the population of point defect (PD) clusters measured by transmission electron microscopy has shown that the dominant sinks for mobile PDs are PD clusters. Thus Mn clustering could be explained by Mn atoms dragged by mobile PD fluxes towards sinks such as PD clusters or GBs. According to the model, most of the dragging occurs via isolated interstitials. These results are in very good agreement with previous studies, suggesting a correlation of position between solute-rich clusters and sinks.     

铜偏聚区的高分辨电镜分析

研究铜在钢中的时效强化和沉淀规律具有理论意义和实用价值。应用JEM-2010高分辨电镜研究了Fe-1．18Cu、Fe-1．55Cu高纯钢在时效时组织结构的变化规律,发现,含铜高纯钢固溶处理后,在550℃、650℃时效过程中,首先在铁素体晶粒中析出含铜偏聚区,铜原子偏聚在（001）α晶面上。在时效峰处为富铜的G、P区颗粒,其直径为4—20nm,呈层状的圆饼状,一般5—9层,富铜层和贫铜层相间分布,每一层厚度约为1—2nm。G、P区与铁素体基体半共格。G．P区的富铜区内及周边存在高密度位错和层错。在过时效初期,含铜偏聚区颗粒长大,偏聚区内富铜层和贫铜层的数量增多,富铜层厚度减小,位错密度降低。在铁素体基体上弥散分布的G．P区是含铜高纯钢时效强化的原因。     

Phase decomposition of the γ phase in a Mn–30 at.% Cu alloy during aging

The phase decomposition process of γ phase in a Mn–30 at.% Cu alloy, when aged at 723 K from 2 to 50 h, is investigated with electrical resistivity and magnetic susceptibility measurement. In conjunction with the antiferro-magnetic transition of the Mn-rich regions during cooling to room temperature from the aging temperature, the temperature coefficient of electrical resistivity shows a continuous increase in a certain temperature range. The temperature where the coefficient has the maximum increasing rate is defined as the T_N temperature of the Mn-rich regions. It was found that the T_N temperature was 20–30 K higher than the concomitant f.c.c.–f.c.t. transformation temperature T_t, determined with the minima of Young’s modulus in the aged samples. The increment of temperature coefficient of electrical resistivity involved in the magnetic transition is used to estimate the changes of volume fraction for Mn-rich regions vs aging time. At the same time, the paramagnetic feature above the spin-freezing transition temperature for quenched Cu-rich alloys is summarized, and the Mn concentration in Cu-rich regions of aged samples is calculated. It should be noted that Mn and Cu-rich regions had already formed in the 2 h-aged Mn–30 at.% Cu sample, and longer aging further enriched Mn or Cu, while the volume fraction of Mn-rich regions decreased slightly with aging time. Electrical resistivity measurement sensitive to Mn-rich regions and the magnetic susceptibility measurement for Cu-rich regions have shown the compositional heterogeneity in decomposed phases. TEM observation confirms the interconnectivity of the two regions in the aged microstructure. All the results support the hypothesis that the decomposition of γ phase in Mn–Cu alloys proceeds in the spinodal manner.     

Electrochemical characteristics of 316l stainless steel processed with a thermally treated Ni- and Cr-rich surface coating

The influence of a thermally treated Ni-Cr rich protective coating on the corrosion behavior and contact resistance of stainless steel in a 0.1NH₂SO₄+ 2 ppmHF electrolyte at 80 °C was evaluated using electrochemicals, interfacial contact resistance (ICR) measurements and X-ray photoelectron spectroscopy. Through a low-cost, continuous production line, the Ni-rich coating film for stainless steels was developed by dipping steel samples in acrylic resin and CrO₃ solutions with different levels of NiSO₄·6H₂O added as a nickel source. Each sample was then heated at 800 for 10 min in a hydrogen-reducing environment. It was shown that an increase in residual Ni content in the surface coating noticeably lowered the interfacial contact resistance and raised the corrosion resistance, depending on the remaining nickel content and the thickness of the surface coatings. In support of the XPS depth profile, this was ascribed to the relative enrichment of the Ni element and the detectable reduction of oxygen content in the coating, which could be associated with the significant evaporation of acrylic resin that occurred during thermal treatment. The optimum Ni composition in the resultant coating film, achieved through the addition of 15 wt.% NiSO₄·6H₂O to the acrylic resin and CrO₃ solution, was estimated to be about 10 wt.%.