正电子湮没研究Al、Nb共掺CaCu_3Ti_4O_(12)陶瓷高介电常数机理

关于CaCu_3Ti_4O_(12)陶瓷的高介电常数机理,目前广泛接受的是非本征的内阻挡层电容模型。该模型认为在多晶中元素变价、缺陷和非化学计量比等导致的半导化晶粒被绝缘晶界层,即内阻挡层所包围。其中内阻挡层的厚度对材料的介电性能影响较大,而扫描电子显微镜(SEM)测试表明样品晶界呈稀烂的果酱状,SEM难以测量晶界区域绝缘内阻挡层厚度。本文采用正电子湮没技术表征其厚度,通过对CaCu_3Ti_4O_(12)陶瓷共掺不同浓度的Al、Nb(CaCu_3Ti_(4-x)Al_(0.5x)Nb_(0.5x)O_(12),x=0.2%、0.5%、5.0%)改变其晶粒和晶界的微观结构,研究CaCu_3Ti_4O_(12)陶瓷高介电常数机理。正电子湮没结果显示,掺杂样品符合多普勒展宽谱S参数的变化趋势与平均寿命的变化趋势一致。x=0.5%掺杂样品的介电常数最高,其平均寿命、S参数和湮没长寿命成分均最小,阻挡层最薄。实验结果验证了描述CaCu_3Ti_4O_(12)陶瓷高介电常数机理的内阻挡层电容模型的预测。     

Er2Ti2O7烧绿石基玻璃陶瓷固化体的制备工艺研究

为获得含单一钛酸盐烧绿石的玻璃陶瓷固化体,本文以Er₂Ti₂O₇作为钛酸盐烧绿石代表,在传统的烧结法制备工艺基础上,通过热雾喷解和晶核掺入的技术改进,分别研究了烧结温度、烧结时间、玻璃与陶瓷晶核质量配比等参数对Er₂Ti₂O₇基玻璃陶瓷固化体物相及结构的影响规律。XRD结果表明：在不同的烧结温度、烧结时间和质量配比下,均能获得含单一Er₂Ti₂O₇烧绿石的玻璃陶瓷固化体,Er₂Ti₂O₇前驱体在玻璃中的相稳定性好,未发生相分解,玻璃组分亦未受陶瓷相的影响而析出第二相;玻璃组分对陶瓷颗粒存在张应力作用,玻璃含量越高,Er₂Ti₂O₇的晶胞常数越大;提高烧结温度和烧结时间均有利于增强固化体中Er₂Ti₂O₇的结构有序性,但烧结温度效果强于烧结时间。SEM结果表明：Er₂Ti₂O₇在玻璃基体上呈四方形生长,与玻璃界面清晰,相容性好。固化体的物性测试结果表明,玻璃组分占比将直接影响固化体的表观孔隙率和致密度。根据以上结果可知,新工艺制备的样品具有相纯度高、烧绿石相与玻璃相容性好、两相比例可调等优点,较好地解决了钛酸盐烧绿石在玻璃基体中易发生相分解的问题。     

Fe掺杂CuAlO_2的微结构和热电性能的正电子湮没研究

测量了CuAl1-xFexO2样品的X射线衍射图、热电性能、符合正电子湮没辐射多谱勒展宽谱和寿命谱。结果表明,在CuAlO2中加入少量的Fe(x≤0.10),样品的正电子湮没辐射多谱勒展宽谱的3d信号增强,正电子S参数、正电子平均寿命和电阻率降低;当Fe含量较高(x0.10)时,随Fe含量增加,CuAl1-xFexO2样品的正电子湮没辐射多谱勒展宽谱的3d信号降低,正电子S参数、正电子平均寿命和电阻率升高。CuAl1-xFexO2室温Seebeck系数随样品中缺陷浓度升高。讨论了Fe掺杂对CuAlO2微结构和热电性能的影响。     

钙钛锆石的自蔓延高温合成与热力学分析

基于自蔓延高温合成法,采用Fe₂O₃、CrO₃和Ca(NO₃)₂为氧化剂,Ti为还原剂制备了钙钛锆石。共设计了4个体系,计算了各体系的绝热温度,测量了各体系的实际燃烧温度,并探索了Ca(NO₃)₂为氧化剂时,TiO₂与Ti摩尔比（TiO₂∶Ti）对燃烧温度的影响。结果显示,所有体系均能自持发生,但以Fe₂O₃和CrO₃为氧化剂时,产物的主要物相为烧绿石(Ca₂Ti₂O₆)、Zr₅Ti₇O₂₄、钙钛矿(CaTiO₃)及少量TiO₂,以Ca(NO₃)₂为氧化剂时,各体系的主要物相均为钙钛锆石(CaZrTi₂O₇)、CaTiO₃及少量TiO₂。同时,以Ca(NO₃)₂为氧化剂时,随TiO₂∶Ti的降低,燃烧温度和绝热温度均逐渐升高。     

钙含量对钙钛锆石-钡硼硅酸盐玻璃陶瓷结构的影响

采用熔融-热处理工艺制备SiO₂-Na₂O-B₂O₃-BaO-CaO-TiO₂-ZrO₂体系玻璃陶瓷,利用差热分析法（DTA）、傅氏转换红外线光谱分析仪（FTIR）、X射线衍射仪（XRD）、扫描电子显微镜（SEM）等技术手段研究了晶核剂（CaO、TiO₂和ZrO₂）总含量为45%时,不同钙含量（CaO∶TiO₂∶ZrO₂=x∶2∶1（摩尔比）,x=0.5～6）对玻璃陶瓷晶相和显微结构的影响,并采用粉末静态浸泡法（PCT）测试了C₂（即x=2）玻璃陶瓷样品的抗浸出性能。结果表明：玻璃网络结构主要由［SiO₄］、［BO₃］和［BO₄］构成,随着Ca含量的增加,更多的B以［BO₄］加入玻璃网络中,玻璃转变温度T_g逐渐升高,放热峰温度逐渐降低,但峰强逐渐增高;x＜2时,样品中除CaZrTi₂O₇晶相外还有其他晶相（如TiO₂和ZrO₂）出现;当x=2和4时,样品中只有单一的CaZrTi₂O₇晶相;x=6时,有星状的CaZrTi₂O₇和柱状的CaTiO₃晶相生成。PCT实验结果表明：B、Na、Ca元素的归一化浸出率随浸泡时间的增加而降低,并在28 d后保持不变,分别为8.4、7.8、2.2 mg/(m²•d),与硼硅酸盐玻璃固化体浸出率处于同一数量级。     

掺杂Cr2O3对UO2芯块烧结行为的影响

提高燃料燃耗的一个有效手段是通过增大UO₂晶粒尺寸来减少元件内部气体压力,在大晶粒UO₂芯块中,裂变气体到达晶界表面的距离增加,因而裂变气体的释放速率降低,元件内部气体压力的增高缓慢。本文研究了添加Cr₂O₃对UO₂晶粒尺寸的影响。对纯UO₂、添加0.5% Cr₂O₃及5% Cr₂O₃ 3种配方的芯块进行了试验,在5%H₂Ar保护下,以10 ℃/min和5 ℃/min的升温速率升温至1 700 ℃,然后烧结2 h或4 h,对比纯UO₂芯块与添加Cr₂O₃的芯块发现,添加Cr₂O₃可有效增大晶粒尺寸;较长的烧结时间可促进晶粒长大;较低的升温速率也使晶粒长大。烧结过程产生液相烧结,液相浸润晶粒边界,促进晶粒长大。     

添加纳米Y2O3的ODS-HT9钢的显微结构和性能

为了研究纳米Y₂O₃对HT9钢的显微结构和力学性能的影响,采用粉末冶金工艺,制备了纳米Y₂O₃含量为0.1%~0.9%的ODS-HT9钢样品,测定了样品的抗拉强度、伸长率、维氏硬度等力学性能,利用透射电子显微镜（TEM）观察和分析了样品中纳米Y₂O₃颗粒的分布状况、形状和相结构,利用扫描电子显镜（SEM）观察了样品拉伸断口的形貌。研究表明,球磨和热压烧结后,纳米Y₂O₃颗粒能够均匀地分布于基体中,相结构和形状未发生明显变化。弥散分布的纳米Y₂O₃硬质颗粒,具有明显的弥散强化作用,导致ODS-HT9钢的抗拉强度和维氏硬度随Y₂O₃含量的增加而显著增加,伸长率显著降低。Y₂O₃含量低于0.7%时,样品以韧性断裂为主,进一步增加含量,断裂方式将由韧性断裂转变成脆性断裂。纳米Y₂O₃含量为0.3%~0.5%的ODS-HT9钢,抗拉强度达到了913~936 MPa,伸长率为10.7%~11.2%,具有良好的综合力学性能。本文研究结果有助于ODS-HT9钢高温性能的研究及其在反应堆中的实际应用。      

P2O5对模拟高放玻璃固化体析晶和抗浸出性能的影响

针对高放废液硼硅酸盐玻璃固化体易析出辉石晶相的问题,本文采用P₂O₅部分替代硼硅酸盐基础玻璃配方中的MgO和CaO,研究了P₂O₅掺量(质量分数为0～8%)对玻璃固化体析晶和抗浸出性能的影响。结果表明,当P₂O₅掺量为0～3%时,样品为无定形态,在850℃热处理6 h后,P₂O₅掺量为0～2%的样品主要析出辉石晶相,而P₂O₅掺量为3%的样品析出了少量硅酸钙晶相,辉石晶相基本消失;当P₂O₅掺量高于3%时,样品析出球形Na₃Ca₆(PO₄)₅晶体,且析晶度随P₂O₅掺量的增加而升高。²⁹Si MAS NMR和¹¹BMAS NMR分析表明,随着P_...     

Al2O3对独居石玻璃陶瓷固化体的影响

本文研究了Al₂O₃掺量对独居石玻璃陶瓷固化体结构和化学稳定性的影响。用傅里叶变换红外光谱（FTIR）和X射线衍射（XRD）方法表征样品结构,用溶解速率法和全谱直读等离子体发射光谱（ICP-OES）分别测定样品在浸出液中浸泡后的失重速率及各元素的浸出浓度,以研究固化体的化学稳定性。研究结果表明：当Al₂O₃掺量为4%（摩尔分数）时,在980 ℃下保温3 h得到的独居石玻璃陶瓷固化体具有较高的化学稳定性,浸泡14 d时其质量浸出率最低,约为8.1 ng/(cm²•min),其中Ce、La元素在浸出液中均未检出;固化体的主晶相为独居石,结构中含有大量稳定的正磷酸基团［PO₄］^3-和少量的焦磷酸基团［P₂O₇］^4-,不存在偏磷酸基团［PO₃］^-。     

采用凝胶注模成型工艺研制Al2O3-B4C环形芯块

凝胶注模成型是一种原位成型工艺,是制备复杂形状的陶瓷部件的理想工艺。本文采用凝胶注模成型工艺制备Al₂O₃-B₄C环形芯块,主要研究了高固相、低黏度陶瓷浆料的制备,胶凝成型,Al₂O₃-B₄C材料的烧结致密化等。结果表明：实验制备的Al₂O₃-B₄C环形芯块的壁厚为1 mm左右,B₄C含量在0.5%~12%之间,芯块的烧结密度在65%TD~93%TD之间。Al₂O₃-B₄C环形芯块满足压水堆可燃毒物材料设计的要求。     

Transformation of Al2O3 to LiAlO2 in Pb–17Li at 800 °C

A FeCrAl substrate was pre-oxidized for 2 h at 1000 °C to thermally grow an external Al₂O₃ scale and then isothermally exposed to Pb–17 at.% Li for 1000 h at 800 °C to determine if this layer would protect the underlying alloy from dissolution. After exposure, a small mass gain was measured, indicating that the layer did inhibit dissolution. However, characterization of the external layer determined that it had transformed to LiAlO₂ with an increased thickness and a much larger grain size than the original layer. This observation has implications for the use of Al₂O₃ as a permeation barrier in Pb–Li cooled fusion blanket systems.     

Gd2O3-Nd2O3-ZrO2-CeO2体系的高温固相反应研究

为研究Gd₂O₃-Nd₂O₃-ZrO₂-CeO₂四元氧化物体系的高温固相反应,以Gd₂O₃、Nd₂O₃、ZrO₂、CeO₂混合粉体为原材料,在1 673 K和1 773 K温度下煅烧24、48、72 h,分别制备了系列样品,并对合成样品进行了XRD和SEM分析。结果表明,合成产物为具有缺陷萤石相且伴有少量烧绿石相的Gd_2-xNd_xZr_2-xCe_xO₇（0≤x≤2）晶体化合物。随着煅烧温度的升高和煅烧时间的延长,产物中立方烧绿石相的化合物增多,晶粒尺寸变大,且有少量未知相生成。进而探讨了锆基陶瓷固化多核素的潜在应用,并提出了未来研究的相关热点问题。     

DBD plasma assisted atomic layer deposition alumina barrier layer on self-degradation polylactic acid film surface

In this work, the plastic of polylatic acid(PLA) film is coated by alumina(Al_2O_3)through dielectric barrier discharge plasma assisted atomic layer deposition(DBD PA-ALD) for the proposal of the barrier property enhancement. The influence of ALD Al_2O_3 thickness on properties of barrier, mechanical, optical and degradation is investigated in detail. It is obtained that the growth rate of Al_2O_3 in DBD PA-ALD is as quick as 0.12 nm/cycle. After coated～40 nm Al_2O_3, the water vapor transmission rate of PLA is reduced by two orders of magnitude.Additionally, it is noticed that the tension strength of the coated film is improved slightly,whereas the light transmission rate is decreased with the increase of Al_2O_3 thickness. The degradation test shows that Al_2O_3 coating almost does not affect the self-degradation rate of PLA film.     

Radiation effects on MgAl2O4–yttria stabilized ZrO2 composite material irradiated with Ne ions at high temperatures

Spinel (MgAl₂O₄) and yttria stabilized ZrO₂ (YSZ) are candidates for fuel materials for use in nuclear reactors and the optical and insulating materials for fusion reactors. In our previous studies, the amorphization of spinel under 60 keV Xe ion irradiation at RT was observed. On the other hand, amorphization could not be confirmed in YSZ single crystals under the same irradiation conditions. In the present study, the damage evolution process of polycrystalline spinel–YSZ composite materials has been studied by in situ TEM observation during ion irradiation. The irradiation was performed with 30 keV Ne⁺ ions at a flux of 5 × 10¹³ ions cm⁻² s⁻¹ at 923 K and 1473 K, respectively. The observed results revealed a clear difference in morphology of damage depending on irradiation temperature and crystal grains. In the irradiation at 923 K, defect clusters and bubbles were formed homogeneously in YSZ grains. On the other hand, at 1473 K, only bubble formation was observed. The bubbles grew remarkably with increasing ion fluence in both grains. Even though the growth of the bubbles was observed in both grains, the average diameter of grown bubbles in spinel grains was larger than those in YSZ ones. The bubbles tended to form along the grain boundary at both temperatures.     

Improvement of the electrical resistivity of epoxy resin at elevated temperature by adding a positive temperature coefficient BaTiO_3-based compound

The DC electrical resistivity-temperature characteristic is an important property for insulating materials to operate at a high stress level. In order to improve the DC electrical resistivity at elevated temperature in a targeted way, a positive temperature coefficient(PTC) material(Ba Ti O3-based compound(BT60)) was selected as the filler in this paper, whose electrical resistivity has a PTC effect when the temperature exceeds its Curie temperature. The BT60 was treated with hydrogen peroxide and(3-Aminopropyl) triethoxysilane. Epoxy composites with different loadings of BT60 fillers(0 wt%, 0.5 wt%, and 2 wt% of epoxy) were prepared, denoted as EP-0, EP-0.5, and EP-2. It was shown that BT60 was able to maintain the DC breakdown strength when its loading was less than 2 wt% of epoxy. As the temperature exceeds 60 °C,BT60 will compensate for the negative temperature coefficient effect of epoxy resin to some extent. The electrical resistivity of EP-2 was improved by 55% compared with that of neat epoxy at 90 °C. It was found that the potential barrier at the grain boundary of BT60 and the deep traps in the interface between BT60 and the epoxy resin hinder the migration of carriers and thus increase the electrical resistivity of epoxy composite.     

The impact of dielectrics on the electrical capacity,concentration, efficiency ozone generation for the plasma reactor with mesh electrodes

This paper presents experimental results concerning the effect of dielectric type on ozone concentration and the efficiency of its generation in plasma reactor with two mesh electrodes.Three types of dielectric solid were used in the study; glass, micanite and Kapton insulating foil. The experiments were conducted for voltage ranges from 2.3 to 13 k V. A plasma reactor equipped with two 0.3?×?0.3 mm~2 mesh electrodes made of acid resistant AISI 304 mesh was used in the experiments. The influence of the dielectric type on the concentration and efficiency of ozone generation was described. The resulting maximum concentration of the ozone was about 2.70–9.30 g O_3 m~(-3), depending on the dielectrics used. The difference between the maximum and the minimum ozone concentration depends on the dielectric used,this accounts for 70% at the variance. The reactor capacity has also been described in the paper; total C_t and dielectric capacitance C_d depending on the dielectric used and its thickness.     

Copper canister lifetime limited by a sulfide intrusion in a deep geologic repository

Korea has continuously implemented an ambitious nuclear energy deployment program since 1978. Korea currently operates 20 units, 16 PWRs and four CANDUs and constructs four and reviews license application of two more units. Also, Korea plans to build two more units by 2016. In addition, according to the new “Green Growth Plan while reducing the emission of carbon dioxide” Korea will introduce 10–12 units by 2030. This will inevitably result in more burdens on the safe management of spent nuclear fuels. Korea Atomic Energy Research Institute has developed a final disposal concept for Spent Nuclear Fuel (SNF) named KRS. KRS proposes to emplace SNF in a deep geologic formation such as a crystalline rock. Two key engineered barriers are applied to retard the potential release of a radionuclide from an embedded SNF; a waste container and an engineered barrier. Such an engineered barrier is composed of domestic calcium bentonite and the waste container is composed of an outer copper layer and an inner steel layer. The outer layer, a copper layer is dedicated to protect a waste container against corrosion. The main corrosion mechanism to corrode a copper waste container is a pitting whose speed of corrosion is 5–25 times higher than that of a uniform corrosion. In this paper, a special mass transfer resistance model is developed to predict the migration of sulfide from a fracture to a waste container surface via a bentonite layer. Based on it the lifetime of a copper canister layer limited by a pitting corrosion is estimated. Results show that under normal conditions, a copper layer can sustain its integrity for up to more than millions of years.     

Tritium diffusivity in crystal grain of Li2TiO3 and tritium release behavior under several purge gas conditions

It has been reported by the present authors that behavior of tritium release from solid breeder grain is consisted of diffusion in grain, tritium transfer at surface layer and surface reactions on grain surface such as adsorption or isotope exchange reactions. Tritium release curves estimated using the tritium release model gave good agreement with observed tritium release curves from Li₄SiO₄, Li₂ZrO₃ or LiAlO₂.

Tritium release behavior from Li₂TiO₃ under humid purge gas, dry purge gas and dry purge gas with hydrogen conditions is discussed in this study, tritium release curves using the release model that we proposed previously give a good agreements with experimental tritium release curves. Tritium effective diffusivity in the crystal grain of Li₂TiO₃ is also estimated in this study using a curve-fitting method applied to the release curves obtained under the humid purge gas condition. It is discussed that change of color of Li₂TiO₃ surface under hydrogen purge gas condition is observed and this phenomenon might affect tritium release behavior from Li₂TiO₃.