反应堆用国产石墨的摩擦表面形貌分析

为探讨石墨材料在氦气和高温条件下的摩擦机理,利用扫描电子显微镜对国产细颗粒石墨和粗颗粒石墨摩擦试验后的表面进行了观察。结果表明,两种石墨在不同试验条件下的摩擦机理不完全相同。但无论那种石墨,只要摩擦表面出现塑性变形,则材料的摩擦系数较大;摩擦表面出现塑性变形和摩擦系数之间存在对应关系,但是否出现塑性变形与氦气和高温条件没有直接关系。     

核级石墨失重率对其氧化速率的影响

采用热重分析方法研究600⁷50℃温度范围内IG-110核级石墨在空气中的氧化行为,分析失重率对其氧化速率的影响。利用随机孔隙模型拟合了IG-110、H-451、NBG-18及NBG-10等4种核级石墨的结构参数,并确定了各自的失重率影响因子表达式。结果表明,随着氧化反应的进行,核级石墨的氧化速率随失重率的增大呈现先增大后减小的趋势,氧化速率的最大值出现在30%750℃温度范围内IG-110核级石墨在空气中的氧化行为,分析失重率对其氧化速率的影响。利用随机孔隙模型拟合了IG-110、H-451、NBG-18及NBG-10等4种核级石墨的结构参数,并确定了各自的失重率影响因子表达式。结果表明,随着氧化反应的进行,核级石墨的氧化速率随失重率的增大呈现先增大后减小的趋势,氧化速率的最大值出现在30%⁴0%失重率范围。使用随机孔隙率模型可以较好地模拟失重率对氧化速率的影响,其中石墨结构参数随核级石墨平均粒径的增加而减少。     

N36锆合金氧化层微观形貌及润湿特性实验研究

研究了国产N36锆合金包壳在600、700℃和800℃常压下形成的氧化层微观形貌和表面润湿特性。对N36锆合金样件进行氧化,并测量了氧化层厚度和表面接触角。对样件表面进行扫描电子显微镜（SEM）观测获得样件的表面微观形貌,利用能谱仪（EDS）对样件表面进行局部扫描获得了成分元素种类和含量分布,分析了氧化温度和氧化时间对于N36锆合金表面润湿性的影响规律。结果表明,氧化后的样件表面润湿性增强,氧化层表面裂纹的尺寸、深度、内部结构都会影响表面润湿性。随着氧化温度升高,裂纹尺寸有增加的趋势。在同一氧化温度下,随着氧化时间的增长,样件表面裂纹的尺寸和数量都有增加的趋势。本文研究有助于深入了解N36锆合金包壳材料表面氧化的微观特性。     

荷电离子轰击靶材料损伤潜径迹的原子水平观测研究

叙述了用扫描隧道显微镜和原子力显微镜观测研究荷电离子轰击靶材料的损伤潜径迹的状况和进展，观测研究了Ａｕ离子和Ｈ＾＋轰击高定向石墨的ＳＴＭ。给出了损伤形貌、损伤范围、表面损伤数密度和离子注入剂量的关系，并对损伤过程进行了分析和讨论。     

核级石墨氧化腐蚀模型研究

高温气冷堆内应用到大量核级石墨材料,对其长期氧化腐蚀行为进行研究至关重要。文章建立了综合考虑石墨内部孔隙率变化及失重率影响的石墨氧化模型,对气体在石墨内部的瞬时氧化腐蚀情况进行了模拟计算。提出氧化深度的概念,研究发现反应温度越高,反应气体在石墨内部的氧化深度越小;并与实验结果及其他模型的计算结果进行了对比,验证了模型的有效性。     

石墨在高纯氦中的高温氧化研究

研究了石墨在高纯氦中的氧化动力学行为。氧化后的样品用扫描电子显微镜进行分析，对可能的氧化机制进行了讨论。实验结果表明：高纯度、高强度、高密度石墨，即“三高”石墨在８００℃高纯氦中的氧化速率最低，等静压石墨次之，０１０石墨最高。     

HTR-10堆芯氧化模拟

对10 MW高温气冷堆(HTR-10)的堆芯模型进行简化,研究燃料元件在正常运行工况下的氧化情况,包括水蒸汽氧化及水蒸汽和氧气的共同氧化情况。结果表明,在燃料元件平均驻留期内石墨材料的水蒸汽腐蚀比较均匀,且主要发生在温度较高的底部;而氧气和水蒸汽对石墨材料的氧化则比较剧烈,底层燃料元件的石墨材料表面被腐蚀掉。     

核级石墨微观孔隙有效扩散系数研究

有效扩散系数是描述石墨内部扩散传质的重要参数,传统经验公式中的单一平均孔径假设无法反映石墨内部复杂的孔隙孔径分布规律及其对扩散的影响,现有核级石墨的有效扩散系数计算公式与实验结果相差较大。考虑到受Knudsen扩散影响,并根据核级石墨微观孔隙孔径分布规律及扩散理论将孔径范围分为两类,从而对有效扩散系数计算公式进行了修正。采用压汞仪对IG110核级石墨未氧化及不同温度下等温氧化样品进行了孔径分析,采用本文修正公式计算了有效扩散系数并与实验测量结果进行了比较。同时对失重率、温度和压力对有效扩散系数的影响进行了讨论。结果发现,修正公式计算结果与核级石墨扩散系数的实验结果相符,提高了核级石墨有效扩散系数的计算精度。有效扩散系数随失重率的增加而升高,失重率低于20%时增长明显。有效扩散系数与温度呈0.528次方关系,与压力大致呈-0.33次方关系。     

基于巴西圆盘试验的国产石墨拉伸强度及特性研究

拉伸强度是石墨构件设计和结构完整性评价的一个重要参数，为研究国产石墨的拉伸强度及试样尺寸、石墨颗粒粒径、微观组织等对拉伸强度的影响，本文选用3种典型国产石墨，即粗颗粒、细颗粒和超细颗粒石墨，对每种石墨的4种不同尺寸规格的试样在拉伸试样机上开展巴西圆盘试验，采用高速相机捕捉劈裂破坏过程，使用扫描电镜观测断口形貌。对比分析了裂纹的扩展过程及破坏形式，测得了拉伸强度并分析了其分布特点，研究了试样尺寸、石墨颗粒粒径、微观组织等对拉伸强度的影响。结果表明：石墨劈裂试验过程满足巴西圆盘试验有效性的要求，试样尺寸越大，石墨颗粒粒径越大，越易产生二次裂纹和局部压缩破坏；通常石墨拉伸强度随试样尺寸的增大而增大，但试样尺寸较小时要综合考虑试样尺寸和颗粒粒径的影响，且材料密度越小尺寸效应越明显；石墨拉伸强度随颗粒粒径的增大呈下降趋势，表现出显著的颗粒粒径效应；石墨拉伸强度具有较大的分散性，其与石墨颗粒粒径表现出明显的相关性，细颗粒石墨拉伸强度的均匀性较粗颗粒石墨好得多，同时超细颗粒石墨明显优于细颗粒石墨；石墨的微观组织对拉伸强度有显著影响，粗颗粒石墨有较多较大的原生孔隙等缺陷，其拉伸强度最小，细颗粒石墨次之...     

核级石墨微观孔隙有效扩散系数研究

有效扩散系数是描述石墨内部扩散传质的重要参数,传统经验公式中的单一平均孔径假设无法反映石墨内部复杂的孔隙孔径分布规律及其对扩散的影响,现有核级石墨的有效扩散系数计算公式与实验结果相差较大。考虑到受Knudsen扩散影响,并根据核级石墨微观孔隙孔径分布规律及扩散理论将孔径范围分为两类,从而对有效扩散系数计算公式进行了修正。采用压汞仪对IG110核级石墨未氧化及不同温度下等温氧化样品进行了孔径分析,采用本文修正公式计算了有效扩散系数并与实验测量结果进行了比较。同时对失重率、温度和压力对有效扩散系数的影响进行了讨论。结果发现,修正公式计算结果与核级石墨扩散系数的实验结果相符,提高了核级石墨有效扩散系数的计算精度。有效扩散系数随失重率的增加而升高,失重率低于20%时增长明显。有效扩散系数与温度呈0.528次方关系,与压力大致呈-0.33次方关系。     

The effect of porosity on the thermal conductivity of nuclear graphite

During service in a high-temperature reactor, graphite will be oxidized by impurities such as water vapour present in the helium coolant. Oxidation will affect the thermal conductivity of the graphite and hence the fuel temperature. This report describes experiments on the effect of oxidation at 1000°C by water vapour of a semi-isotropic moulded graphite. The value of thermal conductivity at room temperature decreases with increasing weight loss, but not linearly, the decreases being most rapid at low weight losses. The percentage change in thermal conductivity is approximately linear with the increase in open porosity.     

Strength Degradation of Oxidized Graphite Support Column in VHTR

Air-ingress events caused by large pipe breaks are important accidents considered in the design of Very High Temperature Gas-Cooled Reactors (VHTRs). A main safety concern for this type of event is the possibility of core collapse following the failure of the graphite support column, which can be oxidized by ingressed air. In this study, the main target is to predict the strength of the oxidized graphite support column. Through compression tests for fresh and oxidized graphite columns, the compressive strength of IG-110 was obtained. The buckling strength of the IG-110 column is expressed using the following empirical straight-line formula: σ _cr,buckling = 91.34—1.01 (L/r). Graphite oxidation in Zone 1 is volume reaction and that in Zone 3 is surface reaction. We notice that the ultimate strength of the graphite column oxidized in Zones 1 and 3 only depends on the slenderness ratio and bulk density. Its strength degradation oxidized in Zone 1 is expressed in the following nondimensional form: σ/σ₀ = exp(—kd), k = 0.114. We found that the strength degradation of a graphite column, oxidized in Zone 3, follows the above buckling empirical formula as the slenderness of the column changes.     

Oxidation behavior of IG and NBG nuclear graphites

This work studies the oxidation-induced characteristics of four nuclear graphites (NBG-17, NBG-25, IG-110, and IG-430). The oxidation characteristics of the nuclear graphites were measured at 600 °C. The surface properties of the oxidation graphites were characterized by means of scanning electron microscopy, X-ray photoelectron spectroscopy, and contact angle methods. The N₂/77 K adsorption isotherm characteristics, including the specific surface area and micropore volume, were investigated by means of BET and t-plot methods. The experimental results show an increase in the average pore size of graphites; they also show that oxidation produces the surface functional groups on the graphite surfaces. The surface area of each graphite behaves in a unique manner. For example the surface area of NBG-17 increases slightly whereas the surface area of IG-110 increases significantly. This result confirms that the original surface state of each graphite is unique.     

Investigation of oxidation behaviors of nuclear graphite being developed and IG-110 based on gas analysis

The oxidation behaviors of the nuclear graphite being developed were investigated using gas chromatograph at 873–1373 K. The oxidation experiments were carried out with the gas flow rate of 0.2 L/min and the oxygen concentrations of 7, 10 and 20 mol%. The oxidation reaction began at 973 K and was accelerated with the increase of temperature. At 1173–1273 K, the oxidation was limited by oxygen supplied to graphite and the reaction rate held steady. From 1273 to 1373 K, the oxidation rate increased obviously due to the significant reaction between CO₂ and graphite. At the low temperature regime (973–1073 K), the apparent activation energies with the oxygen mole fractions of 7%, 10% and 20% were 298, 324 and 321 kJ/mol, respectively. Scanning electron microscope was applied to reveal the pore development of the graphite oxidized at different temperatures. The effect of CO combustion at temperature below 1173 K was discussed based on the oxidation behaviors of the graphite being developed and IG-110. It was suggested that the ASTM D7542-15 standard should be adjusted to fit some popular graphite, such as graphite IG-110.     

The modeling of graphite oxidation behavior for HTGR fuel coolant channels under normal operating conditions

The oxidation of graphite in normal operating conditions is a very important factor when evaluating the service time of the graphite structural material in a high temperature gas-cooled reactor (HTGR). This paper deals with the modeling of graphite oxidation by steam in the helium channel of a fuel block. The FEM software COMSOL is used: the turbulent flow of the coolant is simulated by using the k-? model and the chemical reaction is expressed by the Langmuir-Hinshelwood equation. Calculations were carried out for steam pressures around 1 Pa and for different temperature distributions. The influence of burn-off and the diffusion in graphite porosities were both considered in the oxidation. Results show that oxidation mainly occurred on the graphite surface at the bottom of the core because of the higher temperature. The thickness of graphite with a burn-off higher than 8% was about 1 mm at the core base. Less than 15% of steam was consumed in the coolant channel of the fuel assemblies. Calculations also showed that the mean gasification rate in one channel for the second service time was larger than the first service time.     

Oxidative erosion of graphite in air between 600 and 1000 K

The oxidative erosion of seven types of graphite has been investigated by heating in air at temperatures between 600 and 1000 K. The specimens include pyrolytic graphite, fine-grain graphites, carbon-fibre composites (CFC), and graphites doped with Si and Ti. The weight loss was measured using a microbalance, the surface morphology by scanning electron microscopy, and the composition of the surface layer by MeV ion beam techniques. Pyrolytic graphite is least affected by erosion, while pure and Si-doped CFCs erode particularly fast. Typical erosion rates for specimens with a surface area of ?4 cm² are below 0.2 μg/m² s at 600 K for all graphite types, and at 900 K range from 0.34 mg/m² s for pyrolytic graphite to about 9 mg/m² s for the strongest eroding types. The temperature dependence of the erosion rate of all types of graphite studied is well described by an activation energy of 1.7 eV. The erosion rates of these graphites are by far lower than the removal rates for deposited amorphous hydrocarbon layers. In contrast to all other types, the Ti-doped graphite absorbs a significant amount of oxygen reaching up to ?5% of its original mass. Once the oxygen uptake is saturated, it erodes with rates similar to those of the strongest eroding types.     

Ductility Loss of Zircaloy Cladding by Inner-Surface Oxidation during High Temperature Transient

Under a LOCA transient in LWRs, ruptured Zircaloy clad tubes would be oxidized at the inner surface as well as outer surface by steam flowing in reactor core. In order to determine whether the inner-surface oxidation influences mechanical properties of clad tubes during the reflood stage of a LOCA, the ring compression tests were conducted on oxidized tube specimens and segments sectioned from ruptured claddings obtained from rod-burst/oxidation tests ranging from 1,200 to 1,500 K.

The degradation of the fracture load and the deflection at 373 K are largely influenced by the hydrogen absorption during the inner-surface oxidation. The oxidation temperature and the time dependence of the ductility loss of Zircaloy clad tubes can be represented by iso-deflection lines. The iso-deflection lines due to the hydrogen absorption limit the permissible oxidation condition to a lower temperature and shorter period of exposure time, comparing with sole oxygen uptake.     

孔隙率对核级石墨氧化的影响

核级石墨在高温气冷堆中作为结构材料、慢化材料和反射层材料等被广泛应用,其氧化性能对高温气冷堆在进水或进气事故下材料的腐蚀行为有重要影响。初始孔隙率分布及孔隙率在氧化过程中的变化均对石墨氧化造成影响。本文以核级石墨IG-110、H-451、NBG-18和A3-3为例,以直径为6 cm的石墨球为研究对象,在一维瞬态氧化模型的基础上,分析了初始孔隙率分别服从均匀分布、正态分布和对数正态分布时对石墨氧化的影响。从模型简化和高温气冷堆安全分析角度保守考虑,建立石墨氧化模型时,核级石墨初始孔隙率可取均匀分布,此时石墨的整体失重率最大。