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。     

Cement-waste interactions: Hardening self-compacting mortar exposed to gamma radiation

For the disposal of high level radioactive waste and for attenuation of the emitted radiation, the Belgian supercontainer concept considers the use of cylindrical concrete containers: the radwaste (encapsulated in a canister and stainless steel overpack) is embedded in a hardened self-compacting concrete buffer, and for closure of the supercontainer the remaining gap is filled by casting a self-compacting mortar (filler and lid). As a consequence, this cementitious layer, surrounding the radwaste, will be exposed immediately to the heat-emitting radioactive waste and gamma radiation with dose rates up to 20 Gy/h during hardening and hydration of the cementitious matrix.In this research study, the effect of gamma radiation on the mechanical properties (e.g. compressive strength) and the microstructure of the cementitious samples is investigated thoroughly. By means of compressive strength determination and by analysing the microstructure of the cementitious samples, the effect of gamma radiation during the hardening process of the samples is identified. Small self-compacting mortar cubes were cast and irradiated immediately by gamma rays during hardening. The effect of the total absorbed dose (Gy) and the applied dose rate (Gy/h), in combination with different hardening times at first exposure and total irradiation times is determined. Furthermore, the impact of the composition of the cementitious mortar (e.g. by changing the cement type and the water-to-cement ratio (W/C-ratio)) is investigated.Throughout the test program it was found that a strength loss due to gamma irradiation can be expected, influenced by the total received dose and by the applied dose rate. Furthermore, the age at which irradiation starts (hardening time at first exposure), plays a role in the effect of the gamma irradiation. A correlation between the strength of the mortar samples and its microstructure is found by means of fluorescence microscopy on thin sections and nitrogen adsorption tests: by applying gamma radiation the capillary porosity, the pore volume distribution and the specific surface of the pores is affected. Scanning electron microscopy (SEM) also revealed a change in microstructure due to gamma radiation.     

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。     

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.     

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］^-。     

The potential for using slags activated with near neutral salts as immobilisation matrices for nuclear wastes containing reactive metals

The UK currently uses composite blends of Portland cement and other inorganic cementitious material such as blastfurnace slag and pulverised fuel ash to encapsulate or immobilise intermediate and low level radioactive wastes. Typically levels up 9:1 blast furnace slag:Portland cement or 4:1 pulverised fuel ash:Portland cement are used. Whilst these systems offer many advantages, their high pH causes corrosion of various metallic intermediate level radioactive wastes. To address this issue, lower pH/weakly alkaline cementitious systems have to be explored.While the blast furnace slag:Portland cement system is referred to as a composite cement system, the underlying reaction is actually an indirect activation of the slag hydration by the calcium hydroxide generated by the cement hydration, and by the alkali ions and gypsum present in the cement. However, the slag also can be activated directly with activators, creating a system known as alkali-activated slag. Whilst these activators used are usually strongly alkaline, weakly alkaline and near neutral salts can also be used. In this paper, the potential for using weakly alkaline and near neutral salts to activate slag in this manner is reviewed and discussed, with particular emphasis placed on the immobilisation of reactive metallic nuclear wastes.     

Vitrification of high chrome oxide nuclear waste in iron phosphate glasses

A simulated high level waste (HLW) containing 4 mass% chrome oxide, whose overall composition is representative of the high chrome oxide wastes at Hanford WA USA, was easily vitrified in a phosphate glass at temperatures ranging from 1150 °C, for waste loadings of 55 mass%, to 1250 °C for waste loadings of 75 mass%. Even at these high waste loadings, these wasteforms had an excellent chemical durability. The best chemical durability was achieved when the O/(Si + P) atomic ratio was between 3.5 and 3.8. These wasteforms were also resistant to crystallization although trace amounts of crystalline Cr₂O₃ were present in wasteforms containing more than 70 mass% HLW. It is concluded that up to 45 mass% of the total HLW at Hanford, especially that containing as high as 4.5 mass% chrome oxide, could be directly vitrified into an iron phosphate glass, that meets all of the current chemical durability requirements by simply adding 25-35 mass% P₂O₅ to the waste and melting the mixture at 1150-1250 °C for a few (<6) hours.     

Reduction of Cesium Leaching Ratio from Cementitious Resin Forms Using Natural Active Silica

Cesium adsorption behavior of active silica, which is a natural acid clay composed of cristobalite and quartz, was evaluated for its applicability as Cs adsorbent to be added to cementitious waste forms containing spent ion exchange resin. Since active silica carried the Cs exchangeable silanol group (—SiOH) originally, the Cs distribution coefficient was remarkably high (<10⁴). It increased in saturated Ca(OH)₂ solution, simulating the cement paste, due to formation of new silanol groups. With its addition to the cementitious forms with ¹³⁴Cs adsorbed ion exchange resin solidified by slag cement, the Cs leaching ratio was reduced to below 1/10 that without active silica.     

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 environment, mechanical conditions, and materials characteristics on AE behavior during corrosion fatigue processes of an austenitic stainless steel

Acoustic emission (AE) behavior during corrosion fatigue (CF) processes has been studied in a commercial grade 304 austenitic stainless steel with special attention to the effect of environment, mechanical conditions, and materials characteristics. Precracked compact tension specimens were tested under cyclic tension-tension load, polarized potentiostatically in 1N H₂SO₄ + 0.5M HaCl or 1N H₂SO₄ solutions at room temperature. Valuable AE signals discriminated from environmental and mechanical noises by source location were monitored at the loading phase near the maximum load. The experimental results showed that the AE activity observed in corrosive environments increased significantly with the acceleration of crack growth rates, compared with that observed in air (inert environment). Detailed SEM observations found cleavage-like cracking, intergranular-like cracking, separations, etc. on the crack surfaces. The AE sources which provided the high AE activity during CF crack growth were shown to be such microcracking processes as cleavage-like cracking, intergranular-like cracking, and separations caused by the cooperation of environments (intergranular corrosion or hydrogen), mechanical conditions (triaxial stress), and materials characteristics (non-metallic inclusions or carbides precipitated along grain boundaries by sensitization). The effect of these three factors on the AE behavior and cracking mechanisms is discussed in detail.     

On the formation of U–Al alloys in the molten LiCl–KCl eutectic

U–Al alloy formation has been studied in the temperature range of 400–550 °C by electrochemical techniques in the molten LiCl–KCl eutectic. Cyclic voltammetry showed that underpotential reduction of U(III) onto solid Al occurs at a potential about 0.35 V more anodic than pure U deposition. Open circuit potential measurements, recorded after small depositions of U metal onto the Al electrode, did not allow the distinction between potentials associated with UAl_x alloys and the Al rest potential, as they were found to be practically identical. As a consequence, a spontaneous chemical reaction between dissolved UCl₃ and Al is thermodynamically possible and was experimentally observed. Galvanostatic electrolyses were carried out both on Al rods and Al plates. Stable and dense U–Al deposits were obtained with high faradic yields, and the possibility to load the whole bulk of a thin Al plate was demonstrated. The analyses (by SEM-EDX and XRD) of the deposits indicated the formation of different intermetallic phases (UAl₂, UAl₃ and UAl₄) depending on the experimental conditions.     

Separation of clean aggregates from contaminated concrete waste by thermal and mechanical treatment

As part of a fundamental research for the volume reduction of dismantled concrete, an investigation was carried out addressing the separation of the aggregates and the distribution of the radioactivity into the aggregates of contaminated concrete generated from dismantled nuclear facilities. Radioisotope ⁶⁰Co was artificially used as a model contaminant for non-radioactive crushed heavy weight concrete taken from the Korea Research Reactor 2 (KRR-2) and light weight concrete from the uranium conversion plant (UCP) by thermal and mechanical treatment. The results showed that most of the ⁶⁰Co nuclide was easily separated from the gravel and aggregate, and concentrated mainly into the porous fine cement paste. By thermal and mechanical separation treatment, the clean aggregate can be recovered up to 80% from radioactively contaminated concrete waste. The final wastes of formed cement paste were produced by thermal and mechanical treatment. Heavy and light cement pastes were vitrified. Volume reductions of the cement pastes were achieved at about 1/3 and 1/2.5, respectively.     

碱矿渣胶凝材料固化废TBP的配方初步研究

核工业中产生的放射性废磷酸三丁酯（TBP）存在巨大的潜在危害,其处理是一世界性难题,国内尚处于理论研究阶段。本文针对废TBP碱度大和有机物盐份高的特征,提出了碱激发胶凝材料的固化处理方法,并研究了激发剂用量、水解产物包容量和养护时间对固化体的机械性能、抗水性、抗冻融性、水化程度、碱度、矿物组成以及活性Al、Si含量的影响。与硅酸盐水泥和矿渣水泥相比,碱矿渣胶凝材料在固化TBP水解产物方面凸显优越性,当包容量为14.49%时,碱矿渣胶凝材料固化体28 d的强度为18.90 MPa,而硅酸盐水泥固化体的强度仅8.69 MPa。碱矿渣胶凝材料中Cs和Sr的抗浸出性、抗冻融和抗冲击性能均明显优于矿渣水泥和硅酸盐水泥。     

Investigation of the Solidification of Spent Filter Materials on Slags from the Leningrad Nuclear Power Plant

The results of investigations of the solidification of pulps of filter materials and slags, produced during the operation of the Leningrad nuclear power plant, by incorporating them into inorganic binding materials are presented. Slag-cement binder (mixture of finely milled metallurgical slag with Portland cement) was used as the matrix material. The solution of sodium hydroxide and sodium silicate served as the solidifying liquid. The water binding ratio (from 0.54 to 0.63) gave good fluidity in cement test in all cases.Slag-cement binder and metallurgical slag were used for solidifying slags from bottoms containers. Bentonite clay was added to the binder to localize the ¹³⁷Cs present in the wastes.It is shown that solid compounds containing up to 32 mass% filter-materials pulp or 36–77 mass% slags can be obtained by using as the binder metallurgical slag or a mixture of metallurgical slag with Portland cement. The quality of the compounds (mechanical strength, water resistance, leach rate of radionuclides) satisfy the regulatory requirements.     

中子辐照对耐事故燃料FeCrAl合金力学性能的影响研究

FeCrAl合金具有良好的抗高温氧化和力学性能,能够作为燃料包壳材料。为研究FeCrAl合金的辐照力学性能,开展了不同元素成分含量和2×1019 cm?2、8×1019 cm?2 2种中子注量辐照下的FeCrAl合金力学性能试验,并在室温和380℃下测试了FeCrAl合金的拉伸性能,获得了不同Cr和Al含量FeCrAl合金的抗拉强度和屈服强度,并研究了Al含量、Cr/Al含量配比及中子辐照对FeCrAl合金力学性能的影响。研究表明,FeCrAl合金强度随着Al含量增加大致呈增加趋势;经2×1019 cm?2中子辐照后,FeCrAl合金强度有较大提升;再经8×1019 cm?2中子辐照后,FeCrAl合金强度升高不明显。该研究结果为耐事故燃料（ATF）包壳材料的研发选型提供了重要的数据支撑。      

液压下压力管线活动缺陷声发射信号研究

在液压试验装置上,对含预制裂纹的压力管开展了缺陷扩展声发射信号试验研究.全程不间断监测压力管道疲劳裂纹扩展的声发射信号,并对采集到的信号进行分析处理.结果表明:管道缺陷声发射信号的幅度和能量随加载时间逐步增大,可以用于鉴别管道是否存在活动缺陷;在缺陷贯穿前,声发射信号的幅度、能量和计数急剧增加,可以预报管道缺陷的贯穿泄漏.     

用D-D中子发生器测量水泥生料中的元素含量

以D-D中子发生器作为中子源,用瞬发γ中子活化分析（PGNAA）检测水泥生料中主要元素Si、Al、Fe和Ca及其氧化物的百分含量。水泥生料中各元素被中子辐照而释放瞬发γ射线,通过测量γ射线的能量和强度,可对其进行定性和定量分析。测量结果与化学化验方法所得结果的相对偏差好于7.0％,在允许范围内,有较好的重复性。与化学化验方法相比,该方法不破坏样品、用时短、可同时测量多种元素、精确度和准确度高,能满足工业生产的要求。     

The effect of organic retarders on grout thickening and setting during deep borehole disposal of high-level radioactive waste

Deep borehole disposal (DBD) is being increasingly seen as a viable and potentially superior alternative to comparatively shallow mined repository concepts for disposal of some high-level radioactive wastes. We report here details of proof-of-concept investigations into the use of cementitious grouts as sealing/support matrices for use in low temperature DBD scenarios. Using the cementitious grout to fill annular space within the disposal zone will not only support waste packages during placement, but will also provide a low permeability layer around them which will ultimately enhance the safety case for DBD. Grouts based on Class G oil well cement are being developed. The use of retarders to delay the accelerated onset of thickening and setting (caused by the high temperature and pressure in the borehole) is being investigated experimentally. Sodium gluconate and a polycarboxylate additive each provide sufficient retardation over the range 90–140 °C in order to be considered for this application. Phosphonate and sulphonate additives provide desirable retardation at 90 °C. The additives did not affect grout composition at 14 days curing and the phases formed are durable at elevated temperature and pressure.     

几种钎料对钛合金/不锈钢钎焊接头的钎缝强度与界面的影响

采用4种成分的银基钎料制备了钛合金/不锈钢钎焊接头,用力学性能试验、金相试验、扫描电镜分析及电子探针分析方法,测量了钎缝强度,分析了断口形貌和钎缝界面组织.研究表明:不锈钢/Ag95CuNiLi/钛合金钎缝强度可达220 MPa,在不锈钢/Ag95CuNiLi扩散区形成了脆性相;不锈钢/Ag88Al10MnSi/钛合金钎缝强度为242 MPa,不锈钢/ Ag88Al10MnSi一侧的钎缝区易形成裂纹;不锈钢/Ag85Al8Sn/钛合金钎缝强度只有123 MPa;不锈钢/Ag85Al8SnNi/钛合金钎缝强度可达280 MPa,钎料与母材冶金结合较好.     

Elemental analysis of limestone samples from Ewekoro limestone deposit in southwest Nigeria

Limestone samples of different colours from Ewekoro limestone deposit in Ogun State, Nigeria were subjected to elemental analysis by proton-induced X-ray emission (PIXE) and proton-induced gamma-ray emission (PIGME) techniques. The irradiation was by 2.5 MeV proton beams from the ion beam analysis (IBA) facility of the 3 MV Van de Graaff accelerator at the Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights. Elemental composition and concentrations of 22 major, minor and trace elements were determined. The NIST geological standard, NBS278, was analysed for quality assurance. The concentrations of the major elements (Ca, Fe, K and Al) are similar in the samples while the other major elements differed. Calcium accounts for about 38%, giving 86.8% CaCO₃ content in the limestones. The major elements (Al, Ca, Fe, Si, S and K), present in the limestones, were also found to be enriched in airborne particulate matter studied by earlier workers, thus confirming cement dust as the major contributor to the particulate matter within and around cement factories.