氧化硼对铁磷酸盐玻璃陶瓷固化体的影响

研究了不同B₂O₃掺量对铁磷酸盐玻璃陶瓷高放废物固化体结构和性能的影响。应用溶出速率法（DR）对固化体进行了化学稳定性测试,使用傅里叶变换红外光谱（FTIR）和X射线衍射（XRD）方法研究了样品的结构。研究结果表明：玻璃陶瓷固化体的主晶相为独居石;B₂O₃的引入对玻璃陶瓷固化体的化学稳定性影响较大,以10%（摩尔分数）的B₂O₃代替Fe₂O₃制得的固化体化学稳定性最佳,其28d的质量浸出率约为7.81×10^-9g•cm^-2•min^-1;试样中存在大量正磷酸基团［PO₄］^3-和少量焦磷酸基团［P₂O₇］^4-,无偏磷酸基团［PO₃］^-存在,固化体中的B主要以［BO₄］四面体基团形式存在。     

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。     

掺钆铈独居石陶瓷固化体在THMC耦合作用下的化学稳定性

以氧化钆、十水草酸铈和磷酸二氢铵为原料,采用热压烧结制备掺钆铈独居石陶瓷固化体,借助X射线衍射（XRD）、场发射扫描电镜（FESEM）、能谱（EDS）和电感耦合等离子体发射光谱-质谱（ICP-MS）等分析手段,研究掺钆铈独居石陶瓷固化体的热压烧结及固化体在热-水-力-化学(THMC)耦合作用下的化学稳定性。结果表明,采用热压烧结技术,实现了单相Ce_0.9Gd_0.1PO₄陶瓷固化体的低温（1150～1200 ℃）、快速（2 h）烧结,固化体的相对密度达99.62%;在THMC耦合作用下（温度为90～200 ℃(0.101～1.554 MPa),pH=5～9）,固化体具有优异的化学稳定性,浸出时间为42 d时,模拟次锕系核素Gd的归一化浸出率在10^-6～10^-5 g/(m²•d）数量级;温度和pH值对Ce的归一化浸出率影响较小;温度对Gd的归一化浸出率没有影响;与弱碱性（pH=9）水溶液相比,在弱酸性（pH=5）和中性（pH=7）水溶液中,Gd的归一化浸出率相对较高。     

掺钕钙钛锆石基玻璃陶瓷制备及浸出性能研究

采用熔融-热处理工艺制备了掺钕钙钛锆石基玻璃陶瓷,研究了不同热处理工艺对玻璃陶瓷晶相结构的影响,用粉末静态浸泡法（PCT法）对玻璃陶瓷的浸出性能进行了评价。结果表明,玻璃陶瓷的玻璃转变温度（T_g）和析晶峰温度分别为580 ℃和740 ℃。采用先制备玻璃再进行热处理的方法（二步法）很容易生成CaTiO₃晶相,而采用从熔融温度降低到核化温度成核,再升高到晶化温度进行热处理的方法（一步法）,可获得稳定的2M型CaZrTi₂O₇晶相,且CaZrTi₂O₇晶粒呈树枝状分布在玻璃基质中。玻璃陶瓷固化体中B和Na元素的归一化质量损失在14 d后达到稳定值（约1 mg/m²）,Nd元素的归一化质量损失在28 d后达到稳定值（约0.2 mg/m²）,均较硼硅酸盐玻璃固化体的低1个数量级。     

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_...     

热-水-力-化学耦合作用下Ca0.86Nd0.14Ti0.86Al0.14SiO5固溶体的化学稳定性

以CaCO₃、Nd₂O₃、TiO₂、SiO₂、Al₂O₃为原料,用固相法制备掺钕榍石固溶体（Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅）。采用PCT法进行浸泡实验,借助X射线衍射（XRD）、扫描电镜（SEM）、电感耦合等离子体发射光谱（ICP-OES）等分析手段,研究掺钕榍石固溶体在热 水 力 化学（THMC）耦合作用下的化学稳定性。结果表明,在pH值为5～9、温度150～200 ℃、压强0.476～1.554 MPa的耦合作用下,Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅固溶体具有良好的化学稳定性;pH值、温度（压力）对Ca_0.86Nd_0.14Ti_0.86Al_0.14SiO₅固溶体中Si⁴⁺、Al³⁺、Nd³⁺的归一化浸出率无明显影响;Ca²⁺在200 ℃（1 554 MPa）时的抗浸出性能较150 ℃时的好;在浸泡初期（1～21 d）Ca²⁺在pH值为9时的抗浸出性能优于pH值为5和7时的,浸泡后期（28、42 d）3种溶液中固溶体的Ca²⁺抗浸出性能趋于一致;Ti⁴⁺在pH值为9时的抗浸出性能较pH值为5和7时的好。     

铁元素对铝热剂SHS核废物固化体性能的影响

研究了铁元素对用自蔓延高温合成（SHS）技术固化处理的核废物固化体的组成结构及化学稳定性的影响。借助XRD、SEM和TG-DSC等测试手段对固化体的矿相组合、微观结构和热稳定性进行了测试分析,采用PCT浸泡法对固化体的抗浸出性能进行了研究。结果表明：不同配比的固化体矿相结构基本相同,矿相的主要组成为Al₂O₃,Fe元素对固化体的矿相结构无明显影响。固化体的微观结构非常致密,结晶良好,但固化产物的气孔数量及孔径随Fe元素含量的增大而增大。在小于1400 ℃时,固化体无明显失重,具有良好的热稳定性。固化体中示踪核素Ce的28 d浸出速率为10^-5～10^-6 g/(m²•d),固化体中Fe的含量在1%~10%范围内波动时,其对Ce、Ca、Si、Al、Fe的浸出速率无明显影响。     

锕系金属（铀和锔）内嵌硼球烯的理论研究

最近发现的全硼富勒烯（硼球烯,D_2d B^-/0₄₀）,开启了硼球烯化学研究的新篇章。类似于富勒烯,金属掺杂也是硼球烯修饰和功能化重要途径。本工作采用密度泛函理论预测了一系列锕系金属掺杂硼球烯［An@B₃₉］ⁿ⁺（An=U,n=3;An=Cm,n=2）。理论计算表明,这些硼球烯均为稳定的金属内嵌硼球烯,其中［U@B₃₉］³⁺的能量最低,结构具有C₃对称性,而［Cm@B39］²⁺为C₁结构。成键性质分析表明,［U@B₃₉］³⁺和［Cm@B₃₉］²⁺均存在σ和π离域键。另外［An@B₃₉］ⁿ⁺中U-B键的共价相互作用强于Cm-B键,且［U@B₃₉］³⁺较［Cm@B₃₉］²⁺更稳定。因此,An-B键的共价特征对于这些锕系金属内嵌硼球烯的形成是必不可少的。本工作扩展了硼球烯体系,并为新型稳定金属内嵌硼球烯的设计提供了理论线索。     

(Sr0.1Th0.2Nd0.3La0.2Gd0.2)2Zr2O7高熵烧绿石固化体的制备及化学稳定性

以金属硝酸盐为原材料,通过溶胶-喷雾热解-高温烧结法制备了(Sr_0.1Th_0.2Nd_0.3La_0.2Gd_0.2)₂Zr₂O₇高熵烧绿石固化体。利用X射线衍射(XRD)、扫描电镜(SEM)、Raman光谱对固化体结构进行表征,通过MCC-1浸出实验方法分析了固化体化学稳定性。研究结果表明：高熵烧绿石固化体为纯相高熵烧绿石结构,最佳烧结温度为1 500℃。随着烧结温度增加,固化体晶粒和密度明显增加。浸出实验结果显示：La、Gd、Zr、Nd元素42 d归一化浸出率为10^-6 g/(m²·d)量级,Sr、Th元素的42 d归一化浸出率分别为10^-5 g/(m²·d)和10^-3 g/(m²·d)量级,固化体表现出良好的化学稳定性。     

人造岩石固化体SrCeTi2O7的合成与性能研究

采用⁸⁸Sr模拟放射性核素⁹⁰Sr,Ce⁴⁺模拟四价锕系放射性核素。以分析纯SrCO₃、CeO₂和TiO₂为主要原料,通过高温固相反应制备SrCeTi₂O₇人造岩石固化体。对固化体的烧成工艺、物理性能、晶体结构及微观形貌进行研究,并对固化体的热稳定性及抗浸出性能进行探讨。结果表明,选择配方n(SrCO₃)∶n(CeO₂)∶n(TiO₂)＝1∶1∶2,在1 450 ℃下保温5 h可合成结构致密、晶型发育完整的SrCeTi₂O₇人造岩石固化体;Dicvol程序指标化结果表明,该固化体化合物属四方晶系,晶胞参数为a＝0.387 33(4) nm,c＝0.388 07(5) nm;SrCeTi₂O₇人造岩石固化体具有良好的热稳定性,经高达800 ℃热处理后样品仍保持原有物相不变;PCT-B粉末浸泡法测试结果表明,SrCeTi₂O₇人造岩石固化体具有较好的抗浸出性能,浸泡周期28 d时Sr、Ce和Ti的浸出率分别为3.51×10^-4、8.23×10^-8和2.02×10^-7 g/(m²·d)。     

Na_2O/Al_2O_3摩尔比对模拟高放废液硼硅酸盐玻璃固化体结构和性能的影响

研究了Na2O/Al2O3摩尔比(n)对模拟高放废液硼硅酸盐玻璃固化体结构和性能的影响。利用红外光谱分析了不同Na2O/Al2O3摩尔比时硼硅酸盐玻璃固化体的结构变化,并用溶解速率法(DR)和全谱直读等离子发射光谱(ICP-OES)表征了所制备出固化体的化学稳定性。结果表明:在研究组分范围内,当n1.0时,硼硅酸盐玻璃固化体结构中Al以[AlO4]四面体的形式存在,但[BO3]三角体的量较大;随着Na2O/Al2O3摩尔比的增加(n=1.0),固化体结构中[BO3]三角体向[BO4]四面体转变,Al仍以[AlO4]四面体的形式存在,固化体结构稳定性增加;Na2O/Al2O3摩尔比继续增加(n=1.5或2.0),固化体成分中由于Al含量已很少而使[AlO4]含量过少,对固化体结构网络致密性的影响起主要作用,且此时成分中存在过多的碱金属离子在结构中起断网作用,玻璃固化体网络结构变疏松。在Na2O/Al2O3摩尔比为1.0时,玻璃固化体有相对较佳的结构稳定性和化学稳定性,浸泡56d后的失重速率为10-9 g/(cm2·min)数量级,且浸出液中各浸出离子的平均浓度最低。     

Characterization of monazite glass-ceramics as wasteform for simulated α-HLLW

Two monazite glass-ceramic wasteforms were sintered by mixing the lanthanum metaphosphate glass powder with the oxide powder of the components in simulated α-HLWs. The co-existence of components Al and Mo in an iron phosphate melt separated the melt into two immiscible glass melts, namely aluminum iron phosphate glass (Gb) and molybdenum iron phosphate glass (Gg). 24 wt% of ZrO₂, together with P₂O₅ and proper amounts of Fe and Mo formed a zirconium pyrophosphate glass (Gg1), which was immiscible with the phase Gg. The iron ions in the wasteforms were all in Fe³⁺, 1/3 of which was in 4-fold coordination. The O/P and O/(P + 1/3Fe³⁺) ratios for the glass phases were Gg1 3.70, Gb 3.89-3.98, Gg 4.23-4.25, and Gg1 3.58, Gb 3.47-3.42, Gg 3.74-3.69, respectively. The dissolution rates of two wasteforms were 0.3008 and 0.2598 g/m²d, respectively.     

Laser-joined Al2O3 and ZrO2 ceramics for high-temperature applications

A laser process is presented that has been specially developed for joining oxide ceramics such as zirconium oxide (ZrO₂) and aluminium oxide (Al₂O₃). It details, by way of example, the design of the laser process applied for to producing both Al₂O₃-Al₂O₃ and ZrO₂-ZrO₂ joints using siliceous glasses as fillers.The heat source used was a continuous wave diode laser with a wavelength range of 808-1010 nm. Glasses of the SiO₂-Al₂O₃-B₂O₃-MeO system were developed as high-temperature resistant brazing fillers whose expansion coefficients, in particular, were optimally adapted to those of the ceramics to be joined. Specially designed measuring devices help to determine both the temperature-dependent emission coefficients and the synchronously determined proportions of reflection and transmission.The glass-ceramic joints produced are free from gas inclusions and macroscopic defects and exhibit a homogenous structure. The average strength values achieved were 158 MPa for the Al₂O₃ system and 190 MPa for the ZrO₂ system, respectively.     

Radiation effects on PbO-Al2O3-B2O3-SiO2 glasses by FTIR spectroscopy

The infrared absorption spectra of PbO-Al₂O₃-B₂O₃-SiO₂ glasses have been measured in the spectral range 600-4000 cm⁻¹ before and after absorbed dose of 50 Gy, 4 kGy and 50 kGy to investigate the structural change due to irradiation. The structural change due to composition has also been discussed. The experimental results clearly indicate that after irradiation, a significant change in structure of lead alumino borosilicate glass network is observed. It was shown that BO₄ groups decreases and BO₃ groups increases with the increase of Al₂O_3.     

高放核废料磷酸盐玻璃陶瓷固化研究进展

磷酸盐玻璃陶瓷是固化“难溶”核废料的优异基材,具有高的废料包容量和优异的稳定性,因而,磷酸盐玻璃陶瓷固化是高放核废料固化处理的重要研究方向之一。本文简要综述了高放核废料磷酸盐玻璃陶瓷固化体的类型、固化机理、固化体设计、稳定性及其制备,并对其研究做了展望。其今后研究方向主要包括：（1） 磷酸盐玻璃固化体的中长期化学稳定性、蚀变规律和抗腐蚀机制的研究;关注其物理性能、热稳定性和辐照稳定性;（2） 磷酸盐玻璃陶瓷固化体的简洁制备工艺技术及其工艺原理,及其对设备和电极的侵蚀和寿命的影响。     

Effect of carbide on Al2O3/B4C burnable poison sintered in Ar

Al₂O₃–14 wt%B₄C composites with 0–1 wt% C addition were sintered in Ar at 1550–1650 °C. The influence of the C additive on the B loss, densification behavior, and microstructure of the Al₂O₃–B₄C composites were investigated. The results show that there are B₂O₃, H₃BO₃ and Al₁₈B₄O₃₃ exist between Al₂O₃ and B₄C interface, which result in B loss because of B₂O₃'s high vapor tension at above 1500 °C. The presence of Al₁₈B₄O₃₃ grains formed by chemical reaction of Al₂O₃ with surface oxides on B₄C inhibit the densification of pellets by reducing the specific free surface energy of the Al₂O₃. However, the added C eliminates those oxides to reduce B loss because of its higher activity than B₄C, and it also coarsens Al₂O₃ grain although the density of pellets is decreased by gas products.     

Use of Al2O3 layer as a dielectric in MOS based radiation sensors fabricated on a Si substrate

The use of Al₂O₃ dielectric in MOS based radiation sensors has been investigated. Their response has been compared with conventional MOS capacitors with a SiO₂ dielectric. The study includes gamma radiation effects with dose up to 4 Gy. The effect of radiation has been determined from the valance band shift in C-V curves. The amount of charge induced by the radiation has been calculated and compared with the response of MOS capacitors with SiO₂ with the same and different thicknesses. Fading properties have been studied and compared. Results show that MOS capacitors with Al₂O₃ dielectric exhibit sensitivity greater than that obtained from MOS capacitors with SiO₂. This higher sensitivity is attributed to higher trapping efficiency in the Al₂O₃ layer.     

Ion guiding through capillaries in uncoated Al2O3 membranes

We made an experimental study on ion guiding through capillaries in uncoated Al₂O₃ membranes using a variety of ions such as O¹⁺, O³⁺, and O⁶⁺. The incident energy was varied within the range of 30-150 keV. The results were compared with others using coated PET and Al₂O₃ capillary membranes as well as with the so-called scaling law discovered by Stolterfoht and his co-workers. Good agreement of our results with the scaling law was found. However, our membranes showed extraordinarily strong guiding ability. The reason lies in that our membranes were uncoated. A slower charge drift speed along the insulating capillary wall and a much larger equilibrium charge Q_∞ seems to exist in our experiment.     

Structural characterization of Nd-doped Hf-zirconolite Ca1−xNdxHfTi2−xAlxO7 ceramics

Because of its high incorporation capacity and of the high thermal neutron capture cross-section of hafnium, Hf-zirconolite (CaHfTi₂O₇) ceramic can be envisaged as a potential waste form for minor actinides (Np, Am, Cm) and plutonium immobilization. In this work, Nd-doped Hf-zirconolite Ca_1−xNd_xHfTi_2−xAl_xO₇ (x = 0; 0.01 and 0.2) ceramics have been prepared by solid state reaction. Neodymium has been used as trivalent actinide surrogate. The ceramic samples structure has been studied by X-ray diffraction and refined by the Rietveld method. This revealed that Nd³⁺ ions only enter the Ca site, whereas part of Hf⁴⁺ ions substitute titanium into Ti(1) sites and Al³⁺ ions mainly occupy the Ti(2) split sites and Ti(3) sites of the zirconolite structure. Using various spectroscopic techniques (electron spin resonance, optical absorption and fluorescence), the environment of Nd³⁺ cations in Hf-zirconolite has been studied and compared with that of Nd³⁺ cations in Zr-zirconolite (CaZrTi₂O₇). Different local environments of Nd³⁺ cations have been detected in Hf-zirconolite that can be attributed to the existence of an important disorder around Nd in the Ca site probably due to the statistical occupancy of the next nearest cationic site of neodymium (a split Ti site) by Ti⁴⁺, Al³⁺ cations and vacancies. No significant differences were observed concerning Nd³⁺ cations environment and distribution in Hf- and Zr-zirconolite ceramics.